Professional Documents
Culture Documents
CONTENTS
CONSIDERATIONS 18
1.7 REFERENCES 22
1
1.1 The Perspective
Dyes may be defined as substances that, when applied to a substrate provides co-
lour by a process that alters, at least temporarily, any crystal structure of the coloured
substances. Such substances with considerable colouring capacity are widely employed
in the textile, pharmaceutical, food, cosmetics, plastics, photographic and paper indus-
tries. The dyes can adhere to compatible surfaces by solution, by forming covalent bond
Dyes generally have rather complicated structures which are made by reactions involv-
ing building blocks known as intermediates [1, 2]. Most of these are aromatic com-
pounds with substituent groups such as –NH2, -OH, -NO2 and –SO3H which alter the reac-
tivity of the cyclic compound and sometimes the color of the dye. Both inorganic and or-
ganic materials are needed to make dyes and intermediates, but the backbone of the
raw-material sequence is
Dyes add value to products far beyond their cost. Frequently the color of a product
is the reason for its sale. Some dyes have special uses, such as radiation detectors and
photosensitive product to his customer. Dyes sales in 1980 were estimated at $608 mil-
Chapter 1 Introduction And Objectives
lion. Every dye sale is estimated to influence $10 in product sales, so the effect is far
greater than the cost. Typical dye molecules appear complicated and confusing, but their
synthesis follows an orderly procedure, using about 1000 intermediates and compara-
tively few chemical conversions. A dye must be colored, but it must also be able to im-
part color to something else on a reasonably permanent basis before it can be consi-
2
dered as a dye. Most dyes contain considerable unsaturation, and some part of the dye is
usually in the form of aromatic rings with nitrogen unsaturation of several types com-
mon to many dyes, for example the quinoid structure which appears frequently. Many
correlations have been made and more attempted between chemical structure and color.
The term dyes and intermediates refers to those compounds which are prepared
from the original coal tar constituents by various chemical procedures and which, in
turn, can be converted into commercial dyes by relatively simple further transforma-
tions. A typical example is aniline, which is prepared from benzene in various ways, and
which can be converted into numerous dyes. The reactions used in the preparation of
intermediates are, for the most part, simple operations. Frequently, they proceed quanti-
tatively according to the rules of stoichiometry. In other cases, side reactions are en-
countered which complicate the reaction and greatly reduce the yield. It is one of the
important tasks of the dye chemist to study these undesirable side reactions sufficiently
to understand their nature and then, if possible, to select the reaction conditions which
will favor only the main reaction leading to the desired intermediate. This end is not al-
ways attained, because often the set of conditions which will eliminate the side reactions
is not known, but the chemist must always bear in mind the possibility of achieving
Chapter 1 Introduction And Objectives
acid (H-acid) illustrates this point. This compound has been known for nearly fifty years
and is still being studied extensively in many laboratories, yet to this day has not been
prepared in satisfactory yield. In many cases, so-called quantitative yields are obtained
but the product is not a pure compound. Thus, the reaction yields the calculated quantity
3
of product, but this is a mixture of isomeric or analogous compounds which must be se-
parated by some type of physical method. The isomeric nitrotoluenes (ortho, meta, and
para), for example, are always obtained in mixture, and special methods have had to be
evolved to separate the pure individuals economically. Sometimes a circuitous route can
directly from β-naphthylamine, but can be prepared under the proper conditions from
β-naphthol. As mentioned, the basic operations of dye chemistry utilize simple chemical
and, in these cases, careful calculations must be made to determine which procedure is
most advantageous. The least expensive process is often not necessarily the best when
other factors are taken into account. For example, the question of apparatus may enter,
for the process if a small quantity of the material is to be produced. Furthermore, con-
These often cannot be used at all (e.g. primuline), but may be valuable or even in-
are carried out must always be considered. Unlike preparations done in the laboratory,
those in the plant cannot be carried out in glass equipment except in unusual cases. Fur-
thermore, it must be remembered that the chemicals often attack the apparatus, so it’s
4
The first synthetic dye, Mauveine, was discovered by Perkin in 1856. Since then
stream of new products because of the quickly changing world in which we live. The ear-
ly dyes industry saw the discovery of the principal dye chromogens (the basic arrange-
ment of atoms responsible for the color of a dye). Indeed, apart from one or two notable
exceptions, all the dyes used today were discovered in the 1800s. The introduction of
the synthetic fibers nylon, polyester, and polyacrylonitrile during the period 1930-1950,
produced the next significant challenge. The discovery of reactive dyes in 1954 and their
commercial launch in 1956 heralded a major breakthrough in the dyeing of cottons; in-
tensive research into reactive dyes followed over the next two decades and, indeed, is
still continuing today. The oil crisis in the early 1970s, which resulted in a steep increase
in the prices of raw materials for dyes, created a drive for more cost-effective dyes, both
heterocyclic azo and benzodifuranone. These themes are still important and ongoing, as
are the current themes of product safety, quality, and protection of the environment.
There is also considerable activity in dyes for high-tech applications, especially in the
The scale and growth of the dyes industry has been inextricably linked to that of
the textile industry. World textile production has grown steadily to an estimated 45 ×
106 t in 2000. The two most important textile fibers are cotton, the largest and polyester.
Consequently, dye manufacturers tend to concentrate their efforts on producing dyes for
these two fibers. The estimated world production of dyes in 2000 was 2.0 × 10 6 t [4].
5
Synthetic dyes are extensively used in many fields of up to-date technology, e.g., in vari-
ous branches of the textile industry, of the leather tanning industry in paper production,
chemical cells, and in hair colorings [6-10]. Moreover, synthetic dyes have been em-
ployed for the control of the efficacy of sewage and wastewater treatment, for the de-
termination of specific surface area of activated sludge for ground water tracing, etc [11,
12]. Synthetic dyes exhibit considerable structural diversity. The chemical classes of
dyes employed more frequently on industrial scale are the azo, anthraquinone, sulfur,
emphasized that the overwhelming majority of synthetic dyes currently used in the in-
dustry are azo derivatives. It should be noted that azo-keto hydrazone equilibria can be
a vital factor in the easy breakdown of many of the azo dye system [13].
Basis for colour Unlike most organic compounds, dyes possess colour due to four basic
least one chromophore (colour-bearing group), 3) have a conjugated system, i.e. a struc-
ture with alternating double and single bonds, and 4) exhibit resonance of electrons,
Chapter 1 Introduction And Objectives
which is a stabilizing force in organic compounds [1]. When any one of these features is
lacking from the molecular structure the colour is lost. In addition to chromophores,
most dyes also contain groups known as auxochromes (colour helpers), examples of
which are carboxylic acids, sulfonic acid, amino, and hydroxyl groups. While these are
not responsible for colour, their presence can shift the colour of a colourant and they are
6
most often used to influence dye solubility. Table 1.1 shows the relationships between
Other factors like chromophoric groups, conjugated systems and resonance, which con-
tribute to colour are illustrated in Figure 1.1. The structures in Figure 1.1b demon-
system. This is shown in Figure 1.2, where it can be seen that placement of an azo group
7
Figure 1.1 (a) Chromophoric groups present in organic dyes, (b) conjugated sys-
tems in vitamin A and β-carotene and (c) resonance structures for malachite
green.
It is evident that doubling the length of the conjugated system in Vitamin A to give
providing target colours. This is illustrated in Figure 1.3, where the following effects of
8
• Adding groups of increasing electron-donating ability to the azobenzene structure
tion provide a bathochromic effect. In this regard, nitro groups are especially bene-
classes, viz. dyes and pigments [2]. The key distinction is that dyes are soluble in water
and/or an organic solvent, while pigments are insoluble in both types of liquid media.
Chapter 1 Introduction And Objectives
Dyes are used to colour substrates to which they have affinity. Pigments can be used to
colour any polymeric substrate but by a mechanism quite different from that of dyes, in
that surface only colouration is involved unless the pigment is mixed with the polymer
9
1.2.2 Considerations in the Design of Dyes
Dye-substrate Affinity Dyes containing one or more azo groups (i.e. azo dyes) com-
prise by far the largest family of organic dyes. Prominent types are 1) acid dyes for poly-
amide and protein substrates such as nylon, wool, and silk; 2) disperse dyes for hydro-
phobic substrates such as polyester and acetate, and 3) direct and reactive dyes for cel-
lulosic substrates such as cotton, rayon, linen, and paper. Generally, the synthesis of azo
dyes involves two steps. Step 1 is the conversion of an aromatic amine to a diazo com-
pound (i.e. Ar-NH2, Ar-N2+), a process known as diazotization, and step 2 is the reaction
of the diazo compound with a phenol, naphthol, aromatic amine, or a compound that has
an active methylene group, to produce the corresponding azo dye, a process known as
diazo coupling (e.g. Ar-N2+ + Ar’-OH Ar-N=N-Ar’-OH). This process is suitable for forming
both azo dyes and pigments. Typical structures of colourants that fall into the two
groups are shown in Figure 1.4. Since the effectiveness of a dyeing or printing process
often hinges on the affinity between the dye and substrate, dyes are designed with a
specific substrate. In this regard, dyes must be designed that have a) greater affinity for
the substrate than the medium (usually water) from which it is applied and b) a high de-
gree of permanence under end-use conditions (e.g. stability to fading upon exposures to
water (wet fast) and/or sunlight (light fast)). The availability of colourants for a specific
Chapter 1 Introduction And Objectives
substrate type is the result of a deliberate molecular design process that takes the target
10
Figure 1.4 Some commercial azo dyes and pigments.
cation method. The former approach is adopted by practicing dye chemists, who use
terms such as azo dyes, anthraquinone dyes, and phthalocyanine dyes. The latter ap-
proach is used predominantly by the dye user, the dye technologists, who considers
reactive dyes for cotton and disperse dyes for polyester. Very often, both terminologies
are used, for example, an azo disperse dye for polyester and a phthalocyanine reactive
This system for the classification of dyes is by chemical structure, which has two advan-
tages, first, it readily identifies dyes as belonging to a group that has characteristic prop-
erties, for example, azo dyes (strong, good all-round properties, cost-effective) and anth-
11
raquinones dyes (weak, expensive) and second, there are a few (about a dozen) chemi-
our Index (CI) [16]. Because the most important textile fibers are cotton and polyester,
majority of the dye types are those which are used for dyeing these two fibers, including
polyester-cotton blends. Other textile fibers include nylon, polyacrylonitrile, and cellu-
lose acetate.
Reactive Dyes These dyes form a covalent bond with the fiber, usually cotton, although
they are used to a small extent on wool and nylon. This class of dyes, first introduced
commercially in 1956 by ICI, made it possible to achieve extremely high wash fastness
over direct dyes is that their chemical structures are much simpler, their absorption
spectra show narrower absorption bands, and the dyeings are brighter. The principal
chemical classes of reactive dyes are azo (including metallized azo), triphendioxazine,
Disperse Dyes These are substantially water-insoluble nonionic dyes for application to
hydrophobic fibers from aqueous dispersion. They are used predominantly on polyester
Chapter 1 Introduction And Objectives
and to a lesser extent on nylon, cellulose, cellulose acetate, and acrylic fibers.
Direct Dyes These water-soluble anionic dyes, when dyed from aqueous solution in the
presence of electrolytes, are substantive to, i.e., have high affinities for, cellulosic fibers.
Their principal use is the dyeing of cotton and regenerated cellulose, paper, leather, and,
to a lesser extent, nylon. Most of the dyes in this class are polyazo compounds, along
12
with some stilbenes, phthalocyanines, and oxazines. After treatments, frequently applied
to the dyed material to improve wash fastness properties, include chelation with salts of
dye-complexing resin.
Vat Dyes These water-insoluble dyes are applied mainly to cellulosic fibers as soluble
leuco salts after reduction in an alkaline bath, usually with sodium hydrogensulfite. Fol-
lowing exhaustion onto the fiber, the leuco forms are reoxidized to the insoluble keto
forms and after treated, usually by soaping, to redevelop the crystal structure. The prin-
Sulfur Dyes These dyes are applied to cotton from an alkaline reducing bath with so-
dium sulfide as the reducing agent. Numerically this is a relatively small group of dyes.
The low cost and good wash fastness properties of the dyeing make this class important
Cationic (Basic) Dyes These water-soluble cationic dyes are applied to paper, polyacry-
lonitrile (e.g. Dralon), modified nylons, and modified polyesters. Their original use was
for silk, wool, and tannin-mordanted cotton when brightness of shade was more impor-
tant than fastness to light and washing. Basic dyes are water-soluble and yield colored
cations in solution. For this reason they are frequently referred to as cationic dyes. The
Chapter 1 Introduction And Objectives
Acid Dyes These water-soluble anionic dyes are applied to nylon, wool, silk, and modi-
fied acrylics. They are also used to some extent for paper, leather, ink-jet printing, food,
and cosmetics.
13
Solvent Dyes These water-insoluble but solvent-soluble dyes are devoid of polar solubi-
lizing groups such as sulfonic acid, carboxylic acid, or quaternary ammonium. They are
used for coloring plastics, gasoline, oils, and waxes. The dyes are predominantly azo and
anthraquinone, but phthalocyanine and triarylmethane dyes are also used. The classifi-
14
padded on cloth and
baked on or
thermofixed
Oxidation hair, fur, and aromatic amines and aniline black and
bases cotton phenols oxidized on the indeterminate
substrate structures
Reactive cotton, wool, silk, reactive site on dye re- azo, anthraquinone,
and nylon acts with functional phthalocyanine,
group on fiber to bind formazan, oxazine, and
dye covalently under basic
influence of heat and pH
(alkaline)
Solvent plastics, gasoline, dissolution in the azo, triphenylmethane,
varnishes, lacquers, substrate anthraquinone,
stains, inks, fats, and phthalocyanine
oils, and waxes
containing products on
fiber
15
1.4 Equipment and Manufacture
There are usually several reaction steps or unit processes. The basic steps of dye
The reactor itself, in which the unit processes to produce the intermediates and
dyes are carried out, is usually the focal point of the plant [4]. Operations subsequent to
reaction are often referred to as workup stages. These vary from product to product,
whereby intermediates (used without drying wherever practical) require less finishing
operations than colorants. The reactions for the production of intermediates and dyes
are carried out in bomb-shaped reaction vessels made from cast iron, stainless steel, or
steel lined with rubber, glass (enamel), brick, or carbon blocks. These vessels have ca-
pacities of 2-40 m3 (app. 500-10,000 gallons) and are equipped with mechanical agita-
Chapter 1 Introduction And Objectives
on the nature of the operation. Jackets or coils are used for heating and cooling by circu-
lation of high-boiling fluids (e.g. hot oil or Dowtherm), steam, or hot water to raise the
temperature, and air, cold water, or chilled brine to lower it. Unjacketed vessels are of-
ten used for reactions in aqueous solutions in which heating is effected by direct intro-
16
duction of steam, and cooling by addition of ice or by heat exchangers. The reaction ves-
sels normally span two or more floors in a plant to facilitate ease of operation. Products
are transferred from one piece of equipment to another by gravity flow, pumping, or
blowing with air or inert gas. Solid products are separated from liquids in centrifuges, in
filter boxes, on continuous belt filters, and, perhaps most frequently, in various designs
of plate-and-frame or recessed-plate filter presses. The presses are dressed with cloths
of cotton, Dynel, polypropylene, etc. The plates and frames are made of wood, cast iron,
When possible, the intermediates are used for the subsequent manufacture of
other intermediates or dyes without drying because of saving in energy costs and han-
dling losses. This trend is also apparent with dyes. The use of membrane technology
with techniques such as reverse osmosis to provide pure, usually aqueous, solutions of
dyes has become much more prevalent. Dyes produced and sold as liquids are safer and
easier to handle and save energy costs. However, in some cases products, usually in the
form of pastes discharged from a filter, must be dried. Even with optimization of physi-
cal form, the water content of pastes varies from product to product in the range of 20-
80 %. Where drying is required, air or vacuum ovens (in which the product is spread on
trays), rotary dryers, spray dryers, or less frequently drum dryers (flakers) are used.
Chapter 1 Introduction And Objectives
Spray dryers have become increasingly important. They require little labour and accom-
plish rapid drying by blowing concentrated slurries (e.g. reaction masses) through a
small orifice into a large volume of hot air. Dyes, especially disperse dyes, that require
wet grinding as the penultimate step are now often dried this way. In this case their final
standardization, i.e., addition of desired amounts of auxiliary agents and solid diluents, is
17
performed in the same operation. The final stage in dye manufacture is grinding or mill-
ing. Dry grinding is usually carried out in impact mills. Dry grinding is an inevitable con-
sequence of oven drying, but more modern methods of drying, especially continuous
drying, allow the production of materials that do not require a final stage. The ball mill
has been superseded by sand or bead mills, while wet millings have become increasingly
unless they pose little health risk under end-use conditions. Consequently, environ-
mental safety is an essential consideration in molecular design. In this regard, the raw
materials employed in the manufacture of synthetic dyes should not involve compounds
known to pose health risks. This would include a large group of aromatic amines [17]
that are either cancer-suspect agents or established mutagens in the standard Salmo-
nella mutagenicity assay [18]. It is clear, therefore, that dye design must take into con-
systems. In the case of azo dyes, the enzyme-mediated formation of genotoxic aromatic
amines as metabolites must be considered, since it is possible that the intact dye is safe
but not all of its metabolites. For instance, the use of Direct Red 28, an azo dye (Figure
Chapter 1 Introduction And Objectives
1.6) could lead to the formation of the bladder carcinogen benzidine if this dye were
Due to large-scale production and extensive application, synthetic dyes can cause
considerable environmental pollution and are serious health-risk factors. Although, the
18
development of ecofriendly technologies, reduced consumption of freshwater and lower
output of wastewater, the release of important amounts of synthetic dyes to the envi-
ronment causes public concern, legislation problems and is a serious challenge to envi-
ronmental scientists [19, 20]. Because of their commercial importance, the impact and
toxicity of dyes that are released in the environment have been extensively studied [21].
As several thousand different synthetic dyes that are employed exhibit various
in the environment and health hazards involved in their use is still incomplete. Tradi-
handling wastewater of synthetic textile dyes because of the chemical stability of these
pollutants. A wide range of methods has been developed for the removal of synthetic
dyes from waters and wastewaters to decrease their impact on the environment. The
19
tion, etc. [22]. The efficacy of the various methods of dye removal, such as chemical pre-
cipitation, chemical oxidation, and adsorption along with their effects on subsequent
biological treatment is also reported [23]. Chemical oxidation was very effective but the
Surveys in recent years have indicated that the textile industry is contributing in-
creasingly to the declining environment. Due to the use of strong chemicals like, strong
acids and alkalis, solvents, heavy metal catalysts, toxic amines and high temperatures,
these dyes are not fit to be released in the environment. However, as these chemicals
and dyes are used intrinsically in various processes in the textile industry, there is in-
creased land and water degradation. This causes a serious threat to the surroundings.
This also constantly forces the industry to increase its efforts on improving processes
The biggest contributors to the pollution from textile industry are the dyeing and
finishing processes. The main problem or difficulty encountered with treating these
dyestuffs is that these are highly complex structures and hence not easily bio-
degradable. So it becomes difficult to separate them from the waste water released into
the water bodies [27, 28]. Approximately 2 % of dyes produced annually and discharged
into effluent are from manufacturing operations while 10 % of dyes are discharged in
Chapter 1 Introduction And Objectives
effluents from textile and associated industries [29]. Various efforts have been made in
the direction of synthesizing new types of dyes molecules and waste water treatment so
as to reduce the level of water pollution resulted in due to this industry out of which few
have been successful viz. coagulation/flocculation, reverse osmosis techniques, and acti-
20
vated carbon absorption [30]. However, these methods result in transferring the conta-
minants from one phase to the other while leaving the problem as it is [31].
gen bonds, which results in forming of toxic, carcinogenic compounds due to the afore-
mentioned biological degradation [32-34], though one can regain the color by making
contact of oxygen with the anaerobic degradation products [35]. Color removal is re-
stricted in big amounts by these problems using bacteria. Photocatalysis is one of the
[36, 37]. TiO2 is being increasingly used and can be used in the development of a useful
process for reducing water pollution caused by dyeing compounds due to their efficien-
cy in the mineralization and the mild conditions required. In addition, it can oxidize
most of the organic contaminants to CO2 and H2O [38, 39]. It is common and well known
that in order to decrease water pollution, the fixation levels of reactive dyes need to be
increased. The main reactive system for cellulose has been firmly established as the
chlorotrazinyl and vinylsulphone groups. Due of this, reactive dyes with more than one
reactive group in the dye molecule have been the subject of continuous investigations.
Classification of reactive groups is done on the basis of the number of reactive groups
contained in the dye molecule, as mono-, bi- and poly-functional reactive systems [40].
Chapter 1 Introduction And Objectives
Such dye properties can be achieved by appropriately modifying the molecular structure
of the dye.
21
1.6 Aim and Scope of the Work
1. To synthesize new modified reactive dyes with 3-sulphonyl 4-amino phenyl beta
hydroxy ethyl sulphone sulphate ester (sulfo para vinyl sulfone) reactive group.
4. To evaluate the exhaustion and fixation values of newly synthesized dyes and to
5. Explore the efficiency of TiO2 for development of process efficient and as cost effi-
cient material to promote sufficient waste water treatment with the synthesized
dyes.
1.7
1.7 References
[1] E.N. Abrahat in, Dye and their Intermediates, Chemical Publishing, New York,
[2] R.L.M. Allen in, Colour Chemistry, Thomas Nelson and Sons Lt., London, 1971,
Chapter 1 Introduction And Objectives
pp. 11-13.
Verlag GmbH and Co., Weinheim, Germany, 2003, Chapter 1, pp. 1-12.
22
[5] P. Gregory in, The Chemistry and Applications of Dyes, D.R. Waring, G. Hallas
[6] J. Sokolowska-Gajda, H.S. Freeman, A. Reife, Dyes Pigm. 1996, 30, 1–20.
[7] I. Kabadasil, O. Tunay, D. Orhon, Water Sci. Technol. 1999, 40, 261– 7.
95, 163– 8.
[9] D. Wrobel, A. Boguta, R.M. Ion, J. Photochem. Photobiol. A Chem. 2001, 138, 7 –
22.
[10] C. Scarpi, F. Ninci, M. Centini, C. Anselmi, J. Chromatogr. A 1998, 796, 319– 25.
[11] B.L. Sorensen, R.J. Wakeman, Water Res. 1996, 30, 115– 21.
[12] D. Orhon, S. Sozen, E. Gorgun, E. Cokgor, N. Artan, Water Sci. Technol. 1999, 39,
177– 84.
[13] E. Forgacs, T. Cserhati, G. Oros, Environ. Int, 2004, 30, 953– 971.
[14] IARC Monograph on, Some Aromatic Amines, Organic Dyes, and Related Expo-
[15] J.R. Aspland, Textile Dyeing and Colouration, Association of Textile Chemists and
[16] Colour Index, 3rd ed., Volume 4, The Society of Dyers and Colourists, Bradford,
UK, 1971.
Chapter 1 Introduction And Objectives
[17] Anon. ‘Ecological and Toxicological Association of Dyes and Pigments Manufac-
turers’, Textile Chemists and Colorist, “German Ban of Use of Certain Azo Com-
pounds in Some Consumer Goods: ETAD Information Notice No. 6”, 1996,
23
[18] D.M. Maron, B.N. Ames, Mutat. Res, 1983, 113, 173–215.
[21] C.C.I. Guaratini, M.V.B. Zanoni, Quim. Nova 2000, 23, 71–8.
[22] O.J. Hao, H. Kim, P.C. Chiang, Crit. Rev. Environ. Sci. Technol. 2000, 30, 449– 502.
[23] O. Tunay, I. Kabdasli, G. Eremektar, D. Orhon, Water Sci. Technol. 1996, 34, 9–16.
[25] S.M. Fergusson, Master’s Thesis, Diploma Textile Industries, RMIT University,
Leeds, 2008.
[26] A. Al-Kdasi, A. Idris, K. Saed, C.T. Guan. Global Nest Int. J. 2004, 6, 222-230.
[28] J.Z. Liu, T. L. Wang, T. L. Ji. J. Mol. Catal. B: Enzym. 2006, 41, 81-86.
[31] C V. Philippe, B. Roberto, V. Willy, J. Chem. Tech. Bio. Technol. 1998, 72, 289-302.
[32] M. A. Brown, S. C. Devito, Crit. Rev. Environ. Sci. Technol, 1993, 23, 249-324.
[36] S. Dai, W. Song, T. Li, Y. Zhuang, Adv. Environ. Sci. 1996, 4, 1–9.
24
[37] M. H. Perez, G. Penuela, M. I. Maldonado, O. Malato, P. F. Ibanez, I. Oller, W. Gern-
[38] M. Abu Tariq, M. Faisal, M. Saquib, M. Muneer. Dyes Pigm. 2008, 76, 358–365.
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