METHOD FOR MODIFYING A YARN OR TEXTILE FABRIC

Abstract

The present invention relates to a method for modifying a textile yarn or fabric by immobilising a cyclodextrin derivative on said yarn or fabric, said process comprising a step (a) of contacting said textile yarn or fabric with said cyclodextrin derivative and with a bridging agent such as 1,2,3,4-butanetetracarboxylic acid, optionally in the presence of a catalyst such as cyanamide,

to obtain a textile yarn or fabric on which the cyclodextrin derivative of formula (I) is immobilised.

Claims

1. A method for modifying a textile yarn or textile fabric by immobilising on said yarn or fabric a cyclodextrin derivative comprising a group reactive towards organophosphorus agents, said cyclodextrin derivative having the following formula (I): ##STR00011## in which: n is 1, 2 or 3; Y is a linker selected from the following groups: —O—(CH.sub.2).sub.m—, m being 1, 2, or 3, preferably 1 or 3; ##STR00012## —NH—C(═O)—(CH.sub.2).sub.p—, p being 0, 1, or 2, preferably 0 or 2; —CONH—(CH.sub.2).sub.q—, q being 1, 2, or 3, preferably 1 or 3; —C(═O)O—(CH.sub.2).sub.r—, r being 1, 2, or 3, preferably 1 or 3; —OC(═O)—(CH.sub.2).sub.s—, s being 0, 1, or 2, preferably 0 or 2; —O—CH.sub.2—C≡C—(CH.sub.2).sub.t—, t being 1, 2, or 3, preferably 1 or 3; Nu has the following formula (II): ##STR00013## in which: either R is COOH and X is C—I═O, or R is CH═N—OH and X is N or N.sup.+—(C.sub.1-C.sub.6)alkyl, or R is CO—NH—OH and X is N, said method comprising a step (a) of contacting said textile yarn or fabric with the cyclodextrin derivative of formula (I) and with a bridging agent selected from the group consisting of 1,2,3,4-butanetetracarboxylic acid, succinic acid, citric acid, oxalic acid and mixtures thereof, optionally in the presence of a catalyst or coupling agent selected from the group consisting of cyanamide, N,N,N′,N′-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, O(N-succinimidyl)-1,1,3,3-tetramethyluronium tetrafluoroborate (TSTU), O-(5-norbornene-2,3-dicarboximido)-N,N,N′,N′-tetramethyluroniumtetrafluoroborate (TNTU) and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, to obtain a textile yarn or fabric on which the cyclodextrin derivative of formula (I) is immobilised.

2. The method according to claim 1, wherein step (a) is carried out in the presence of a catalyst or coupling agent selected from the group consisting of cyanamide, N,N,N′,N′-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, O[N-succinimidyl)-1,1,3,3-tetramethyluronium tetrafluoroborate (TSTU), O-(5-norbornene-2,3-dicarboximido)-N,N,N′,N′-tetramethyluroniumtetrafluoroborate (TNTU) and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride.

3. The method according to claim 1, wherein the bridging agent is 1,2,3,4-butanetetracarboxylic acid and wherein the catalyst is cyanamide.

4. The method according to claim 1, wherein the cyclodextrin derivative fulfils the following formula (IV): ##STR00014##

5. The method according to claim 1, wherein the textile fabric is a fabric whose textile is selected from the group consisting of synthetic fibres or natural or artificial cellulosic fibres, alone or in a blend, and is in particular selected from the group consisting of cotton, linen, hemp, viscose, cellulose acetate, polyvinyl alcohol, and acrylic.

6. The method according to claim 1, wherein step (a) is carried out at a temperature below 130° C., and preferably for a time between 1 and 20 minutes.

7. The method according to claim 1, further comprising, after step (a), a step (b) of rinsing the textile fabric on which the cyclodextrin derivative of formula (I) is immobilised, said step (b) preferably being carried out at a temperature of less than 40° C., for a period of less than 90 minutes, in particular by soaking the textile fabric in an aqueous solution whose pH is between 5.5 and 7.65.

8. A modified textile fabric on which is immobilised a cyclodextrin derivative of the following formula (I): ##STR00015## in which: n is 1, 2 or 3; Y is a linker selected from the following groups: —O—(CH.sub.2).sub.m—, m being 1, 2, or 3, preferably 1 or 3; ##STR00016## —NH—C(═O)—(CH.sub.2).sub.p—, p being 0, 1, or 2, preferably 0 or 2; —CONH—(CH.sub.2).sub.q—, q being 1, 2, or 3, preferably 1 or 3; —C(═O)O—(CH.sub.2).sub.r—, r being 1, 2, or 3, preferably 1 or 3; —OC(═O)—(CH.sub.2).sub.s—, s being 0, 1, or 2, preferably 0 or 2; —O—CH.sub.2—C≡C—(CH.sub.2).sub.t—, t being 1, 2, or 3, preferably 1 or 3; Nu has the following formula (II): ##STR00017## in which: either R is COOH and X is C—I═O, or R is CH═N—OH and X is N or N.sup.+—(C.sub.1-C.sub.6)alkyl, or R is CO—NH—OH and X is N.

9. A modified textile fabric obtained by the method according to claim 1.

10. Use of a modified textile fabric according to claim 8 for the trapping and degradation of organophosphorus nerve agents.

11. Use of a modified textile fabric according to claim 8 as a self-decontaminating textile.

Description

DESCRIPTION OF THE FIGURES

[0064] FIG. 1 shows the SEM images of different fabric samples (untreated, treated and unrinsed, treated and rinsed).

[0065] FIG. 2 shows the hydrolysis of paraoxon to para-nitrophenol.

[0066] FIG. 3 shows the recyclability tests.

[0067] FIGS. 4 and 5 show the efficiency results of Example 6. FIG. 4 shows the results for rinsing at pH=7.65 and FIG. 5 shows the results for rinsing at pH=5.5.

[0068] FIGS. 6 and 7 show the efficiency results of Example 7. FIG. 6 shows the results for rinsing at pH=7.65 and FIG. 7 shows the results for rinsing at pH=5.5.

EXAMPLES

Example 1: Preparation of the Modified Textile Fabric

[0069] 1. Immobilisation of Cyclodextrin Derivative

[0070] The immobilisation of the cyclodextrin derivative of formula (1) below:

##STR00007##

was achieved on cotton by using a bridging agent, 1,2,3,4-butanetetracarboxylic acid (BTCA), to crosslink the oligosaccharide units of the scavenger (1) and graft them onto the textile substrate.

[0071] The textile substrate (cotton, size 5×5 cm, i.e. 225 cm.sup.2) was immersed for 2 minutes in a bath containing β-cyclodextrin derivative (1) (10%), 1,2,3,4-butanetetracarboxylic acid (BTCA, 6%), cyanamide (5%) and ammonium biphosphate (ADHP, 1%).

[0072] Derivative (1) was prepared by the company Provepharm.

[0073] BTCA, cyanamide, and ADPH were supplied by Sigma-Aldrich.

[0074] After fulling at a pressure of 1.5 bar, the impregnated fabric was pre-dried for 30 minutes at 80° C. Fixation was carried out at 120° C. for 10 minutes.

[0075] 2. Rinsing Protocol

[0076] A rinsing protocol was developed to allow the removal of excess derivative (1) and residual reagents used for immobilisation, avoiding excessive detachment of the immobilised derivative (1) from the substrate.

[0077] The fabric was rinsed by soaking in 200 mL of 20 mM phosphate buffer solution at pH 7.65 for 15 minutes at room temperature without shaking. The rate of immobilisation deposited after rinsing was estimated to be 6.7 g-m-2 by determining the mass gain of the fabric sample.

[0078] 3. Strength of the Derivative Lock-In (1)

[0079] Samples were analysed by scanning electron microscopy (SEM) combined with energy-dispersive X-ray (EDX) microanalysis in order to reveal the presence of the element iodine (and therefore the derivative (1)).

[0080] Four fabric samples were analysed: [0081] Control (untreated) fabric (Sample I) [0082] Treated, unrinsed fabric (Sample II) [0083] Treated, rinsed fabric (Sample III) [0084] Fabric treated, rinsed and rub-aged according to the Crokmeter* manual test (Sample IV) *The device is equipped with a 16 mm-diameter pin that moves back and forth straight along a length of 104 mm with a downward force of 9N (Ref.: Standard EN NF ISO 105-X12:2016).

[0085] The following results are obtained as shown in Table 1 below:

TABLE-US-00001 Iodine (%) Sample I — Sample II 1.22 Sample III 0.92 Sample IV 0.88

[0086] The SEM images obtained are shown in FIG. 1.

[0087] SEM-EDX microscopy of the sample allows the detection of the element iodine in samples II, III and IV, thus proving the presence of the derivative (1) immobilised on the substrate. This element is always detected after rinsing, and after the rub test. The fact that no sample mass was lost before or after the Crokemeter test further demonstrated that the immobilisation of derivative (1) is both resistant to rinsing and to rubbing of the support.

Example 2: Efficiency of the Modified Textile

[0088] Evaluation of the Activity of the Treated Fabric on the Degradation of Methyl-Paraoxon

[0089] 2 samples of a size of 5×5 cm were assembled and sewn.

[0090] The resulting assembly was used in the rest of the protocol.

[0091] Sodium hydrogen phosphate, phosphoric acid, cetyltrimethylammonium chloride and methyl-paraoxon were supplied by Sigma-Aldrich.

[0092] (1) A 20 mM phosphate buffer solution at pH 7.65 was prepared by dissolving 1.42 g of anhydrous sodium hydrogen phosphate in 500 mL of milliQ® water. The pH was adjusted to 7.65 by adding a phosphoric acid solution and checked with a pH meter.

[0093] (2) A 13 mM cetyltrimethylammonium chloride solution was obtained by dissolving 416 mg of the product in 97 mL of the buffer prepared in (1) and 3 mL of dimethylsulphoxide.

[0094] (3) A 16.67 mM methyl-paraoxon solution was obtained by dissolving 41.2 mg of the product in 10 mL of anhydrous methanol. This solution was stored in a sealed vial at 0° C.

[0095] (4) The fabric assembly is immersed in 16.2 mL of the cetyltrimethylammonium chloride solution prepared in (2). If necessary, the pH is stabilised between 7.35 and 7.65 by adding sodium hydrogen phosphate. The solution is thermostated at a temperature of 25° C. 500 μL of the methyl-paraoxon solution prepared in (3) is added and the medium is mixed manually with a glass rod for 5 seconds. The absorbance of the solution is measured at 400 nm at regular 4-minute intervals over a maximum of 28 minutes. The experiment was repeated three times.

[0096] (5) Spontaneous hydrolysis of methyl-paraoxon was evaluated under the same conditions and in the absence of the fabric assembly. The absorbance values obtained were deducted from the measurements in (4) to determine the actual efficiency of the treated fabric.

[0097] Under these conditions, 32% of the initial amount of methyl-paraoxon is degraded after 20 minutes in the presence of the fabric assembly.

Example 3: Determination of the Average Immobilisation Rate of “Accessible and Active” β-Cyclodextrin Derivative Expressed in g per m.SUP.2 .of Fabric

[0098] (6) A 1 mM solution of the β-cyclodextrin derivative is obtained by dissolving 29.5 mg of product in 20 mL of 13 mM cetyltrimethylammonium chloride solution containing 3% dimethylsulfoxide prepared in (2).

[0099] (7) A 0.5 mM solution of the β-cyclodextrin derivative is obtained by diluting 10 mL of the solution prepared in (6) in 10 mL of 13 mM cetyltrimethylammonium chloride solution containing 3% dimethylsulfoxide prepared in (2).

[0100] (8) A 0.25 mM solution of the β-cyclodextrin derivative is obtained by diluting 10 mL of the solution prepared in (7) in 10 mL of 13 mM cetyltrimethylammonium chloride solution containing 3% dimethylsulfoxide prepared in (2).

[0101] (9) 30 μL of the solution prepared in (3) is added to 970 μL of the solution prepared in (6). The solution is thermostated at a temperature of 25° C. The absorbance of the solution is measured at 400 nm continuously over a period of 30 minutes. Each experiment was repeated three times.

[0102] (10) 30 μL of the solution prepared in (3) is added to 970 μL of the solution prepared in (7). The solution is thermostated at a temperature of 25° C. The absorbance of the solution is measured at 400 nm continuously over a period of 30 minutes. Each experiment was repeated three times.

[0103] (11) 30 μL of the solution prepared in (3) is added to 970 μL of the solution prepared in (8). The solution is thermostated at a temperature of 25° C. The absorbance of the solution is measured at 400 nm continuously over a period of 30 minutes. Each experiment was repeated three times.

[0104] (12) Three linear calibration curves were obtained at: T0+4 min, T0+8 min and T0+12 min by linear regression of the absorbance values measured in (9), (10) and (11).

[0105] (13) The amount of active β-cyclodextrin derivative immobilised on the fabric assembly is the average of the three values calculated from the linear calibration curve equations obtained for T0+4 min, T0+8 min and T0+12 min.

[0106] The immobilisation rate was thus evaluated at 5.3 g.Math.m.sup.−2.

Example 4: Conditions of Use of the Treated Textile Substrate

[0107] The fabric assembly after a first use in example 2 is immersed in 17 mL of MilliQ® water for 1 min without stirring. It is taken and successively immersed four times in 17 mL of MilliQ® water for 5 min without stirring. After drying in the open air, it is subjected to a second decontaminant activity evaluation under the experimental conditions of example 2 (1.sup.st recycling).

[0108] The fabric assembly after a second use is removed and successively immersed four times in 17 mL of MilliQ® water for 5 min without shaking. After drying in the open air, it is subjected to a third decontaminant activity evaluation under the experimental conditions of example 2 (2.sup.nd recycling).

[0109] A significant attenuation of the decontamination capacity is observed during the 2.sup.nd and 3.sup.rd use (FIG. 3).

[0110] Additionally, a fabric assembly made under the conditions of example 2 is immersed in 16.2 mL of the cetyltrimethylammonium chloride solution prepared in (2) (example 2). If necessary, the pH is stabilised between 7.35 and 7.65 by adding sodium hydrogen phosphate. The solution is thermostated at a temperature of 25° C. After 20 minutes, the fabric assembly is removed. 500 μL the methyl-paraoxon solution prepared in (3) (example 2) is added and the medium is mixed manually with a glass rod for 5 seconds. The absorbance of the solution is measured at 400 nm at regular 4-minute intervals over a maximum of 28 minutes. The hydrolysis kinetic profile of methyl-paraoxon is similar to that obtained with the fabric assembly in example 2 (FIG. 2).

[0111] These analyses show that the scavenger is removed from the textile substrate under decontamination conditions, i.e. a buffered solution (7.35<pH<7.65), which makes it possible to preserve a decontamination efficiency equivalent to that obtained in the homogeneous phase of the cyclodextrin derivative (IV) during a single use of the treated textile substrate (“disposable” system) and to consider the used fabric assembly to be a non-toxic waste product.

Example 5: Preparation of Prototype Sponges and Evaluation of Their Effectiveness Against a Chemical Weapon

[0112] 1. Immobilisation of Cyclodextrin Derivative (1) and β-Cyclodextrin

[0113] The immobilisation of the cyclodextrin derivative of formula (1) below:

##STR00008##

[0114] was carried out using the same protocol as in Example 1, only the size of the cotton used was changed from 15×15 cm to A4.

[0115] The same protocol as described above was also used to immobilise β-cyclodextrin of the formula below in place of derivative (1).

[0116] 2. Rinsing Protocol

[0117] The rinsing protocol is identical to that used in Example 1, regardless of the immobilised derivative (derivative (1) or β-cyclodextrin).

[0118] 3. Efficiency of the Modified Textile

[0119] Twenty samples of size 5×9 cm were assembled in pairs and sewn with the modified textile obtained with derivative (1) (Assemblies A=sponges A).

[0120] Twenty samples of size 5×9 cm were assembled in pairs and sewn with the modified textile obtained with β-cyclodextrin (Assemblies B=sponges B).

[0121] Twenty samples of size 5×9 cm were assembled in pairs and sewn together with the unmodified textile (Assemblies C=sponges C).

[0122] The different assemblies (=sponges) obtained were used in the rest of the protocol.

[0123] Decontamination Efficiency of the Material [0124] Contamination Protocol

[0125] 8 stainless steel specimens of 5×5 cm are contaminated with soman at a rate of

5 g/m.sup.2 by depositing 25 drops of 0.5 μL. Three test tubes were extracted for 90 minutes in 175 mL weighing bottles containing 25 mL of ethyl acetate and a 1 mL sample was analysed by gas chromatography to determine the initial contamination level.

[0126] The remaining five test tubes are placed in front of five uncontaminated test tubes. These will be used to determine the transfer of contamination from contaminated plates to uncontaminated ones when using the sponges. [0127] Decontamination Protocol—Measurement of Residual Contamination and Contamination Transfers

[0128] A sponge (5×9 cm), attached with aluminium adhesive to a 500 g metal mass, is applied for 1 to 2 s to the contaminated sample and then moved to the uncontaminated sample (also 1 to 2 s pause). As soon as the sponge application is complete, the samples are extracted into 175 mL weighing bottles containing 25 mL ethyl acetate (a single 90 min extraction since the material is non-absorbent). A sample from each weighing machine is taken for GC analysis. The sponge is immersed in 20 mL of phosphate buffer (0.1 M, pH 7.4) contained in a 175 mL weighing bottle.

[0129] The samples were analysed by gas chromatography under the following analytical conditions:

TABLE-US-00002 Soman (GD) Injecteur Mode: Splitless Température: 250° C. Gaz vectour: Hélium Colonne VF-5ms (5% diphenylpolysiloxane, 85% dimethylpolysiloxane) ∅ colonne: 0.25 mm Débit gaz vecteur: 1.3 mL/min Température: 50 à 120° C. 10° C./min 120 à 250° C. 15° C./min Paller de 3 minutes Détecteur Type: FPD Température: 280° C. [0130] Results

[0131] The contamination rate measured on 3 stainless steel test tubes not contaminated by 25 drops of 0.5 μL of soman is 403.8±17.3 μg/cm.sup.2.

[0132] The results of the decontamination tests of 5 successive stainless steel plates (5 plates of 25 cm2 contaminated by 25 drops of 0.54 μL of soman) by the three types of sponges, carried out according to the protocol, are in Table 2 and Table 3 below.

TABLE-US-00003 Quantity extracted on stainless Average Measured steel plates amount % Average % quantity Sponge (μg/cm.sup.2) (μg/cm.sup.2) decontamination decontamination Residual Assembly A 13.1 7.8 ± 3.9 96.75 98.1 ± 1.0 quantity 8.8 97.82 8.8 97.83 5.4 98.67 2.91 99.28 Assembly B 20.6 35.4 ± 12.8 94.90 91.2 ± 3.2 29.5 92.71 55.2 86.34 33.5 91.70 38.5 90.47 Assembly C 33.3 20.3 ± 8.2  91.76 95.0 ± 2.0 21.6 94.65 17.9 95.67 17.7 95.61 11.0 97.28

[0133] The decontamination percentages of the stainless steel plates are 98.1% (Assembly A), 91.2% (Assembly B) and 95.0% (Assembly C) respectively. Assembly A (fabric modified with derivative (1)) has a higher decontaminating effect than the reference assembly C (unmodified fabric). Assembly B (β-cyclodextrin modified fabric) has a lower decontaminating effect than reference assembly C.

TABLE-US-00004 TABLE 3 Decontamination efficiency of the TEXT-scavr-OP sponge on five soman-contaminated stainless steel specimens (125 cm.sup.2 at g .Math. m.sup.2) Quantity extracted Measured on stainless steel Average quantity Sponge plates (μg/cm.sup.2) amount (μg/cm.sup.2) Transfer of Assembly A 2.36 2.06 ± 1.15 contamination 0.23 3.34 1.80 2.69 Assembly B 1.33 0.91 ± 0.53 0.46 0.26 1.10 1.42 Assembly C <0.12 0.16 ± 0.08 <0.12 0.31 <0.12 <0.12

[0134] The contamination transfers measured on initially uncontaminated stainless steel plates are 2.06 μg.Math.cm-2 (Assembly A), 0.91 μg.Math.cm-2 (Assembly B) and 0.16 μg.Math.cm-2 (Assembly C) respectively. The values are relatively low for all types of assembly.

[0135] Degradation Kinetics of Soman [0136] Protocol

[0137] Two degradation kinetics follow-ups were carried out: the first with an assembly (A, B or C) having decontaminated a single 5×5 cm stainless steel plate, the second with an assembly (A, B or C) having successively decontaminated five 5×5 cm stainless steel plates.

[0138] The following protocol was then implemented in both cases:

[0139] The sponge is immersed in 20 mL of phosphate buffer (0.1 M, pH 7.4) contained in a 175 mL weighing bottle. At t=15 min, 1 h, 3 h and 6 h, the weighing bottle was manually shaken to homogenise the buffer and 500 μL was taken, neutralised with 0.5 mL citrate buffer (0.2 M, pH 5.5) and extracted with 3 mL ethyl acetate into a 15 mL centrifuge tube. The tube is centrifuged for 1 min at 4000 rpm and a sample of the organic phase is taken for GC analysis.

[0140] At t=24 h, the buffer is neutralised by adding 18 mL of 0.2 M citrate buffer pH 5.5. The sponge is drained, extracted with 25 mL ethyl acetate for 90 min and then a sample of the organic phase is taken for GC analysis. The neutralised medium is homogenised and then 1 mL is taken and extracted with 3 mL of ethyl acetate into a 15 mL centrifuge tube. The tube is centrifuged for 1 min at 4000 rpm and a sample of the organic phase is taken for GC analysis.

[0141] Extraction Coefficient:

[0142] The quantities determined must be corrected by an extraction coefficient, determined beforehand according to the following protocol: A stainless steel plate is contaminated with 25 drops of 0.5 μL of soman and then immersed in a 175 mL weighing bottle containing 20 mL of phosphate buffer (0.1 M, pH 7.4) and 20 mL of citrate buffer (0.2 M, pH 5.5) The medium is thoroughly homogenised using a 10 mL pipette. 1 mL of the mixture is taken and extracted with 3 mL of ethyl acetate into a 15 mL centrifuge tube. The tube is centrifuged for 1 min at 4000 rpm and a sample of the phase is taken for GC analysis.

[0143] The conditions for analysis by gas chromatography are the same as above. [0144] Results

[0145] Kinetics of soman degradation by assemblies (A, B or C) having decontaminated a single stainless steel plate (25 cm.sup.2 at 5 g.Math.m.sup.2)

[0146] The degradation efficiencies of soman by sponges were first determined after “decontamination” of a single 25 cm.sup.2 stainless steel plate contaminated with 25 drops of 0.54 μL soman. The residual contamination on these plates was measured, and the contamination rate was used to deduce the contamination absorbed by the sponges.

TABLE-US-00005 24 h 24 h 24 h 15 min 1 h 3 h 6 h (buffer) (sponge) (total) Assembly A 44.9% 14.2% 0.17% <0.13 — <0.03% <0.16% Assembly B 63.7% 46.3% 19.5% 8.3% 0.32% 0.62% 0.95% Assembly C .sup. 76% 49.1% 15.5% 2.8% <0.13% <0.03% <0.16%

[0147] After 3 h of immersion of the assemblies, only 0.17% of the soman absorbed by assembly A remained in the phosphate buffer, compared to 19.5% by assembly B and 15.5% by assembly C. After 6 h of immersion of the different assemblies, there was no more soman quantified in the phosphate buffer in the case of the test carried out with assembly A, whereas 8.3% and 2.8% of soman still remained for the tests carried out respectively with assemblies B and C. After 24 hours, the tests were stopped and the assemblies were also extracted. There was no difference between assemblies A and C, only the test with assembly B detected 0.62% soman in the assembly and 0.32% in the buffer (a total of 0.95%).

[0148] Kinetics of soman degradation by assemblies (A, B or C) having decontaminated five stainless steel plates (125 cm.sup.2 at 5 g.Math.m.sup.2)

[0149] Following decontamination of the five 25 cm.sup.2 stainless steel plates (contaminated with 25 drops of 0.5 μL soman), the soman degradation efficiencies of the sponges were determined after immersion in phosphate buffer pH 7.4. The contamination absorbed by the sponges was deduced from the contamination rate and the residual amounts measured by the stainless steel plates. It was used to calculate the percentage of residual soman in the buffer and in the sponges.

TABLE-US-00006 24 h 24 h 24 h 15 min 1 h 3 h 6 h (buffer) (sponge) (total) Assembly A 81.7% 50.5% 13.46% 2.51% <0.03% <0.01% <0.03% Assembly B 81.7% 63.9% 29.8% 13.4% <0.07% <0.78% <1.48% Assembly C 74.9% 61.7% 23.7% 6.7% <0.03% <0.01% <0.03%

[0150] Under these more restrictive test conditions, the degradation kinetics are slower but the difference still remains in favour of assembly A. After 6 h of immersion of the assemblies, only 2.51% of the soman absorbed by assembly A remained in the phosphate buffer, compared to 13.4% by assembly B and 6.7% by assembly C. After 24 hours, the tests were stopped and the assemblies were also removed. There was no difference between assemblies A and C (residual level<0.3% in the buffer and assembly), only the test with assembly B detected 0.78% soman in the assembly and 0.7% in the buffer (a total of 1.48%).

Example 6: Other Ways of Preparing the Modified Textile Fabric

[0151] 1. Immobilisation of Cyclodextrin Derivative (1)

[0152] The immobilisation of the cyclodextrin derivative of formula (1) below:

##STR00009##

[0153] was carried out: [0154] either according to a protocol identical to that used in example 1, only the pre-drying time was reduced to 10 minutes; [0155] or according to a protocol identical to that used in example 1, but in the absence of cyanamide, the pre-drying time was reduced to 10 minutes.

[0156] Twelve samples of size 5×5 cm were assembled in pairs and sewn with the modified textile obtained with derivative (1) (Assembly A1).

[0157] Twelve samples of size 5×5 cm were assembled in pairs and sewn with the modified textile obtained with β-cyclodextrine (Assembly A2).

[0158] 2. Rinsing Protocol

[0159] 6 different rinsing protocols were carried out for the two types of assemblies A1 and A2: [0160] either by three successive soaks in 20 mM phosphate buffer solution at pH 7.65 (15 mL) according to the following times: [0161] 3×30 s, [0162] or 3×1 min, [0163] or 3×2 min. [0164] or by three successive soakings in Milli-Q® water at pH 5.5 (15 mL) according to the following times: [0165] 3×30 s, [0166] or 3×1 min, [0167] or 3×2 min.

[0168] 3. Comparative Effectiveness of Assemblies A1 and A2 on Paraoxon Degradation

[0169] The conditions of analysis are identical to those of example 2, the experiment was carried out once for each assembly A1 or A2 having undergone the same type of rinsing.

[0170] The results are depicted depicted in FIGS. 4 and 5.

[0171] Regardless of the A1 and A2 assemblies, the rinsing time increases the rate at which the scavenger is removed from the textile substrate at pH 7.65. At pH 5.5, this removal rate stabilises for rinsing times of between 3×1 min and 3×2 min. The presence of cyanamide has little influence on the rate of scavenger immobilised on the textile substrate.

Example 7: Determination of the Optimal Fixing Conditions For the Preparation of the Modified Textile Fabric

[0172] 1. Immobilisation of Cyclodextrin Derivative (1)

[0173] The immobilisation of the cyclodextrin derivative of formula (1) below:

##STR00010##

[0174] was achieved on cotton by using a bridging agent, 1,2,3,4-butanetetracarboxylic acid (BTCA), to crosslink the oligosaccharide units of the scavenger (1) and graft them onto the textile substrate.

[0175] The textile substrate (cotton, size A4) was immersed for 2 minutes in a bath containing β-cyclodextrin derivative (1) (10%), 1,2,3,4-butanetetracarboxylic acid (BTCA, 10%), sodium hypophosphite (3%) and ammonium biphosphate (ADHP, 1%).

[0176] Derivative (1) was prepared by the company Provepharm.

[0177] BTCA, sodium hypophosphite, and ADPH were supplied by Sigma-Aldrich.

[0178] After fulling at a pressure of 1.5 bar, the impregnated fabric was pre-dried for 10 minutes at 120° C. Fixation was carried out at 180° C. for 3 minutes.

[0179] Twelve samples of size 5×5 cm were assembled in pairs and sewn with the modified textile obtained with derivative (1) (Assembly A3).

[0180] 2. Rinsing Protocol

[0181] 6 different rinsing protocols were carried out according to the procedures described in Example 6 for assemblies A2 and A3.

[0182] 3. Comparative Effectiveness of Assemblies A1 and A3 on Paraoxon Degradation

[0183] The analysis conditions for assembly A3 are identical to those described for assemblies A1 and A2 in Example 6.

[0184] The results are depicted depicted in FIGS. 6 and 7.

[0185] In contrast to assembly A1, and regardless of the rinsing process used, assembly A3 does not accelerate the degradation of paraoxon.