: 913mol/ L LiBr ; PVA PVA, u 2 + Kl K p = 1015 = ( ), WFX2F2 115 ( ) ESR ( ) ESR J ES2FE 1 XGX 116 ( ) 10 5,37

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吏邹
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1 No 4 ATA PL YMERIA SIN IA Aug, ( ) (( ) ) ( ( 386) ) ( ) ( ESR) ( ) :( ) ( ),( ),,,ESR, [1, ],, : Ag + u 2 + Zn 2 +, ;, Ag + [2 ] ( Silk Fibroin) (Viscose cellulose) ( PVA), ( ), ( ) ( ) ( ) ( ) LiBr, AR 112 ( ) p 1015 p, UV2240 p 1015 u 2 + 2Silk u 2 + 2PVA , ; ; Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

2 : 913mol/ L LiBr ; PVA PVA, u 2 + Kl K p = 1015 = ( ), WFX2F2 115 ( ) ESR ( ) ESR J ES2FE 1 XGX 116 ( ) 10 5,37 18h, Fig 1 ESR spectra of copper ( ) complex fiber at room temperature 1 u 2 + 2Sik ; 2 u 2 + 2ellulose ; 3 u 2 + 2A2ellulose,18, 75 %, 95 % [3 ] 75, N 1313mmol/ g, mmol/ g 24h, ( ) u 2 + 2Silk u 2 + 2ellulose ESR 1 2 [4 d x 2y2 ], ESR 2, g g Table 1 u 2 + contents of copper ( ) complex fiber Fiber Functional group ( FG) L content (mmol/ g) u 2 + content (mmol/ g) u 2 + / FG (mol ratio) Silk N ellulose PVA Fibers soaked in cuprammonium solution (0105mol/ L,p 1015) at 25 for 24h,and the bath ratio is Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

3 , g g, A A u 2 + 2PVA ESR Table 2 ESR parameters of the copper ( ) complexe fiber Sample g g A (cm - 1 ) 2 u 2 + 2Silk u 2 + 2ellulose u 2 + 2A2ellulose A2ellulose expresses citric acid modified cellulose u 2 + 2Silk nm, u 2 + [5 2 ], u2n d2d u 2 + 2Silk ( ) ESR ( ), 2 un 4,, Fig 2 UV and visible spectrum of copper ( )2silk fibroin solution at room temperature and = 011 ( Kl), ESR, u 2 + 2Silk p = 1015, [ u 2 + ]/ [ Fibroin residue ] = 1/ 15, [ Fibrion residue] = mol/ L,1 cm cell un 4 3 [1 ] u 2 + PVA, : Kohn [6 ] u 2 + PVA ; Yoki [7 ] u 2 + PVA, PVA u n () 2 n - 2 p 1015 u 2 + 2PVA 2 4,360nm, [8 ] PVA p 1015,p :( ) 433 ; u 2 + 2PVA, ESR ESR u 2 + PVA,, u 2 + 2PVA,PVA (0105mol/ L p 1015), PVA u 2 + 2PVA Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

4 Fig 3 oordination structure of copper ( ) complex fiber Fig 4 UV and visible spectrum of copper ( )2 poly(vinyl alcohol) solution at room temperature and = 011 ( Kl),p = 1015, [ u 2 + ]/ [ PVA residue ] = 1/ 10, [ PVA residue] = 01044mol/ L,1cm cell 3 [2 ] PVA, 2 3,PVA, u 2 +,1,22 ; u 2 +,2,42 u [9 ], u 2 + u 2 + 2ellulose ESR g A u Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

5 4 :( ) [3 ] d 2 2 = ( A / P) + ( g - g e ) + 3/ 7 ( g - g e ) ( g e g, g e = ; P 3d, P = 01036cm - 1 ) [10 ] 2 2, 2 = %, d ; 2 = %, 2 2 u 2 + 2PVA > u 2 + 2ellulose > u 2 + 2Silk 213 ( ), p (1015), ( ), 3, / ml / ml u 2 + 2Silk, u 2 + 2Silk u 2 + 2ellulose u 2 + 2PVA / ml Table 3 The antibacterial activity of copper ( ) complex fiber against staphylococcus aureus Sample u 2 + content (mmol/ g) Initial bacterial no (cell/ ml) bacterial no after culture (cell/ ml) otton u 2 + 2Silk u 2 + 2ellulose u 2 + 2PVA u 2 + 2A2ellulose , u 2 +,,N u 2 + u 2 +, u 2 +,u ; u 2 +,, 2, 2, u ( ),,, u 2 + 2ellulose u 2 + 2PVA p [11 ] Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

6 ( ) (u 2 + 2A2ellulose) u 2 + 2A2ellulose (A) (SP), : 1) : ), (ell ) : 2 2 Na + P Na Na P 2 P 2 ell Na + ell + P 2 2 3) (A2ellulose) : 2 ell 2 2 ell 2 SP ell 2 ell ell 2 ell A2ellulose, u 2 + 2A2 ellulose ESR 1 2 u 4,u 2 + 2ellulose, g g, A, 2, 3 [4 ] 3,, u A2ellulose 012 % 8h, u % Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

7 4 :( ) 437, ( ),, ( ), p REFERENES 1 Nakazima T Sen2 Kako,1993,45 : ku S Sen2 Gakkaish (Sen2 To Kogio),1993,49 : Kirimural J,Nippon Sanshi Shikenjo okoku,1962,17 : hen Deyu( ) hemistry( ),1992, (7) : ojo N,Fukatsu F,ayakawa T,et alj Jpn hem Soc,1969,90 : Kohn W, Toth I Z Naturforsch,1963,18A : Yokoi, Kawata S,Iwaizumi MJ Am hem Soc,1986,108 : atterick J, Thornton P Adv Inorg hem Radiochem,1977,20 : Miyamoto I,Inamoto M,Matsui T,et al Polym J,1995,27 : Kivelson D,Neiman RJ hem Phys,1961,35 : iardelli F, Tschida E,Wghrle D Macromolecule2Metal omplexes,berlin :Springer, RD INATIN STRUTURE AND ANTIBATERIAL ATIVITY F PPER ( ) MPL EX FIBERS EN Wenxing ( ollege of Textile Technology, Zhejiang Instit ute of Silk Textiles, angzhou ) SEN Zhiquan ( Depart ment of Polymer Science & Engineering, Zhejiang U niversity, angzhou ) L IU Guanfeng ( Zhejiang Instit ute of Silk Textiles, angzhou ) SIRAI irofusa ( Faculty of Textile Science & Technology, Shinshu University, Ueda 386 Japan) Abstract The copper ( ) complex fibers were prepared by heterogeneous coordination replacement reaction of silk fibroin,viscose cellulose and poly ( vinyl alcohol) ( PVA) fiber in cuprammonium solution The coordination st ruct ures of t he fiber were st udied by ESR spect ra etc The antibacterial experiment shows t hat t he antibacterial activities of t hese t hree copper ( ) complex fibers are in the following order : u 2 + 2PVA fiber > u 2 + 2ellulose fiber > u 2 + 2Silk fibroin fiber It is verified that the antibacterial activity is related with stability of the coordination structure of the copper ( ) complex fiber That is t he more unstable coordination structure,the better the antibacterial activity A copper ( ) complex fiber of citric acid modified cellulose ( u 2 + 2A2ellulose) with moderate stability of the coordination st ruct ure which has been designed shows good antibacterial activity and washing fast ness,as expected Key words Fiber,opper ( ) complex,oordination st ruct ure,antibacterial activity, ESR Tsinghua Tongfang ptical Disc o, Ltd All rights reserved

桂医大研〔2015〕10号

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