Applied Catalysis A, General 541 (2017) 120140

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Applied Catalysis A, General

journal homepage: www.elsevier.com/locate/apcata

Review Article

The utilisation of wool as a catalyst and as a support for catalysts MARK

Steven J. McNeil , Matthew R. Sunderland, Samuel J. Leighs
Textile Science and Technology Team, Food & Bio-Based Products Group, AgResearch Limited, Christchurch 8140, New Zealand

A R T I C L E I N F O A B S T R A C T

Keywords: Textiles are an emerging class of support material for catalysts, and are available in many dierent structures at a
Wool modest cost from a well-established industry. This review discusses 87 studies of wool and reconstituted wool as
Supported catalysts catalysts, and supports for catalysts, along with informative complementary studies.
Metallic catalysts The catalytic properties of wool itself were investigated in two studies, and it was shown to be an eective
Biological catalysts
solid sulphonic acid catalyst. A wide variety of catalysts have been applied to wool, i.e. metal complexes, metal
Organic catalysts
oxides, metallic particles, enzymes, microbes and small organic molecules. Wool supported catalysts generally
Solid sulphonic acid catalysts
showed good activity, specicity, durability, and re-usability and this is attributable to the amino acid
composition of wool enabling a wide range of protocols for attaching catalysts. Reconstituted wool is an
eective support for enzyme, metal oxide and organic photoactive catalysts and its low toxicity towards cells
makes it a promising support for phototherapy catalysts.
This review has shown the wide breadth of research that has been undertaken on wool catalysts and wool-
supported catalysts and many interesting developments will be made in the future. For instance, hair and
feathers have been used as templates for preparing highly structured materials that may prove eective as
catalysts, and wool warrants investigation in this area. Other areas of particular interest for the future are wool
sulphonic acid catalysts, and supporting organic molecules onto wool to prepare synthetic enzymes.

1. Introduction There is growing interest in supporting catalysts on materials that

Heterogeneous catalysts, where the supported catalyst is in a
dierent phase to at least one of the reactants, have many advantages
compared to homogeneous catalysts. Perhaps the most important
advantages of heterogeneous catalysts is their ready separation from
reactants and products, thereby lowering the risk of the catalysts
contaminating the reaction products, as well as giving easier reuse of
the catalysts. Supported catalysts often show improved stability,
durability, and ease of handling, in comparison to solution and
powdered catalysts, and facilitate continuous (as opposed to batch)
processes. Catalysts targeting dierent reactions can be attached onto a
single support to be used in processes with multiple reaction steps.
Catalysts can be applied to support materials by two types of
processes: physisorption and chemisorption. Physisorption can be
employed with catalysts that are able to form Van der Waals interac-
tions with the support, and such interactions have the advantage of not
altering the chemical structure of the catalyst. The other application
process, chemisorption, leads to stronger bond formation between the
catalyst and support material than physisorption, but it does carry with
it a greater risk of the catalyst being modied and therefore possibly
losing ecacy.
contribute to the activity, specicity and environmental sustainability
of the overall catalysis system. Textiles are an emerging class of support
material for catalysts, and are available in a wide range of structures at
a modest cost from a well-established industry. A wide variety of
materials are used to support catalysts including oxides of silica and
aluminium [1,2], active carbon [3] and polymers [4,5]. The structuring
of supported catalysts oers the potential for high mass transfer, low
pressure drop, high mechanical and chemical stability, along with
predictable scale-up, and for these reasons is increasingly being
investigated as an alternative to random packing [6]. Supported
catalysts are often complex combinations of components such as the
catalytic material itself, support materials, and binding additives, and
can dier considerably in their structure, performance and application
[7]. The selection of catalysts and their support structures will often be
decided by weighing-up parameters such as activity, stability and
overall cost eectiveness [8]. Textiles are a promising catalyst support
material due to the diversity of structures available, their low cost, and
ease of coating with catalytic materials compared to some other support
materials [9]. Wire meshes [10], carbon nanobres [11,12], and many
other textile bre supports have been investigated, including polyacry-
lonitrile, carbon, polypropylene, polytetrauroethylene, cotton and

Corresponding author.
E-mail address: agcanesiswronz@gmail.com (S.J. McNeil).

http://dx.doi.org/10.1016/j.apcata.2017.04.021
Received 20 January 2017; Received in revised form 10 April 2017; Accepted 28 April 2017
Available online 07 May 2017
0926-860X/ 2017 Published by Elsevier B.V.
S.J. McNeil et al. Applied Catalysis A, General 541 (2017) 120140

variety of chemical functionalities to wool [36,37] and are important

for the attachment of catalytic materials as will be discussed in this
review. The terminal carboxyl and amine groups also contribute some
functionality. Table 1 includes the amino acid composition of the
outermost part of the bre, the cuticle, as this has the greatest
interaction with materials such as catalysts that are applied to the
surface of the bre. The hydrophobicity of the wool surface is largely
caused by covalently bound lipids, rather than hydrophobic amino acid
residues [38].
Amino acids and peptides have been used as catalysts, which was
the subject of a review by Jarvo et al. [39]. For example, proline has
been used for various aldol reactions, while poly-L-alanine has been
used in the epoxidation of chalcones. Short peptides containing
alkylated histidine residues have been investigated as catalysts for the
kinetic resolutions of secondary and tertiary alcohols [40]. Amino acids
have been combined with metal ions and used as catalysts. For instance,
the rubidium salt of (S)-proline has been used to catalyse the addition of
malonate to enones [41], and the addition of nitroalkanes to enones
[42].
Fig. 1. Scanning electron micrograph a wool bre. Catalysts are used in the manufacture of wool textiles including,
enzymes for depilation [43], bre modication [44], and euent
nylon [1321]. treatment [45]. Iron and copper catalyse the selective bleaching of
Wool is a long-established bre in apparel and interior textiles, but dark bres [46,47], and organometallic compounds speed-up the curing
it is perhaps less well known that wool is becoming increasingly used in of silicone softeners and resins [48].
technical applications [22]. This is driven by the desire for wool This review is concerned with the use of wool as a catalyst, and as a
producers to increase demand and value for their bre, and the support for catalysts. It will consider wool in its familiar brous form,
recognition of how wools properties [22,23], sustainability [24] and and in reconstituted (i.e. dissolved and then solidied) form, along with
biodegradability [25] make it well-suited for some technical applica- the possibility of using wool as a template for preparing catalysts. Some
tions. The most important technical applications of wool, at present, areas related to the main themes will be touched upon where they are
include building insulation [22], ltration [26,27] and the sorption of informative, including supporting catalysts on textile bres other than
pollutants, particularly indoor air pollutants [28,29], heavy metals wool, and the use of reconstituted non-wool proteins as supports for
[30,31], and hydrocarbons [32]. The utility of wool in technical catalysts.
applications can be enhanced by applying chemical nishes, such as
those used to enhance resistance to re, water, microbes and keratin- 2. Fibre and textile supports for catalysts
consuming insects [33,34].
A typical wool bre is shown in Fig. 1, which clearly illustrates the 2.1. Fibre properties
characteristic scale structure. The complex arrangement of the dierent
morphological components of wool bres has been well described in The length of wool bres ranges between 50 and 300 mm, depend-
various reviews [35,36]. Wool is predominately protein, the amino acid ing on the frequency of shearing and the rate of wool grown. For
composition of which varies to some extent between breeds of sheep comparison cotton bres range from 10 to 60 mm in length. The
and within the same breed, and a typical amino acid composition is diameter of wool bres varies between 17 and 60 m, compared to
given in Table 1. The side chains of the amino acids impart a wide 1222 for cotton. Made-made bres can be prepared in any desired
length and diameter. Some of the key properties of wool and other
bres are compared in Tables 2 and 3. The decomposition temperature
Table 1 of wool is near the middle of the range for polymer bres and wool is
The amino acid composition of clean wool (mole%).
certainly far less resistant to high temperatures than glass and steel
Amino acid Whole bre [36,37] Cuticle [49] Nature of side chain bres. Wool has the greatest equilibrium moisture content and a
relatively low tenacity and high breaking extension. During repeated
Alanine 5.3 5.8 Hydrocarbon extensions, as might be experienced by bres in a catalyst that is
Glycine 8.3 8.2 Hydrocarbon
Isoleucine 3.1 2.7 Hydrocarbon
subjected to intermittent uid ow, wool showed more creep than
Leucine 7.7 6.1 Hydrocarbon nylon, but less than viscose rayon (Table 3). Cotton and acetate bres
Phenylalanine 2.9 1.7 Hydrocarbon did not withstand the 1000 cyclic extensions applied during creep
Valine 5.5 7.5 Hydrocarbon testing.
Serine 10.3 14.3 Polar
Wool does have certain limitations as a support for catalysts, some
Threonine 6.4 4.4 Polar
Tyrosine 4.0 2.8 Polar of which are shared by other organic polymer supports, such as only
Aspartic acida 6.4 3.5 Acidic modest resistance to heat, alkalis, reducing agents and oxidising agents
Glutamic acidb 11.9 8.7 Acidic [52]. As a proteinaceous material, albeit a highly crosslinked one, wool
Arginine 6.8 4.3 Basic is sensitive to long exposures to dry heat and sunlight, becoming
Histidine 0.9 0.8 Basic
Lysine 3.1 2.7 Basic
yellowed and losing mechanical strength. Wool is damaged by pro-
Cystinec 10.5 16.6 Sulphur containing longed exposure to boiling water due to hydrolysis of peptide bonds and
Methionine 0.5 0.3 Sulphur containing crosslinks. This hydrolysis is more rapid in the presence of acid and
Proline 5.9 10.5 Heterocyclic alkalis. Wool is less sensitive to acids than alkalis, and will not be
Tryptophan 0.5 Heterocyclic
signicantly damaged by the acidic conditions that would cause cotton
a
Includes asparagine.
to dissolve. In fact wool is generally dyed under acidic conditions (pH
b
Includes glutamine residues. 26) with sulphuric, formic or acetic acids, and this typically involves
c
Includes the oxidation by-product of cystine, cysteic acid. from one half, to two hours at 98 C. Wool does however, possess

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S.J. McNeil et al. Applied Catalysis A, General 541 (2017) 120140

Table 2
Important properties of bres [50,51].

Melting/decomposition Moisture content Transverse area Tenacity (N/ Breaking extension Work of rupture Initial modulus (N/
point (C) (%)a swelling (%) tex)b (%) (mN/tex) tex)

Wool 225 1622 26 0.110.12 3043 2731 2.33.0

Cotton 150 89 40 0.190.45 5.66.8 5.114.9 3.97.3
Jute 150 14 40 0.31 1.8 2.7 17
Viscose rayon 175205 1416 50114 0.180.27 1627 1931 4.86.5
Nylon 6.6 225260 4.3 1.63.2 0.37 43 101 1.0
Polyester 254260 0.4 0 0.47 37 119 8.8
Polyacrylonitrile 250 12 0.27 25 47 6.2
Polypropylene 160175 0 0 0.65 17 71 7.1
Glass bre 8461056 0 0 0.40.8 1.92.5 3.99.8 2129
Steel wire 1500 0 0 0.26 8.0 18 29

a
Moisture at 20 C, 65% relative humidity.
b
Tex mass in grams per 1000 m.

Table 3 constructions and bre surface coatings, a range of pore and void sizes
Creep behaviour of bres: Cumulative extension (%) after cyclic extensions of 2% [53]. can be achieved. This enables good mass transfer characteristics with
pressure drops comparable to those of monolithic catalysts, as well as
100 extensions 1000 extensions
eliminating diusion as a rate-controlling factor in liquid-phase reac-
Wool 5.1 9.2 tions [54]. The structural design of textiles can also be optimised for
Cotton 5.2 Breaks maintaining catalytic eciencies and allowing for mechanical cleaning
Viscose rayon 11.7 16.0
and handling that can prove dicult with powder and granulated
Nylon 1.0 1.4
Acetate 18.5 Breaks
catalysts. An informative comparison of brous catalysts with powder
and monolithic catalysts has been published [54].
As an example, fabrics of cotton and nylon were chosen as supports
excellent resistance many organic solvents [52]. in a study of immobilised enzymes because of their low-cost, high
enzyme load, high relative activity and good resistance against enzyme
desorption [20]. The researchers noted, The exible construction of
2.2. Textile structures
fabrics enables reactor constructions of any geometry. Their open
structure guarantees an optimal substrate turn-over and the active surface
Fibres can be processed into a wide range of textile structures by
are easily adjustable by the bre diameter.
well-established processes. Textiles oer exibility in structure, as they
An important property of textile structures with regard to support-
can be formed into yarns, fabrics and mats that can be designed,
ing catalysts is their surface area per unit mass. Textile bres typically
manipulated, and packed into a wide range of geometries (see Fig. 2).
have surface areas of between 0.3 and 1.0 m2 per g [55], and most
With a choice of bre diameters between 13 and 45 m [35], textile

Fig. 2. Wool bres arranged in various textile structures, from top left, roving, singles yarn, knitted fabric, needle punched fabric, woven fabric and carpet. Scale bars represents 1 mm.

122
S.J. McNeil et al.
textile structures are of low enough density that the bre surfaces are
not signicantly obstructed. A report into the catalytic degradation of
dyes and phenols in aqueous solutions noted that an important
advantage of textile catalysts and their brous composition, is the
ready access of reacting substances to the reactive outer surface of the
bres [56].
When selecting a support material, the ease of applying the catalyst
is an important consideration. It has been reported that the application
of catalysts to textile supports is facilitated by the capillary action of
textiles allowing for uniform wetting with catalyst agent before
immobilisation, and creating a microuidic environment which in-
creased the eective concentration of catalyst [57].
An interesting application of textile-supported catalysts is in spin-
ning fabric disc reactors, as demonstrated for the hydrolysis of an
emulsied lipid by lipase supported on wool fabric [58]. This system
was thought to give good performance due to the enzyme being
protected from shear-based deactivation, the sieving action of the
fabric reducing the size of the lipid droplets, and the high liquid
hold-up in the wool fabric resulting in increased contact time between
the lipid and enzyme. Increasing the number of layers of fabric in the
reactor increased the eective enzyme loading per liquid pass through
the reactor and thereby increased the conversion [59], (see Section
5.1.2 for details).
3. Wool catalysts
The two published studies of wool catalysts are summarised in
Table 4. Wool powder has been used as a catalyst for the nitroaldol
(Henry) reaction between aromatic and heteroaromatic aldehydes and
nitromethane, to form beta-nitroalcohols [60], see Fig. 3. The wool
powder was purchased from a chemical supply company, and the only
details provided are that it was keratin powder from wool, so it is not
known if the powder was prepared from wool by physical or chemical
means or by a combination. The wool powder was used as received,
without the researchers applying any modications or application of
catalysts. Wool powder was judged to be an eective catalyst, and it
could be recovered from the products and reused, albeit with some
deterioration in performance. In comparison with other biomaterial
catalysts, the wool keratin performed as well as calcium alginate, but
worse than gelatine, broin and chitosan.
Solid acid catalysts are attracting interest as alternatives to liquid
acids [61]. Sulphonated solid acid catalysts are applicable to several
types of reaction [62] and some brous ones, such as polypropylene,
have been investigated [63,64]. The disulphide (SS) crosslinks in wool
can be oxidised to sulphonic acid (SO3H) groups [65]. Compared to
other solid sulphonic acids, oxidised wool has the advantages of a
relatively high level of sulphonic acid groups and more straightforward
and environmentally sustainable preparation [62], see Fig. 4. The
performance of wool-SO3H catalyst was compared to wool supported
iron oxide nanoparticles in the synthesis of polyfunctional heterocyclic
compounds [66]. Wool-SO3H was prepared by treating wool with
Table 4
Summary of wool catalysts.
Reactants Product
Wool powder Aromatic/heteroaromatic Beta-nitroalcohols
aldehydes, nitromethane
Wool- Carbonyl compound, Polyfunctional
sulphonic diamine, isocyanide e.g. heterocyclic
acid acetone, 2,3- compounds, e.g. 2,3-
diaminomaleonitrile, dicyano-N-cyclohexyl-
cyclohexyl isocyanide 5,7,7-trimethyl-
4,5,6,7-tetrahydro-1H-
1,4-diazepine-5-
carboxamide
Applied Catalysis A, General 541 (2017) 120140
potassium permanganate then sodium sulphite and the preparation of
the wool supported iron oxide is described in Section 4.2. The two
catalysts gave good yields of products and exhibited excellent recycl-
ability over four uses. Iron oxide-wool gave a faster reaction and greater
yields than wool-SO3H, i.e. the yields ranged from 18 to 24% for wool-
SO3H, and from 90 to 94% for iron oxide-wool.
4. Wool bres as supports for metallic catalysts
Many types of wool-supported metallic catalysts have been inves-
tigated. Complexed metal catalysts are a well-studied type of catalyst on
wool, and will be discussed in Section 4.1. Five studies of particulate
metal-wool catalyst have been reported and these are discussed in
Section 4.2. Metallic photocatalysts (typically metal oxides) are a
particular type of metallic catalyst that has been the subject of more
investigations than any other type of catalyst on wool, hence, for
clarity, they will be discussed separately from other types of metal-wool
catalysts (see Section 4.3). The various studies are summarised in
Table 5 at the end of this section.
4.1. Complexed metallic catalysts
Many studies have been made into metal-wool complex catalysts,
due to wool being a good absorber of most metal ions. The nitrogen,
sulphur and oxygen atoms in wool coordinate with ions of many
dierent metals to form metal-wool complexes that are capable of
catalysing a wide variety of reactions.
4.1.1. Palladium
Palladium-wool is the most widely studied of all complexed metal-
wool catalysts, due, in part, to palladiums versatility and lower cost
than other noble metals. Most studies with palladium-wool complex
catalysts were concerned with hydrogenation reactions, and all re-
ported that the complex was reuseable. For instance, a palladium-wool
complex was synthesized as a catalyst for the hydrogenation of the
aliphatic aldehydes: propionaldehyde, butyraldehyde, valeraldehyde,
and hexanal, to the corresponding primary alcohols. The mild reaction
conditions contributed to the catalyst maintaining stability for over
50 h of reaction [67].
A palladium-wool complex was prepared by reacting wool with
palladium chloride in ethanol [68], and a possible structure of part of
this complex, as proposed by the authors of this review, is shown in
Fig. 5, where M represents palladium chloride. This complex was
found to catalyse the asymmetric hydration of 1-octene to (S)-(+)-2-
octanol, and 1-decene to (R)-(+)-2-decanol at 70 C under 1 atmo-
sphere of nitrogen. The yields were greatly aected by the palladium
content of the complex and the reaction time. At the optimum
conditions (S)-(+)-2-octanol and (R)-(+)-2-decanol were produced in
yields close to 80%. The palladium-wool complex catalyst was straight-
forward to prepare and could be reused several times without an
appreciable change in catalytic activity. The production of high
molecular weight alcohols such as octanol and decanol is carried out
on a large scale with Ziegler-Natta catalysts, demonstrating that the
palladium-wool catalyst has a clear commercial application.
Further work using a similarly-prepared palladium-wool complex
Reference
has found that it was able to catalyse the asymmetric hydrogenation of
diacetone alcohol to (R)-2-methyl-2,4-pentanediol, and 3-methyl-2-
[60] butanone to (R)-3-methyl-2-butanol at 30 C and 1 atmosphere of
hydrogen [69]. The yields were greatly aected by the palladium
[66]
contents of the complex, and using optimum palladium content, (R)-2-
methyl-2,4-pentanediol and (R)-3-methyl-2-butanol could be obtained
in yields of 73% and 100% respectively. The simple preparation and
reusability were seen as positive features of this catalyst and the very
high chiral specicity of this process could be expected to lead to
specialised applications.
The preparation and evaluation of a palladium-wool complex was
123
S.J. McNeil et al.
Fig. 3. Wool catalysed nitroaldol (Henry) reaction in water and tetrabutylammonium bromide [60].
reported in another study which found it to be an ecient catalyst for
the asymmetric hydration of ortho- and para-substituted styrenes to
benzyl-alcohols, with high enantioselectivity under mild conditions
[70]. The chemical and optical yields of the benzyl-alcohol products
were aected by various parameters, such as the palladium content in
wool, reaction time, and temperature. The highest chemical yields
achieved were around 90%. Re-using the catalyst several times did not
signicantly change the chemical or optical yields of the products. The
mild reaction conditions and high stability of the catalyst were seen as
attractive qualities for industrial processes, suggesting potential large-
scale use. This palladium-wool complex also catalysed the hydration of
styrene, 2-cyclohexen-1-one and 5-hexen-2-one to -methylbenzyl
alcohol, 3-hydroxy-cyclohexanone and 5-hydroxy-2-hexanone respec-
tively, using mild conditions of temperature and pressure [71]. The
reaction yields were 82%, 92% and 99% respectively, and were greatly
aected by the palladium content in the complex, the ratio of substrate
to catalyst, the reaction temperature and the choice of solvent. The
catalyst was very stable and reusable without any loss of catalytic
activity.
A palladium-wool complex was prepared by subjecting wool to an
oxidising pre-treatment, followed by immersion in an aqueous palla-
dium chloride solution [72,73]. The resulting palladium-wool complex
was used in water-mediated coupling reactions of aryl halides with
alkenes and the oxidation of alcohols. A possible structure for this
complex is shown in Fig. 5, which illustrates some of the dierent types
of metal-wool binding. The studies found that aryl bromides could be
coupled to a variety of alkenes at 80 C, in aqueous media under
atmospheric pressure, with yields of over 90%. The palladium-wool
catalyst was found to be stable and low-cost, with negligible leaching of
palladium. Activity was retained for at least ten successive experimen-
tal runs, without the need for any additional activation treatment. This
approach was seen as a practical method of catalysing the important
Heck reaction, which is used to produce a wide variety of products that
are useful in organic chemistry.
The palladium-wool complex prepared as specied in the preceding
paragraph has also been used as a catalyst for the water-mediated
coupling reactions of aryl iodides and aryl bromides with arylboronic
Fig. 4. Sulphonation of wool showing reaction of disulphide bonds and thioester. NB that thioester and ester are only present of the surface of wool [38].
124
Applied Catalysis A, General 541 (2017) 120140
acid (i.e. the Suzuki reaction) [74]. The results of this study showed
that the reactions could be conducted in water under atmospheric
conditions with water-insoluble or even solid aryl halides. The products
could be obtained from the reaction mixtures by simple ltration. This
catalyst system had excellent yields (over 90% in many cases), was
environmental friendly, and the catalyst could be reused.
A palladium-wool catalyst has been used for several Liebeskind-
Srogl desulphurative cross-coupling reactions [75]. The catalyst was
prepared by treating wool with a solution of palladium(II) acetate, and
gave yields of up to 91% in three-component coupling of thioether
derivatives to terminal alkynes and aryl boronic acids. The palladium-
wool complex could be reused at least nine times, which reduced the
level of palladium in the catalyst from 1.6% to 1.4% (by mass),
suggesting there was minimal contamination of the reaction phase.
This palladium-wool catalyst has also been used for carboncarbon
cross-coupling reactions involving the cleavage of disulphide bonds.
Yields up to 88% were achieved and there was negligible leaching of
palladium during ten uses.
A palladium-wool catalyst was prepared and applied in the oxida-
tion of alcohol under optimised conditions, and several parameters such
as the amount of catalyst, base, reaction temperature, and reaction time
were investigated [76]. It was found that 35 mg of palladium-wool
catalysed the oxidation of 0.2 mmol of alcohol to the corresponding
aldehyde or ketone when using water as reaction medium. The catalyst
demonstrated good reusability in this reaction system. The oxidation of
alcohol is used in specialised or small-scale organic synthetic produc-
tion of ketones, with the dominant method utilising oxidation of
hydrocarbons, the industrial potential for these new methods is large,
with acetone being produced in large amounts worldwide.
4.1.2. Platinum
A platinum-wool complex was prepared by the reaction of wool
with chloroplatinic acid in ethanol, and was found to be an eective
chiral catalyst for the asymmetric hydrogenation of some ketones to the
corresponding chiral alcohols at 30 C under 1 atmosphere of hydrogen
[77]. Examples given were 3-methyl-2-butanone to (R)-3-methyl-2-
butanol, 4-methyl-2-pentanone to (R)-4-methyl-2-pentanol, acetophe-
S.J. McNeil et al. Applied Catalysis A, General 541 (2017) 120140

Table 5
Summary of metallic-wool catalyst systems that have been studied.

Type of catalyst/metal Reaction/reactant Product Reference(s)

Metal complex
Palladium Hydrogenation. Primary alcohols [67]
Aliphatic aldehydes
Hydrogenation. Octanol [68]
Octene Decanol
Decene
Hydrogenation. (R)-2-Methyl-2,4-pentanediol [69]
Diacetone alcohol (R)-3-Methyl-2-butanol
3-Methyl-2-butanone
Hydrogenation. Benzyl alcohols [70]
o- & p-substituted styrenes
Hydrogenation. -Methylbenzyl alcohol, [71]
Styrene 3-Hydroxy-cyclohexanone
2-Cyclohexen-1-one 5-Hydroxy-2-hexanone
5-Hexen-2-one
Coupling aryl halides to alkenes Various coupling products [72]
Oxidation of alcohols Aldehydes, ketones [73]
Coupling of aryl halides to aryl boronic acids Biphenyls [74]
Coupling pyrimidin-yl thioether derivatives, Various coupling products [75]
alkynes and aryl boronic acids.
Oxidation of alcohols Aldehydes, ketones [76]
Platinum Asymmetric hydrogenation of ketones Chiral alcohols [77]
Palladium-cobalt Asymmetric hydration of unsaturated -hydroxycarboxylic acids [78]
carboxylic acids
Iron-palladium Hydrogenation. Chloroanilines [79]
Chloro-nitro benzenes Chlorobenzyl alcohols
Chloro-benzyl aldehydes
Iron-palladium Hydration. 1-Bromo-2-propanol [80]
Allyl bromide 1-Chloro-2-propanol
Allyl chloride 1-Amino-2-propanol
Allylamine Lactonitrile
Acrylonitrile Cyclohexanol
Cyclohexene
Rhodium Hydrogenation. (S)-(+)-2-Methyltetrahydrofuran [81]
2-Methylfuran
Osmium Asymmetric dihydroxylation. (R)-(+)-3-Amino-1,2-propanediol [82]
Allylamine (3-aminopropene) (S)-(+)-3-Chloro-1,2-propanediol
Allyl chloride
Copper Oxidation of L-ascorbic acid and D-isoascorbic Dehydroascorbic acid, dehydroisoascorbic acid, hydrogen [83]
acid peroxide
Iron and cobalt phthalocyanines Oxidation. Dimethyl disulphide [84]
Methanthiol Dihydrogen disulphide
Hydrogen sulphide
Cobalt, copper, iron tetrasulpho- Alkylarenes Ketones [85]
phthalocyanines Alcohols Aldehydes and ketones

Metallic particulate
Manganese dioxide Oxidation of alkyl arenes, alcohols and Carbonyl and sulphoxide compounds [88]
sulphides
Manganese dioxide Oxidation and addition. -amino amides, [89]
Toluene/xylene, aromatic amines, 3,4-dihydroquinoxalin-2-amine, 4H-benzo[b][1,4]thiazin-2-
cyclohexyl isocyanide amine, cyanophenylamino-acetamide derivatives
Cobalt, manganese, zinc and Toluene/xylene, phenylenediamine Imidazole derivatives [90]
chromium ferrites Toluene/xylene, aminobenzamide Quinazoline derivatives
Toluene/xylene, phenylenediamine, Quinoxaline derivatives
cyclohexyl isocyanide
Iron oxide Carbonyl compound, diamine, isocyanide Polyfunctional heterocyclic compounds, e.g. 2,3-dicyano-N- [66]
e.g. acetone, 2,3-diaminomaleonitrile, cyclohexyl-5,7,7-trimethyl-4,5,6,7-tetrahydro-1H-1,4-diazepine-5-
cyclohexyl isocyanide carboxamide
Gold chloride Methanol, 3-hexyne 4-Methoxy, hex-3-en-3,4-dimethoxy hexane [91]

Metallic photocatalysta
Titania Stains on textiles, dyes in waste water Colourless compounds [99102,108,109,120]
Titania Live bacteria Inactive bacteria [95,103]
Titania Water (light induced wettability) Hydroxyl radicals, super oxide anions [106,107]
Titania/graphene Dye on textile Colourless compounds [113]
Zirconia Dyes in solution Colourless compounds [119,120]
Zinc oxide Dyes in solution Colourless compounds [121]
Zinc oxide Dyes and food stains on textiles Colourless compounds [122]
Zinc oxide Dye on textile Colourless compounds [123]
Nitrogen-doped zinc oxide/ Dye on textile Colourless compounds [124]
nitrogen-doped titania
Palladium, palladium sulphide and Dyes in solution Colourless compounds [125]
cadmium sulphide
Palladium, palladium sulphide, Water Hydrogen, oxygen [126]
(continued on next page)

125
S.J. McNeil et al.
Table 5 (continued)
Type of catalyst/metal Reaction/reactant
cadmium sulphide
Iron Textile dyes in solution
a
Only a small selection of the many studies of titania-wool are included.
none to (R)-1-phenylethanol and propiophenone to (R)-1-phenyl-1-
propanol. In the case of hydrogenation of 3-methyl-2-butanone to (R)-3-
methyl-2-butanol, when a suitable content of platinum in the wool was
selected, the total yield and yield of the desired optical isomer
amounted to about 100%, and the platinum-wool catalyst could be
reused without any change in the optical catalytic activity. The
platinum-wool catalyst was seen as a relatively cheap, easy to prepare,
active, enantioselective, and stable chiral catalyst for the asymmetric
hydrogenation of ketones.
4.1.3. Palladium-cobalt
A heterobimetallic palladium-cobalt-wool complex was prepared
using palladium chloride, cobalt chloride and wool in ethanol [78].
This was found to be an ecient catalyst for the asymmetric hydration
of unsaturated carboxylic acids with high enantioselectivity via a
simple process under mild conditions. Chemical and optical yields were
aected by parameters such as the combined level of palladium and
cobalt on the wool, the ratio of palladium to cobalt, the reaction time
and temperature, and the amount of water. After using the catalyst ve
times, the chemical and optical yields of the products showed no
signicant changes, thus demonstrating the stability of the complex.
The methods used provided a novel way to produce chiral -hydro-
xycarboxylic acids. Fig. 5 represents a possible structure of the complex,
where M represents a combination of palladium chloride and cobalt
chloride.
4.1.4. Iron-palladium
Complexes of iron-palladium-wool have been synthesised and their
catalytic performances compared with those of a palladium-wool
complex. Of these two complexes, iron-palladium-wool showed the
greater catalytic activity and selectivity for the hydrogenation of
chloro-nitro benzenes and chloro-benzyl aldehydes to chloroanilines
and chlorobenzyl alcohols respectively at room temperature and atmo-
spheric pressure [79]. The ratio of palladium to iron had a signicant
eect on the selective hydrogenation of the substrates, at an optimum
ratio of palladium to iron of 13, chloroanilines were obtained at 100%
yield, and no unwanted hydrogenolysis (dechlorination) occurred.
When the molar ratio of palladium to iron in the complex was 15 to
1, this wool complex could catalyse the hydrogenation of chlorobenzyl
aldehydes to chlorobenzyl alcohols without hydrogenolysis of the
Fig. 5. The possible structure of metal-wool complex (M = metal salt) as proposed by the current authors.
Applied Catalysis A, General 541 (2017) 120140
Product Reference(s)
Colourless compounds [127129]
chloro group.
The iron-palladium-wool complex was also the subject of a study, in
which it was prepared from wool, palladium chloride and iron chloride
in ethanol [80]. This complex, as proposed in Fig. 5, was found to be a
highly active catalyst for the hydration of some alkenes to the
corresponding alcohols. Examples given were allyl bromide to 1-
bromo-2-propanol, allyl chloride to 1-chloro-2-propanol, allylamine to
1-amino-2-propanol, acrylonitrile to lactonitrile and cyclohexene to
cyclohexanol, with yields of 95%, 88%, 91%, 75% and 98% respec-
tively. These reactions were all performed in the presence of water,
butyl ether and phenol at 95 C under 1 atmosphere of nitrogen. The
yields were greatly aected by the ratio of palladium to iron, and the
catalyst was very stable and could be reused several times without a
signicant loss of activity.
4.1.5. Rhodium
A rhodium-wool complex was prepared by the reaction of wool with
rhodium chloride in ethanol, and was found to be an eective chiral
catalyst for the asymmetric hydrogenation of 2-methylfuran to (S)-
(+)-2-methyltetrahydrofuran at 28 C under 1 atmosphere of hydrogen
[81]. Depending on the rhodium content in the rhodium-wool complex,
the yield and optical yield were as high as 54% and 77%, respectively.
The researchers noted that the rhodium-wool complex was a stable,
inexpensive and easy-to-prepare catalyst.
4.1.6. Osmium
A chiral osmium-wool complex was prepared by reacting wool with
osmium tetroxide in tert-butanol [82]. This complex was shown to
catalyse the asymmetric dihydroxylation of allylamine (3-aminopro-
pene) to (R)-(+)-3-amino-1,2-propanediol, and allyl chloride to (S)-
(+)-3-chloro-1,2-propanediol. The optical yields were 84% and 57%,
and the product yields were 80% and 69% respectively. The osmium
tetroxide content in the complex, reaction time, ratio of allylamine to
osmium tetroxide, and solvent, all eected the product and optical
yields. The osmium tetroxide-wool complex catalyst could be reused
without any signicant change in optical catalytic activity.
4.1.7. Copper
To prepare a copper-wool complex catalyst, wool was rst acidied
with acetic acid (to increase the uptake of copper ions), then treated
126
S.J. McNeil et al. Applied Catalysis A, General 541 (2017) 120140

with copper nitrate solution at pH 5.9 for 48 h at room temperature molecules, thus contributing to their ecacy as catalysts [86,87]. The
with occasional shaking [83]. The resulting catalyst contained 0.9% direct utilisation of metal nanoparticles as catalysts is often dicult,
copper by mass. The catalytic action of the copper-wool complex in the due to the tendency for agglomeration caused by van der Waals forces.
oxidation of L-ascorbic acid and D-isoascorbic acid was studied and Supporting matrices serve to minimise aggregation of the nanoparticles,
showed oxidation at pH 8 and above. The catalyst exhibited Michaelis- and provide the desired interface between the nanoparticles and the
Menten behaviour as an oxidase-like catalyst, and was able to be reused reaction media, as well as facilitating the synthesis and reuse of the
ve times without losing activity. catalysts. Five studies on wool supported nanoparticle catalysts have
been reported [66,8891].
A range of oxidation reactions have been studied with nanoparticles
4.1.8. Metallophthalocyanine complexes of various metals
of manganese dioxide supported by wool [88]. The catalyst was
The catalytic activities of metallophthalocyanine complexes have
prepared by the straightforward process of treating wool with potas-
been widely studied because they are inexpensive and straightforward
sium permanganate solution. The wool had a chemical involvement in
to prepare on a large scale, and are chemically and thermally stable.
the process as it reduced the MnO4 ions to MnO2 nanoparticles. The
Various support materials have been investigated, such as charcoal,
manganese dioxide-wool catalyst was evaluated for the aerobic oxida-
organic polymers, and zeolites, but wool bres have the advantages of
tion of alkyl arenes, alcohols and sulphides, to carbonyl and sulphoxide
being easier to handle, able to be manipulated into a wide range of
compounds, with good results. For example, a range of 10 alkyl arenes
structures and amenable to chemical modication by well established
were oxidised to aldehydes and ketones and in each case the yields were
techniques [84].
89% and above, and there was no over-oxidation to carboxylic acids.
Wool that had been cationised with a salt of trimethyl epoxybutane
The activity of manganese dioxide on wool was comparable or slightly
ammonium has been rendered catalytic by treatment with solutions of
greater than its activity when supported on graphite, kieselguhr, silica
phthalocyanine iron(III) [84]. The resulting binuclear phthalocyanine
or cellulose, as assessed for the oxidation of benzyl alcohol.
iron(III)-wool complex contained 0.8% phthalocyanine iron(III) on
The manganese dioxide-wool catalyst described in the preceding
mass of wool (see Fig. 6). Phthalocyanine cobalt(II)-wool complex
paragraph has also been used for the Ugi-type reaction of aromatic
was prepared similarly using phthalocyanine cobalt(II) in place of
hydrocarbons [89]. The catalyst was active in both the oxidation and
phthalocyanine iron(III). The uptake of the metal complexes was
acidic/synthetic stages of the reaction. The catalyst proved durable,
around nine times higher on cationised wool than on untreated wool.
with negligible loss of activity after ve uses. The manganese dioxide-
The binuclear iron(III)-wool complex was used to decompose
wool catalyst gave a greater yield than the corresponding manganese
methanthiol and hydrogen sulphide at room temperature by catalytic
dioxide-cellulose catalyst for the acidic stage, but not for the oxidation
oxidation with atmospheric oxygen [84]. The phthalocyanine iron(III)-
stage of the reaction.
wool complex performed slightly better than the corresponding cobalt
Six types of transition metal ferrite nanoparticles were formed on
complex by removing around 90% of methanthiol and hydrogen
wool and used in tandem oxidative two-component reactions and Ugi-
sulphide in 180 min at 25 C. The methanthiol experiment was repeated
type three-component reactions, to prepare biologically active benzi-
ve times with the same sample of iron(III)-wool complex and it
midazole, quinazolinone and quinoxaline derivatives [90]. The wool
showed no reduction in oxidising capacity. The phthalocyanine cobalt
was rst oxidised with potassium permanganate and then the manga-
(II)-wool complex was almost as stable as the corresponding iron(III)-
nese dioxide formed in the wool was removed by reduction with sodium
wool complex.
sulphite. This converted some of the disulphide bonds into sulphonate
Wool has been used to support cobalt(II), copper(II) and iron(II)
groups, thus enhancing both the subsequent uptake of metal ions and
tetrasulphophthalocyanine catalysts for the aerobic oxidation of alkyl
the attachment of the nanoparticles. The wool was then treated in
arenes and alcohols (see Fig. 6) [85]. Wool and metal(II) trisul-
aqueous solutions of mixtures of iron(III) chloride, and chlorides of
phophthalocyanine sulphonyl chloride were reacted together to give
selected metals, to form wool supported CoFe2O4, MnFe2O4, ZnFe2O4,
covalent bonding. Supporting the metallophthalocyanines on wool
MnCoFe2O4, ZnCoFe2O4 and CrCoFeO4. The catalysts showed good
reduced aggregation of the complexes and thereby increased their
recyclability, with little loss of reactivity during four reuses. The best
activity. The catalysts were recyclable without the loss of activity. Of
results overall, were obtained with CrCoFeO4-wool. Preparing the
the three types of catalyst investigated, the one with cobalt was the
ferrite nanoparticles on wool prevented them aggregating/agglomerat-
most eective overall, followed by the copper, with the iron catalyst
ing into less active particles. The magnetic properties of these wool-
being the least eective for the reactions investigated.
supported catalysts is advantageous, as it helps their recovery from the
reaction products.
4.2. Particulate metallic catalysts Wool supported iron(II,III) oxide (Fe3O4) nanoparticles have been
prepared by treating wool with solutions of iron(II)/iron(III) chlorides
Metal nanoparticles have a high surface area-to-volume ratio and [66]. The wool supported iron oxide was paramagnetic and the
therefore a large fraction of the metal can be exposed to reactant

Fig. 6. The structures of phthalocyanine (left), tetrasulphophthalocyanine (centre) and iron (III), complex (right) as proposed by Yao et al. [84].

127
S.J. McNeil et al.
nanoparticles comprised 15% of the mass of the iron oxide-wool. This
catalyst gave good yields of products in the synthesis of polyfunctional
heterocyclic compounds, and exhibited excellent recyclability over four
uses. The performance of this catalysts was compared to that of oxidised
wool in Section 3.
Gold(I) chloride nanoparticles have been prepared on wool by
suspending wool in acidic gold(III) chloride [91]. The mixture was
shaken to develop the nanoparticles, and the pH was adjusted to 11.2
using potassium hydroxide. The mixture was heated and shaken at
50 C for seven days, before recovering the gold-wool by ltration and
washing with water and air-drying. The gold(I) chloride nanoparticles
that were deposited onto the wool were found to be catalytically active
in the addition of methanol to 3-hexyne. Two unsupported molecular
gold(I) chloride phosphine complexes performed similarly to each
other, but the wool-supported gold chloride nanoparticles retained all
activity after eight reaction cycles compared to only one or two for the
phosphine complexes.
4.3. Metallic photocatalysts
Research into photoactive textiles is largely driven by the textile
industrys interest in oering consumers products with enhanced
functionalities [92]. While it is well known that wool has a lower
resistance towards photodegradation than some other types of textile
bres [93], wool has been investigated as a support for various types of
photocatalysts such as metal oxides, metal sulphides, metal ions and
dyes. Photocatalytic dyes on wool are discussed in Section 6, and
photocatalysts on reconstituted wool are discussed in Section 8.
4.3.1. Titania
The most widely studied photocatalyst on wool, and other textile
bres, is titania (titanium dioxide), due to its high photocatalytic
activity, non-toxicity, ready availability, biocompatibility, and low
price [9496]. Titania in the form of colloids, powders, or a combina-
tion of both, has been applied to wool [97]. Alternatively, titania has
been formed on wool by the hydrolysis and condensation of precursor
compounds such as titanium tetraisopropoxide in the sol-gel process
[93]. The photocatalytic activity of semi-conducting materials such as
titania is caused by light of the appropriate wavelength promoting
electrons from the valence band to the conduction band, see Fig. 7. The
electron vacancies produced in the valence band are strongly oxidizing,
while the electrons promoted to the conduction band are strongly
reducing. The electron vacancies are able to react with water molecules
to generate hydroxyl radicals. The electrons promoted to the conduc-
tion band react with oxygen molecules, reducing them to superoxide
radical anions. There is generally sucient water vapour in the air for
the formation of radicals on titania. It is thought that the hydroxyl
radicals, rather than the superoxide radicals, cause the breakdown of
organic material [98]. Other than the photocatalytic properties that will
be discussed below, titania has other notable light-related properties,
i.e. a high level of whiteness and a strong absorption of ultraviolet light.
Titania has been applied to wool to impart four types of photo-
catalytic activity, i.e. decomposing stains and other organic molecules,
resistance to bacteria, light-induced wettability, and the decomposition
of compounds in wastewater. This topic has attracted considerable
Fig. 7. Photo-excitation of electrons and radical formation in semiconductors.
128
Applied Catalysis A, General 541 (2017) 120140
attention from researchers resulting in several hundred publications,
and only illustrative examples will be discussed here. The interested
reader may like to consult some excellent recent reviews of the subject
[94,95].
The solid-phase decomposition of coloured compounds on textiles is
known as self-cleaning. The decomposition of food stains such as coee,
tea, and fruit juice [99,100], and dyes such as methylene blue and Acid
Blue 113 [99,101,102] have been studied on titania-wool. The radicals
that decompose stains are also capable of reacting with molecules in
bacteria to such an extent that titania treated wool has signicant
resistance to bacteria [103105]. Radicals on titania interact with
molecules of liquid water more strongly than the hydrophobic surface
of wool, giving rise to light-induced wettability [106,107]. This
wettability is reversible, so that when the light source is removed, the
hydrophobicity of the wool surface is restored.
Titania nanoparticles deposited onto wool decoloured an aqueous
solution of Direct Blue 78 dye after 6 h of illumination with ultraviolet
light [108]. Some of the dye had been adsorbed by the wool and a
further 24 h of illumination was required to decolour the fabric. The
photocatalytic activity of the titania-wool fabric was preserved after
three photodegradation cycles. Phenol and various chlorophenols,
which occur in some euent streams, have been decomposed in the
liquid phase by titania treated wool [109].
Achieving adequate adhesion between the wool and the titania can
be challenging [95], and it is thought that CTi3+, OTi3+, and NTi3+
bonds are formed [110]. Several studies have investigated dierent
approaches to enhancing adhesion by modication of the wool surface
using techniques such as microwave-generated afterglow plasma [111],
radio-frequency plasma [99] and ultraviolet light [99]. These pre-
treatments were thought to modify both the physical and chemical
properties of the wool surface, by, for instance, increasing both the
micro-roughness and the number of polar groups [99]. Another
approach to increasing adhesion is to use binders such as carboxylic
acids that form covalent bonds between the wool and titania [106].
Heat treatments are important for imparting photocatalytic activity to
titania particles, and they can increase adhesion to wool [112], but care
must be taken to avoid yellowing the wool. A nanocomposite of
graphene/titania has been prepared on wool, which decoloured methy-
lene blue under sunlight irradiation [113]. The wool had rst been
treated with titanium isopropoxide/graphene oxide suspension, fol-
lowed by reduction with sodium hydrosulphite.
The photoactivity of titania has been enhanced in a number of ways,
some of which may be applicable to titania on wool. For instance,
incorporating silver and other metals [99,114], metal oxides [115],
silica [107], dyes [116] and other materials [110,117] into titania can
increase its photoactivity. Some additives can render titania photo-
catalytic under visible (as opposed to ultraviolet) light [118]. The
photocatalytic activity of titania in liquid-phase reactions can be
increased by applying ultrasound [109].
4.3.2. Zirconia and zinc oxide
Citric acid has been used to bind zirconia particles (15 nm mean
particle diameter) to wool, and the zirconia retained its ability to
decompose the methylene blue [119]. The photocatalytic activities of
wool coated with titania and zirconia by the sol-gel process were
S.J. McNeil et al.
compared by studying the photodegradation of the dyes methylene blue
and Eosin Y. The dyes were readily decomposed under ultraviolet/
visible light with the titania-coated wool giving the most rapid
decomposition of the dyes [120]. The two dyes mentioned above have
also been photochemically decomposed by zinc oxide-wool. The zinc
oxide had been formed from zinc acetate and sodium hydroxide, and
applied to the wool by dip coating, and was able to decompose dyes in
solution [121]. Zinc oxide nanoparticles have also been attached to
wool by butanetetracarboxylic acid and sodium hypophosphite and
were able to decompose stains of dyes (Direct Blue 71 and Disperse Red
1), coee and black mulberry juice on the treated wool under
ultraviolet light [122].
Nitrogen-doped zinc oxide nanoparticles have been formed on wool
by ultrasound-assisted hydrolysis of zinc acetate and ammonia [123].
The treated wool decolourised methylene blue stain in sunlight. This
approach has also been taken to form nitrogen-doped zinc oxide/
nitrogen-doped titania coreshell nanocomposites on wool and the
strong photodecomposition of methylene blue that occurred was
ascribed to a synergy between the zinc oxide and titania [124].
4.3.3. Palladium and cadmium
Wool that had been coated with a combination of palladium,
palladium sulphide and cadmium sulphide has been shown to catalyse
the photodegradation of the dye Rhodomine B under visible light [125].
This combination of materials was found to be a more eective catalyst
for this reaction than pure cadmium sulphide, and this was attributed to
the wool preventing the recombination of photo-generated electrons
and electron holes. In comparison to unsupported cadmium sulphide
particles, the wool-based photocatalyst was reported to have the
advantages of being recyclable and more cost-eective.
Palladium-palladium sulphide-cadmium sulphide-wool has also
been shown to photocatalyse the formation of hydrogen gas from water
[126]. The optimal preparation involved treating wool with 3% by mass
of cadmium acetate, which resulted in the highest visible-light photo-
catalytic activity of 1.6 mmol of hydrogen per hour for 0.15 g of
photocatalyst. This study demonstrated that the palladiumpalladium
sulphide-wool catalyst could improve the eciency of photocatalytic
hydrogen production by combining the oxidation co-catalyst palladium
sulphide, and the reduction co-catalyst palladium. The catalyst was
described as being eco-friendly and recyclable.
4.3.4. Iron
Wool has been treated with ferric chloride to prepare solid photo-
Fenton catalysts [127129]. The iron-wool catalyst showed high
photocatalytic activity in the degradation of Rhodamine B and Acid
Black 234 dyes in water, when the pH was below 6.0. An advantage of
photo-Fenton catalysis is that visible, rather than ultraviolet, light can
be used. However, there are signicant disadvantages such as the need
to use low pH conditions, to add hydrogen peroxide, and to remove the
ferrous and ferric ions from the reaction mixture.
4.4. Summary
The 49 wool supported metallic catalysts systems discussed here are
summarised in Table 5. Metallic photocatalysts were the most widely
studied, followed by metal complexes then metallic particles.
5. Wool bres as supports for biological catalysts
Many studies have shown that enzymes and viable cells can be
immobilised onto dierent types of natural and synthetic polymer
bres, with retention of catalytic activity [130133]. Various types of
enzymes and cells have been immobilised onto wool utilising a range of
immobilisation protocols, and these are discussed below and sum-
marised in Table 6.
Many of the reactions and processes that will be discussed in
129
Applied Catalysis A, General 541 (2017) 120140
connection with supported biological catalysts are of commercial
signicance, particularly for the processing of food, cellulose, starch,
pharmaceuticals and cosmetics, and for environmental and industrial
monitoring [134142]. Thus, there are clear potential commercial uses
for biological catalysts immobilised onto wool.
5.1. Enzymes
5.1.1. Glycosidases
Perhaps the earliest study of enzyme immobilization onto wool was
reported by Masri et al. in 1975 who studied the binding of lactase
[143]. Two immobilisation protocols were investigated; azo coupling
with diazotised wool, and Schi base formation with nitrilated wool,
see Fig. 8. The former approach was unsuccessful, but the latter gave a
material that catalysed the hydrolysis of lactose.
Galactosidases are a type of glycosidase that catalyse the hydrolysis
of galactosides into monosaccharides, and have been immobilised onto
pre-treated wool [144]. Acrylic acid was rst graft polymerised onto
wool using the water-soluble photo-initiator sodium 4-(sulphomethyl)
benzil, and the enzyme was then coupled to the polymer grafted wool
with the water-soluble carbodiimide, 1-cyclohexyl-3-(2-morpholi-
noethyl) carbodiimide metho-p-toluene sulphonate. The activity of
the immobilised enzyme was determined by the hydrolysis of 2-
nitrophenyl--galactopyranoside. Wool had been selected as the cata-
lyst support for this study as it was thought to be a good substrate for
coupling with enzymes because of the similarities between many enzyme
systems and wool. The activity of galactosidase on wool compared
favourably with those reported by other researchers for the same
enzyme on nylon grafted with polyacrylamide [145], and poly(metha-
cryloxybenzoic acid) cross-linked by divinylbenzene [146]. It was
thought that both the amine and carboxyl groups of the enzyme were
involved in attachment to the wool, and that the enzyme was
immobilised on the surface of the polymer grafted wool, rather than
the interior, thus contributing to a high activity [144]. Galactosidases
have also been covalently attached to wool by a polyethyleneimine/
glutaraldehyde protocol, but the resulting activity was poor [147].
Lysozymes are known for their ability to damage the cell walls of
bacteria, making them of interest as antibacterial agents. A lysozyme
has been immobilised onto wool fabric with glutaraldehyde, and
retained 30% of its initial immobilised activity against Staphylococus
aureus after six uses [148,149]. A lysozyme has also been immobilised
onto wool by a crosslinking procedure catalysed by transglutaminase,
and it enhanced the antibacterial and antifungal properties of the wool
[150]. A third approach to the immobilisation of lysozymes onto wool
has been investigated, namely layer-by-layer electrostatic self-assembly
deposition with poly(sodium 4-styrenesulphonate), a protocol which
imparted signicant microbial resistance [151].
Amylase has been immobilised onto wool, cotton, viscose rayon and
polypropylene bres with glutaraldehyde [152]. The supported enzyme
was able to hydrolyse starch, see Fig. 9. Of the dierent combinations of
amylase and support, amylase-cotton and amylase-viscose rayon ex-
hibited the greatest activity. Amylase has also been immobilized onto
wool that had been activated by cyanuric chloride [153]. Increasing the
concentration of cyanuric chloride to 40 g/L increased the immobiliza-
tion eciency to 70%, and the immobilized amylase retained 75% of its
initial immobilised activity after ten experiments. The immobilized and
soluble amylases displayed maximum activities at pH 6.5 and 6.0,
respectively, and the former was more resistant to thermal degradation
and inhibition by metal ions, than the later.
5.1.2. Lipases
The feasibility and limitations of using wool fabric as a substrate for
lipase immobilisation has been investigated [147,154]. Lipase from
Pseudomonas uorescens was attached to wool by a covalent binding
protocol using polyethyleneimine as a spacer and glutaraldehyde as a
cross-linker. The activity of the immobilised enzyme was reasonably
S.J. McNeil et al. Applied Catalysis A, General 541 (2017) 120140

Table 6
Summary of wool-biological catalyst systems that have been studied.

Enzyme/Microbe Attachment Reactant Product(s) Reference(s)

Lactase Azo coupling and Schi base formation Lactose Glucose, galactose [143]
Galactosidase Carbodiimide coupling on acrylic acid grafted wool 2-nitrophenyl--galactopyranoside o-nitrophenol, [144]
galactopyranoside
Galactosidase Polyethyleneimine/glutaraldehyde coupling 2-nitrophenyl--galactopyranoside o-nitrophenol, [147]
galactopyranoside
Lysozyme Glutaraldehyde coupling Live bacteria Inactive bacteria [148,149]
Lysozyme Transglutaminase coupling Live bacteria Inactive bacteria [150]
Lysozyme Layer-by-layer deposition with poly(sodium 4-styrenesulphonate) Live bacteria Inactive bacteria [151]
Amylase Glutaraldehyde coupling Starch Glucose [152]
Amylase Cyanuric chloride pre-treatment, absorption Starch, glycogen, amylopectin, Reducing sugars [153]
amylose, cyclodextrins
Lipase Polyethyleneimine/glutaraldehyde coupling on untreated wool, Olive oil stain on fabric Stain-free fabric [147,154]
and wool pre-treated by chlorination/polyamide resin
Lipase Polyethyleneimine/glutaraldehyde coupling Tributyrin Butyric acid, glycerol [58,155157]
Lipase Azide coupling on ethylacrylate grafted wool Olive oil Fatty acids, glycerol [158]
Lipase Entrapment in casein gel covalently attached to the wool surface p-Nitrophenyl palmitate p-Nitrophenol, palmitic acid [147]
Catalase Anionic dye pre-treatment, adsorption Hydrogen peroxide Water, oxygen [166]
Catalase Layer-by-layer deposition with poly(diallydimethylammonium Hydrogen peroxide Water, oxygen [167]
chloride)
Horseradish Cyanuric chloride pre-treatment, absorption Guaiacol, hydrogen peroxide Not reported [168]
peroxidase
Rhamnosidase Papain pre-treatment, absorption Naringin Rhamnose, prunin [169]
Trypsin Carbodiimide coupling on acrylic acid grafted wool hydrolysis of -benzoyl-arginine-p- Not reported [144]
nitroanilide
Acid phosphatase Carbodiimide coupling on acrylic acid grafted wool hydrolysis of Not reported [144]
p-nitrophenyl phosphate
Lactoferrin Transglutaminase coupling and tyrosine coupling Live bacteria and fungi Inactive bacteria and fungi [150,170172]
Lactoferrin Tyrosinase coupling Live bacteria Inactive bacteria [172]
Bakers yeast Glutaraldehyde coupling Sucrose Glucose, fructose [173]
Microbe-rich sewage Adsorption Synthetic sewage Not reported [174]
sludge

stable, i.e. 80% of its immobilised activity remained after 80 days in a
buer solution in a refrigerator. The pHs for the optimum activities of
the free and immobilized lipase were very similar, suggesting the
microenvironments for the free and immobilised lipase were compar-
able. The lipase-immobilised fabric demonstrated excellent removal of
olive oil stains, and this ability was retained for at least one month of
storage in a dry state. The activity of a galactosidase immobilized onto
wool by this protocol was poor compared to the activity of the lipase,
suggesting the polyethyleneimine/glutaraldehyde immobilisation pro-
tocol is not necessarily applicable to all enzymes [147,154]. Treating
the wool by chlorination followed by the application of a polyamide-
epichlorohydrin resin, enhanced the subsequent immobilisation of
lipase [147,154].
The polyethyleneimine/glutaraldehyde covalent enzyme immobili-
sation protocol discussed in the preceding paragraph [147,154] was
rened in a subsequent study [155]. The immobilised lipase had good
stability, and retained 81% of its initial immobilised activity during ten
replications of a tributyrin hydrolysis procedure. The authors stated
that their work opens up the possibility of using wool as a cheap and
eective lipase support material for continuous lipase reactions/reactors and
possibly enzyme enhanced woollen fabrics.
The polyethyleneimine/glutaraldehyde covalent enzyme immobili-
sation protocol was also used in further studies [58,156,157]. The
optimal pH for the hydrolysis of tributyrin by the immobilised lipase
was found to be slightly dierent to that of the free lipase, suggesting
that there were some dierences in the immediate environments of the
enzyme. The free and immobilized lipase had the same optimal
temperatures of 45 C for the hydrolysis of tributyrin. The immobilized
lipase was stable to reuse (85% retention of activity after six long-term
tributyrin hydrolysis procedures) and storage (76% retention of activity
after 40 weeks at 4 C). Immobilisation increased the thermal stability
of the lipase by a factor of 2.4 times.
A lipase has been covalently attached to wool that had been graft
polymerised [158]. The grafted poly(ethylacrylate) was activated on
the wool by converting it to poly(acrylic acyl azide) before coupling
with the enzyme. This immobilisation protocol greatly increased the
thermal and operational stabilities of the enzyme, along with the
kinetic constant value, as assessed by the hydrolysis of olive oil.
One approach to attaching enzymes and microbes to textiles, is to
encapsulate them in matrices such as silica [159,160] and casein [147].
These matrices can be coated onto the surface of the textiles and retain
signicant levels of enzyme/microbe activity. Such encapsulated
biological catalysts have been applied to textiles made of bres such
as polyester [161], viscose [162], and wool [147]. Lipase has been
attached to wool by entrapment in a casein gel that had been formed on
the surface of wool fabric in the presence of transglutaminase [147].
While this approach was able to immobilise the lipase onto wool, the
loss of enzyme by diusion, and the high mass transfer resistance of the
gel, meant that this approach was seen by the researchers as less
successful than covalent attachment.
5.1.3. Catalase
Catalase is an enzyme which catalyses the decomposition of
compounds such as hydrogen peroxide, thereby helping to protect cells
from damage by reactive oxygen species. Catalase is used in the food,
dairy, and pulp and paper industries [163]. In textile processing it is
used to remove undesirable residues of hydrogen peroxide that are
present on textiles after some types of bleaching [164], and has shown
some potential in treating textile processing euent [165].
Catalase has been immobilized onto a range of supports including
wool, nylon 6, silk, chitosan, amberlite, and poly(vinylpyrrolidone). In
one study, catalase was applied to supports (including wool) which had
been activated by dyeing with an anionic dye [166], see Fig. 10. The
immobilised catalase exhibited the greatest activity on nylon 6 that had
been activated by the sulphonic dye, Cibacron Blue, with around one-
third of the enzyme being active. The optimal pH of the catalase was
not changed by immobilisation, and the immobilised enzyme had
greater stability than free enzyme under the conditions typically

130
S.J. McNeil et al.
Fig. 8. Immobilisation of lactase onto wool, and hydrolysis of lactose [143].
encountered in food processing. Catalase has also been applied to wool
fabric via layer-by-layer electrostatic self-assembly deposition with poly
(diallyldimethylammonium chloride) and was found to be active
against hydrogen peroxide during repeated experiments [167].
5.1.4. Other enzymes
Immobilising horseradish peroxidase onto wool was reported to
have made the enzyme more suitable for several industrial and environ-
mental purposes [168]. The wool had been pre-treated with cyanuric
chloride to enhance subsequent attachment of the enzyme. The
immobilised enzyme retained 50% of its initial immobilised activity
against guaiacol and hydrogen peroxide after seven reuses. Compared
to the free enzyme, the immobilised enzyme demonstrated a broader
optimum pH range, a higher optimum temperature, greater resistance
to trypsin mediated proteolysis, greater storage stability and superior
resistance to denaturation by urea, non-ionic surfactant, isopropanol,
butanol and dioxan.
Naringin is the substance responsible for the bitter taste of grape-
fruit and some orange juices. Naringinase enzyme is used industrially to
decompose naringin in fruit juices to improve their taste, and the
immobilisation of the naringinase alpha-rhamnosidase onto wool and
other supports has been studied [169]. Papain treated silk broin was
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the support that gave the greatest stabilisation of the enzyme, followed
by bovine horn keratin and papain treated wool, and powdered calf
hide collagen.
The enzymes trypsin and acid phosphatase have been immobilised
onto wool that had been modied by the graft polymerisation of acrylic
acid by the protocol discussed in Section 5.1.1 above [144]. Trypsin
activity was measured by the hydrolysis of -benzoyl-arginine-p-
nitroanilide, and acid phosphatase activity was measured by the
hydrolysis of p-nitrophenyl phosphate, and both enzymes demonstrated
signicant activities when supported on wool.
5.2. Lactoferrin
Lactoferrin is a glycoprotein with many functions in living systems,
most notably the binding and transport of iron ions. It is part of the
human immune system and has antimicrobial activity. Lactoferrin has
been covalently bound to wool by a reaction catalysed by transgluta-
minase enzyme [150,170,171]. The wool-supported Lactoferrin showed
good activity against Gram-positive and Gram-negative bacteria, and
fungi. The antibacterial activity of the lactoferrin-wool fabric eect was
halved by ve launderings. Lactoferrin has also been attached to wool
by tyrosinase catalysed coupling, imparting signicant bacterial resis-
S.J. McNeil et al.
Fig. 9. Comparison of the activity of amylase immobilised onto dierent bres. Cotton and polypropylene were grafted with HEMA (2-hydroxyethyl methacrylate). The non-pre-treated
HEMA-g-polypropylene had no measurable activity. [152].
tance, i.e. 76% inhibition of Staphylococcus aureus [172].
5.3. Microbes
The immobilisation of microbes onto bres has been the subject of
signicant amounts of research [132,133,173175]. Two of the studies
were undertaken with wool and are reviewed here. In one investigation,
bakers yeast (Saccharomyces cerevisiae) cells were immobilized onto
wool with glutaraldehyde, and investigated for the continuous hydro-
lysis of sucrose [173], see Fig. 11. When used continuously at 70 C
with 2.0 M of sucrose, the immobilised yeasts activity was constant for
30 days, and only decreased by around 50% during a further 30 days of
use.
The immobilisation of microbe-rich sludge on bres such as wool
[174] has been investigated. The ecacy of wool bre in a submerged
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Applied Catalysis A, General 541 (2017) 120140
aerated lter reactor for the tertiary treatment of sewage was compared
to the ecacy of commercial plastic rings. It was found that the wool
bioreactor performed more consistently than the plastic one. The yield
of sludge from the wool bioreactor was almost half that of the plastic
bioreactor, suggesting that the wool was retaining organic and parti-
culate materials. As the wool gradually degraded, it was concluded that
it should be considered as providing additional sacricial adsorption
capacity rather than an alternative medium.
5.4. Summary
A summary of the published studies on wool supported biological
catalysts is shown in Table 6. As a wide range of attachment protocols
have been investigated, these are also included in Table 6.
S.J. McNeil et al.
Fig. 10. Comparison of the activity of catalase immobilised onto dierent materials [166].
6. Wool bres as supports for organocatalysts
Small organic molecules have been investigated as catalysts in
recent years, and are generally referred to as organocatalysts.
Organocatalysts are non-proteinaceous, metal-free, and exhibit
Brnsted-Lowery or Lewis acidic/basic reactivity, or photocatalytic
activity. Thus, their activity, and selectivity are distinct to those of
metallic and biological catalysts [176]. Within the eld of organocata-
lysts, signicant eort has been directed towards their immobilisation
onto solid materials, including textiles [20,57,177183], but only
photo-active organocatalysts appear to have been studied on wool to-
date, see Table 7 [181183].
Some photo-active organocatalysts produce reactive oxygen species
such as singlet oxygen, under the appropriate illumination, and these
compounds were included in a recent review of photo-induced anti-
microbial and decontamination technologies [184]. Some of the most
common sensitizers are methylene blue, rose bengal (4,5,6,7-tetra-
chloro- 2,4,5,7- tetraiodouorescein), porphyrins, and fullerenes (see
Fig. 12). Rose bengal was formerly used commercially as a dye for wool,
and wool treated with rose bengal photocatalises the oxidation of furan
derivatives to compounds of pharmaceutical importance when illumi-
nated with visible light [181,182]. It should however be noted that
furan and its derivatives are some of the most reactive substrates
towards singlet oxygen, so that it should not be assumed that rose
bengal-wool would necessarily oxidise other compounds. The rose
bengal-wool catalyst could be recovered from the reaction mixture
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Applied Catalysis A, General 541 (2017) 120140
and reused at least four times and the authors opined that rose bengal-
wool catalyst represents a practical alternative to soluble rose bengal for
relatively high photostability, recyclability, sensitizing activity, and sustain-
able development [181]. Wool that had been treated with three
anthraquinone acid dye sensitizers showed photo-induced antimicro-
bial activity and photo-induced grafting of vinyl monomers onto the
wool [183].
One published study concerned the immobilisation of non-photo-
active organocatalysts on nylon fabric [57], and this will be discussed
here as it gives some insights into the potential use of wool in this area.
Ultraviolet light was used to attach three types of organocatalysts, at
levels up to 0.025 mmol per gram of nylon (see Fig. 13). The
immobilised organocatalysts were evaluated in three reactions, (I) the
sterically demanding acylation of phenol with isobutyric anhydride, (II)
intramolecular hydroetherication, and (III) alcoholic desymmetrisa-
tion of a cyclic anhydride. The immobilised organocatalysts showed
excellent stability, activity, enantioselectivity and recyclability for the
various reactions. It was found that the loading of catalyst on the nylon
could be controlled by adding the cross-linker pentaerythritol triacry-
late.
There is interest in a type of organocatalyst known as enzyme-
mimics where cofactors are applied to protein [185]. This does not
appear to have been investigated with wool to-date, but organocatalysts
have been applied to reconstituted hair keratin and are discussed in
Section 8. Reconstituted wool has been studied as a support for a photo-
active organocatalyst and this is also discussed in Section 8.
S.J. McNeil et al. Applied Catalysis A, General 541 (2017) 120140

Fig. 11. Immobilisation of bakers yeast onto wool and the hydrolysis of sucrose [173].

Table 7 7. Wool bres as templates for preparing catalysts

Summary of organocatalyst-wool systems that have been studied.
Templating is an eective way of controlling morphology and
Catalyst Attachment Reactant Product Reference(s)
introducing structural complexity during the preparation of catalysts.
Rose bengal Absorption Furans Oxidised [181,182] Often, the template itself is sacriced during the process by chemical or
furans thermal destruction, see Fig. 14. It appears that wool has not been used
Anthraquinone dyes Absorption Live Inactive [183] as a template for catalysts; hence, this section of the review will discuss
microbes microbes
examples of template materials that are analogous to wool, or show
Anthraquinone dyes Absorption Vinyl Vinyl grafted [183]
monomers wool potential to be substituted with wool. Feather keratin and human hair
have been used as templates to produce hollow brous metal oxides,
which may have catalytic properties [186]. Fibrous oxides of cerium,
cobalt, nickel, tin and aluminium were prepared by surface precipita-
tion of metal salts, followed by ltration, then calcination, where the
keratin template was burnt-o. The brous metal oxides produced were

Fig. 12. Examples of photo-active organocatalysts used on wool. From left, methylene blue, rose bengal, porphyrin, and sodium anthraquinone-2-sulphonate.

134
S.J. McNeil et al. Applied Catalysis A, General 541 (2017) 120140

Fig. 13. Examples of the types of organocatalysts applied to nylon bres by Lee et al.[57]. From left to right, Lewis basic, Brnsted-Lowery acidic, and a chiral cinchona sulphonamide.

Fig. 14. Possible use of wool as templates for catalysts.

hollow and porous, exhibiting the surface morphology of the keratin
bre used, such as the barbules of chicken feathers and the scale
structure of hair.
Human hair has been dip-coated with sinterable particles of alumina
to prepare self-supporting materials with micro-channels [187]. A
range of other bres was also used including, nylon, para-aramide,
polypropylene, and polyimide. The thermal behaviour of the template
bres had a large eect on the structure of the nal material, and good
results were achieved with hair.
Cotton bre has been used as both the carbon source and template
for preparing titanium carbide nanowires [188]. The nanowires were
subsequently used as supports for platinum electrocatalysts, which
exhibited a higher electrochemically active surface area, improved
electrocatalytic activity and greater durability, than a commercial
catalyst of platinum supported on carbon. Platinum electrocatalysts
are of signicant interest, as researchers believe that the performance of
these catalysts, with respect to activity and durability, is limiting the
commercialisation of fuel cells [188].
8. Reconstituted wool and other keratins as supports for catalysts
While many studies have concerned the use of wool bres as a
support for catalysts, only ve studies appear to have been published on
using reconstituted wool for supporting catalysts. Hence, three repre-
sentative studies on feather and hair keratin will also be included in the
following discussion. The studies of reconstituted wool supported
catalysts are summarised in Table 8.
Reconstituted wool, that was prepared by reductive dissolution in
urea, followed by dialysis and lyophilisation, was used as a support for
lysozyme enzyme [189]. The activity of the enzyme was assessed by the
hydrolysis of a suspension of Micrococcus lysodeikticus (now known as
Micrococcus luteus) bacteria. It was found that some of the cysteine
residues in keratin contributed to the mechanical strength of the
reconstituted wool, while other cysteine residues remained in the free
form. Attaching the enzyme to the reconstituted wool by disulphide
bonds proved to be less resistant to hydrolysis than attachment by
thioether bonds.
The eectiveness of a photocatalyst in anticancer therapy was
greatly increased by attaching it to nanoparticles of wool keratin
[190]. Chlorin e6, (see Figs. 15 and 16) which produces cytotoxic
reactive oxygen species from molecular oxygen upon irradiation with
white light, was modied by N-hydroxysuccinimide and 1-ethyl-3-(3-
dimethylaminopropyl)carbodiimide, so it could form a covalent bond
with the amino groups of reconstituted wool. Keratin was extracted
from wool by sulphitolysis followed by dialysis. The reconstituted wool
supported chlorin e6 was then converted into nanoparticles by both
self-assembling and desolvation protocols, to give nanoparticles of
around 200 nm diameter. The nanoparticles were then applied to two
lines of tumour cells, and their photodynamic eectiveness determined.
The photoactivity of the chlorin e6 was increased by supporting it on
reconstituted wool, and it killed around 90% of tumour cells, while
being non-toxic in the absence of illumination. Wool keratin was chosen
as the support because of its excellent biocompatibility, low toxicity to
cells and the many options available for attachment of bioactive

Table 8
Summary of reconstituted wool-supported catalyst systems that have been studied.

Catalyst Attachment Reactant Product Reference

Lysozyme Covalent Live bacteria Hydrolysed bacteria [189]

Chlorin e6 Covalent Live tumour cells Dead tumour cells [190]
Photocatalysts (Azure A and a porphyrin) Electrostatic and covalent Live bacteria Inactive bacteria [192]
(glutaraldehyde)
Palladium(II) tetra-sulphophthalocyanine Electrostatic Styrene, bromobenzene Phenylacetylene, Heck coupling product Sonogashira [193]
bromobenzene coupling product
Gold- and silver- doped manganese dioxide Electrostatic Toluene/xylene, oxygen Aromatic aldehydes [194]
Toluene/xylene, aromatic amines Derivatives of
2-arylbenzo[d]thiazole
2-aryl-1H-benzo[d]imidazole 2-aryl-
4-quinazolinone

135
S.J. McNeil et al. Applied Catalysis A, General 541 (2017) 120140

Fig. 15. Catalysts applied to reconstituted wool. Chlorin e6, Azure A and 5,10,15,20-tetrakis [4-(2-N,N,N-trimethylethylthio)-2,3,5,6 tetrauorophenyl]porphyrin tetraiodide salt.

substances that are possible because of to the wide range of amino acids
residues. Putting the chlorin e6 onto keratin increased its transport
across the tumour cell membranes, to give greater accumulation in the
cytoplasm. The researchers suggested that this high uptake was due to
the sulphonated cysteine (SO3) groups of the keratin [190], as these
groups are known to be recognised by the selectin glycoproteins, which
are over expressed in tumour cells [191].
Keratin materials are of growing interest for medical applications,
so it would be benecial to make them more resistant to the growth of
biolms. One approach to preventing biolms is to attach photocata-
lysts which produce reactive oxygen species which inactivate bacteria.
Wool keratin sponges were formed by sulphitolysis and freeze drying,
then two photocatalysts were attached, namely, Azure A and
5,10,15,20-tetrakis [4-(2-N,N,N-trimethylethylthio)-2,3,5,6 tetrauoro-
phenyl]porphyrin tetraiodide salt (see Fig. 15) [192]. Attachment was
via electrostatic attraction and covalent bonding with glutaraldehyde.
Both of the keratin supported photocatalysts were active against Gram-
positive and Gram-negative bacteria, while supporting the growth of
broblast cells.
Graphene oxide is an appealing support for catalysts because it has
high thermal and mechanical stability and can be dispersed in water.
However, its binding of some types of catalysts is very poor. To
overcome this limitation, a group of researchers have used wool protein
to increase the binding of a catalyst to graphene oxide [193]. A solution
of wool protein was prepared by dissolution in mercaptoethanol/1-
butyl-3-methylimidazolium chloride. Graphene oxide nanosheets

Fig. 16. Photochemical destruction of cells by chlorin e6 immobilised onto reconstituted wool [190].

136
S.J. McNeil et al.
(which had been acylated) were treated by the wool protein solution for
12 h then washed and dried. Then the catalyst (palladium(II) tetra-
sulphophthalocyanine) was applied. The resulting catalyst contained
0.86% by mass of palladium, and was evaluated in a series of aqueous
coupling reactions in which yields were as high as 99%. The wool
protein improved catalytic activity and the catalyst was reused ve
times without signicant loss of activity.
Pyrolysed reconstituted wool has been successfully employed as a
support for gold- and silver-doped magnesium dioxide nanoparticles
[194]. Reconstituted wool was prepared by dissolving wool in 1-butyl-
3-methylimidazolium chloride, then precipitating in water. The recon-
stituted wool was then pyrolysed at 500 C in a nitrogen atmosphere,
then ground into a powder in a mortar and pestle. Manganese dioxide
nanoparticles were formed on the pyrolysed wool protein by treatment
in magnesium chloride and potassium permanganate under sonication.
The manganese nanoparticles were then doped with gold or silver by
treatment with soluble salts of the metals. The catalysts prepared
contained 8.0% (by mass) of manganese dioxide and either 0.2% gold
or 0.4% silver [194]. The catalysts were successfully used in two classes
of oxidative reactions. Namely, the oxidation of the primary carbon-
hydrogen bonds of toluene and xylene, and oxidative coupling reactions
toluene and xylene with amines, see Table 8 for details. The dispersion
of the doped manganese nanoparticles across the surface of the
pyrolysed wool protein increased catalytic activity compared to the
unsupported/aggregated form. There was no signicant loss of activity
with four reuses. It was thought that the nitrogen content of the
reconstituted wool contributed to the catalytic activity, basicity and
oxidation stability of the resulting pyrolysis material [195].
Human hair has been dissolved by reduction, to give polypeptides
with an average molecular weight of 4500 Da, which were then
complexed with nicotinamide adenine dinucleotide, a coenzyme found
in all living cells (see Fig. 17) [196]. This complex was shown to
catalyse the oxidation of glutaraldehyde to glyceric acid. In a related
study, this human hair protein was complexed with the coenzyme avin
adenine dinucleotide (see Fig. 17) to catalyse the dehydrogenation of
succinic acid to fumaric acid [197]. The thiol groups in the reduced hair
keratin were thought to stimulate the catalytic activity of the coen-
Fig. 17. Catalysts applied to reconstituted human hair, and feathers. From left, nicotinamide adenine dinucleotide, avin adenine dinucleotide, 1-(2-bromoethyl)-3-carbamoylpyridinium
and 1-propyl-3-chloroformylpyridinium.
137
Applied Catalysis A, General 541 (2017) 120140
zyme. It has been shown that the adenine moiety of the avin adenine
dinucleotide is the site of bonding with the keratin [198]. Reconstituted
human hair keratin has also been used to support the organic catalysts
1-(2-bromoethyl)-3-carbamoylpyridinium bromide and 1-propyl-3-
chloroformylpyridinium bromide (see Fig. 17). These organic catalysts
are model compounds for nicotinamide adenine dinucleotide, and were
covalently bound to the keratin, and shown to eectively reduce N-
methylacridinium and ,,-triuoroacetophenone [199]. These re-
sults demonstrated that modied, non-enzyme protein (i.e. keratin,
modied by organic catalysts) could behave like an enzyme, in this case
oxidoreductase, and that a protein can assist the activity of enzyme
models.
Granules of keratin extracted from feather were used for the
immobilisation of lactase, with glutaraldehyde employed as a cross-
linking agent [200]. The enzyme retained a high level of activity
against lactose during immobilisation, and in a column reactor, the
half-life of the enzyme was between 50 and 100 days. A problem
reported with the granules of keratin was that they formed a gel
containing approximately 90% of water, which slowed the diusion of
reactants and products to and from the enzyme respectively. This
diculty was also discussed in Section 4.1.2 in connection to lipase in
casein gel.
Reconstituted feather keratin that was complexed with palladium
has been shown to be an ecient catalyst for the coupling reactions of
aryl bromides with arylboronic acid in aqueous media under mild
reaction conditions [201]. The biaryl compounds produced were
precipitated from the reaction mixture with yields generally over
90%. The catalyst was recovered from the reaction solution by simple
ltration, and could be reused at least seven times.
9. Conclusions
This review has discussed 87 studies of wool and reconstituted wool
as catalysts and supports for catalysts, see Table 9. Only two of these
studies considered the catalytic properties of wool itself. A wide variety
of catalysts have been applied to wool, i.e. metal complexes, metal
oxides, metallic particles, enzymes, microbes and small organic mole-
S.J. McNeil et al.
Table 9
Types of catalysts studied on wool.
Support/type of catalyst Catalysts
Wool
Wool, oxidised wool
Wool supported catalyst
Metal complex Palladium, platinum, palladium-cobalt, iron-palladium, rhodium, osmium, iron, cobalt, copper, phthalocyanine
complexes
Metallic Manganese dioxide, ferrites(cobalt, manganese, zinc, chromium), iron oxide, gold chloride
particulate
Metallic photocatalysta Titania, zirconia, zinc oxide, palladium, palladium sulphide, cadmium sulphide, iron
Enzymes Glycosidases, lipases, Catalase, Peroxidase, Nariginase, Trypsin, Acid Phosphatase
Lactoferrin Lactoferrin
Microorganism Yeast, sewage sludge
Organic Rose bengal and anthroquinone dyes
Reconstituted wool supported catalysts
Metal complex Palladium(II) tetra-sulphophthalocyanine
Metallic particulate Gold- and silver-doped manganese dioxide
Enzyme Lysozyme
Organic Chlorin e6, Azure A, porphyrin
Total
a
Incomplete with respect to titania, of which there may be up to several hundred.
cules. Wool supported catalysts generally showed good activity,
specicity, durability, and re-usability. Many of these catalysts are
used in processes of commercial signicance.
Wool shares many of the benets of other catalyst supports such as
reducing aggregation of catalysts (particularly nanoparticles) and the
associated loss of activity, facilitating reuse of catalysts and enabling
continuous (as opposed to batch) processing. More specic advantages
include biocompatibility with some catalysed reactions, biodegradabil-
ity, and being readily available and modestly priced. The larger variety
of functional groups present in wool, compared to most other supports,
allows for a wider range of binding mechanisms. The reactivity of wool
has been utilised to prepare catalyst on the bre surface, i.e. reducing
permanganate ions in the synthesis of catalytic manganese dioxide
nanoparticles.
The ability to process wool bre into a range of yarns, fabrics
(knitted, woven and nonwoven) and other structures by existing
equipment is advantageous for practical applications in catalysis.
Wool can be dissolved and reconstituted into solids of various forms,
thus giving further options for supporting catalysts. Wool does have
certain limitations, some of which are shared by other organic polymer
supports, such as susceptibility to damage from heat (above 100 C),
alkalis, reducing agents and oxidising agents. Wool does have excellent
resistance to mild acids and many organic solvents. None of the
common organic textile bres can match the strength, thermal stability
and chemical inertness of glass and steel bres. But from the point of
view of attaching catalyst, chemical inertness is a disadvantage, and
there may be some applications where the high breaking extensions of
organic bres are advantageous, i.e. 35% for wool, 2% for glass bre,
and 8% for steel wire.
Dierent attributes of wool are important to dierent types of
catalysts. For instance, oxidised wool has been shown to be an eective
solid sulphonic acid catalyst. This activity is derived from disulphide
bonds, and these do not occur in other common, non-keratinous bres.
Wool is an eective support for metallic catalysts because it can
complex a wide range of catalytic metal compounds, to give high
loadings and strong attachment. Wool assists metallic photocatalysts by
preventing the recombination of photo-generated electrons and holes.
Wool is a good support for biological catalysts because it is essentially a
protein, with a wide variety of amino acid side-chains, giving it a
similar composition to enzymes, which enhances compatibility and
overall activity. The only type of organocatalysts to have been
investigated on wool to-date are photocatalysts. Reconstituted hair,
modied by organic catalysts, can behave like an enzyme and the thiol
138
Applied Catalysis A, General 541 (2017) 120140
Number of studies reviewed
2
19
5
24
23
4
2
3
1
1
1
2
87a
groups in the hair were thought to stimulate the catalytic activity of the
organic catalyst. Wool possesses signicant levels of thiol/disulphide
groups. Wool represents a low cost, readily processed and easy-to-
modify protein that could be coupled with organic molecules to prepare
synthetic enzymes.
Reconstituted wool is an eective support for enzyme, metal oxide
and organic photo-active catalysts. Reconstituted wool has low toxicity
towards cells, making it a promising support for medical catalysts such
as those used for phototherapy. It is believed that the nitrogen content
of reconstituted wool contributed to the catalytic activity, basicity and
oxidation stability of the resulting pyrolysis material. Fibres of keratin
(hair and feathers) have been used as templates for preparing highly
structured materials that may prove eective as catalysts.
Catalysts have been attached to wool by many chemical and
physical methods. Some metallic catalysts were simply complexed to
wool. Groups in wool such as amines and carboxylic acid, enable
covalent attachment by various protocols, which gives very strong
attachment, while often retaining high levels of catalytic activity.
Enzymes and microbes have been attached by cross-linking, most
frequently with glutaraldehyde, and by the formation of disulphide
and thioether bonds, azoic coupling and formation of Schi bases. In
some studies, the wool was modied to enhance the subsequent
attachment of catalysts by polymer grafting, diazotisation, oxidation,
nitrilation and applying anionic dyes. Catalysts have been entrapped in
materials such as casein gel on the surface of wool bres, but the loss of
catalysts by diusion, and the high mass transfer resistance observed,
are signicant disadvantages of this approach.
10. Future prospects
This review has shown the wide breadth of research that has been
undertaken on wool catalysts and wool-supported catalysts. There is a
need for studies that directly compare the performances of dierent
support materials, that use catalyst application methods optimised for
each support, and the same determination of catalytic performance.
One of the most exciting applications of wool in this area is
sulphonic acid catalysts, as this is an emerging area of research and
wool only requires a simple, environmentally sustainable, modication
to produce a high level of sulphonic acid groups. Another exciting
application is the supporting and activating of organic molecules to
prepare synthetic enzymes. This is appealing as it utilises the fact that
both wool and enzymes are largely proteins.
Wool does not appear to have been studied as a template to-date,
S.J. McNeil et al.
but there is no apparent reason why it would not be suitable, and it
warrants investigation. Another application where wool has yet to be
investigated is the supporting of ionic liquid catalysts. Fibres such as
polypropylene have shown good performance in ionic liquid catalysts,
and it is reasonable to speculate that the surface properties of wool are
likely to be compatible with some types of ionic liquids.
Future research should build on the strengths of wool, while being
mindful of its limitations, to make it a useful catalyst/catalyst support
for niche applications, thereby expanding the range of catalysts
available to end-users.
Acknowledgements
This work was funded by AgResearch core funding from the New
Zealand Government Ministry of Business, Innovation and
Employment.
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