Silkworms

Silk degumming Silk Screening Silk-screen inks Silkworm Silky II Polydek Sillemanite Silkmanite Sillimanite [12141-45-6]... 

Fibers (see Fibers, survey) used in textile production can have a wide variety of origins plants, ie, ceUulosic fibers (see Fibers, cellulose esters) animals, ie, protein fibers (see Wool) and, in the twentieth century, synthetic polymers. Depending on the part of the plant, the ceUulosic fibers can be classified as seed fibers, eg, cotton (qv), kapok bast fibers, eg, linen from flax, hemp, jute and leaf fibers, eg, agave. Protein fibers include wool and hair fibers from a large variety of mammals, eg, sheep, goats, camels, rabbits, etc, and the cocoon material of insect larvae (sUk). Real sUk is derived from the cocoon of the silkworm, Bombjx mori and for a long time was only produced in China, from which it was traded widely as a highly valuable material. 

Second-generation juvenoids incorporate more substantial stmctural departures from neotenin and are more resistant to metaboHc and environmental degradation. Epiphenonane, 2-ethyl-3-[3-ethyl-5-(4-ethylphenoxy)-pent-3-en-yl] 2-methyloxirane (131), has a rat oral LD q of 4000 mg/kg. It and similar juvenoids are used in China and Japan to prolong the last larval instar of the silkworm so that silk production is increased 10—15%. Fenoxycarb, ethyl [2-(4-phenoxyphenoxy)ethyl] carbamate (132) (mp 53°C, vp 0.0078 mPa at 20°C), is soluble in water to 6 mg/L. The rat oral LD q is >16,800 mg/kg. Fenoxycarb has a wide spectmm of activity, interfering with the developmental processes of fleas, cockroaches, and ants. 

Philosamia gnthia ricini = wild-type silkworm silk. 

Secondary Structure. The silkworm cocoon and spider dragline silks are characterized as an antiparaHel P-pleated sheet wherein the polymer chain axis is parallel to the fiber axis. Other silks are known to form a-hehcal (bees, wasps, ants) or cross- P-sheet (many insects) stmctures. The cross-P-sheets are characterized by a polymer chain axis perpendicular to the fiber axis and a higher serine content. Most silks assume a range of different secondary stmctures during processing from soluble protein in the glands to insoluble spun fibers. 

Crystallinity. Generally, spider dragline and silkworm cocoon silks are considered semicrystalline materials having amorphous flexible chains reinforced by strong stiff crystals (3). The orb web fibers are composite materials (qv) in the sense that they are composed of crystalline regions immersed in less crystalline regions, which have estimates of 30—50% crystallinity (3,16). Eadier studies by x-ray diffraction analysis indicated 62—65% crystallinity in cocoon silk fibroin from the silkworm, 50—63% in wild-type silkworm cocoons, and lesser amounts in spider silk (17). 

Commercial and Artificial Processing. Commercially, silkworm cocoons are extracted in hot soapy water to remove the sticky sericin protein. The remaining fibroin or stmctural sdk is reeled onto spools, yielding approximately 300—1200 m of usable thread per cocoon. These threads can be dyed or modified for textile appUcations. Production levels of sdk textiles in 1992 were 67,000 metric tons worldwide. The highest levels were in China, at 30,000 t, foUowed byJapan, at 17,000 t, and other Asian and Oceanian countries, at 14,000 t (24). Less than 3000 metric tons are produced annually in each of eastern Europe, western Europe, and Latin America almost no production exists in North America, the Middle East, or Africa. 1993 projections were for a continued worldwide increase in sdk textile production to 75,000 metric tons by 1997 and 90,000 metric tons by 2002 (24). 

Films or membranes of silkworm silk have been produced by air-drying aqueous solutions prepared from the concentrated salts, followed by dialysis (11,28). The films, which are water soluble, generally contain silk in the silk I conformation with a significant content of random coil. Many different treatments have been used to modify these films to decrease their water solubiUty by converting silk I to silk II in a process found usehil for enzyme entrapment (28). Silk membranes have also been cast from fibroin solutions and characterized for permeation properties. Oxygen and water vapor transmission rates were dependent on the exposure conditions to methanol to faciUtate the conversion to silk II (29). Thin monolayer films have been formed from solubilized silkworm silk using Langmuir techniques to faciUtate stmctural characterization of the protein (30). ResolubiLized silkworm cocoon silk has been spun into fibers (31), as have recombinant silkworm silks (32). 

Thermal Properties. Spider dragline silk was thermally stable to about 230°C based on thermal gravimetric analysis (tga) (33). Two thermal transitions were observed by dynamic mechanical analysis (dma), one at —75° C, presumed to represent localized mobiUty in the noncrystalline regions of the silk fiber, and the other at 210°C, indicative of a partial melt or a glass transition. Data from thermal studies on B. mori silkworm cocoon silk indicate a glass-transition temperature, T, of 175°C and stability to around 250°C (37). The T for wild silkworm cocoon silks were slightly higher, from 160 to 210°C. 

Silk (qv) suture is made from the threads spun by the silkworm Bombjx mori. The fiber is composed principally of the protein fibroin and has a natural coating composed of sericin gum. The gum is usually removed before braiding the silk yams to make sutures in a range of sizes. Fine silk sutures may be made by simply twisting the gum-coated silk yams to produce the desired diameter. White silk is undyed. Silk is either dyed black with logwood extract or blue with D C Blue No. 9. The suture may be uncoated or coated either with high molecular weight polydimethylsiloxane or with wax. 

FIGURE 4.50 FVjrifIcation of mRNA on Toyopearl HW-65F. Column Toyopearl HW-65F. 25 mm X 90 cm. Sample 40 mg of poly(A) RNA/5 ml of formamide, sample from silkworm. Elution 20 mA1 sodium citrate, 5 mM EDTA, 0.5% SDS, 6 M urea, pH 3.5. Flow rate 24 ml/hr. Detection UV at 254, total mRNA activity (—), mRNA activity for major plasma proteins (------------). 

Recently, a variety of natural peptides that form transmembrane channels have been identified and characterized. Melittin (Figure 10.35) is a bee venom toxin peptide of 26 residues. The cecropins are peptides induced in Hyalophora cecropia (Figure 10.36) and other related silkworms when challenged by bacterial infections. These peptides are thought to form m-helical aggregates in mem-... 

Fibers obtained from living organisms are known as animal fibers, e.g., wool, which is obtained from domestic sheep silk fiber, which is produced by the silkworm... 

Named bombykol, the sex pheromone secreted by the female silkworm moth has the formula C16H280 and the systematic name (10 ,12Z)-10,12-hexa-decadien-l-oJ. Draw bombykol showing correct geometry for the two double bonds. 

The structures of some natural protein-based materials, such as silk and wool, result in strong, tough fibers. Spiders and silkworms use proteins as a structural material of remarkable strength (Fig. 19.22). Chemists are duplicating nature by making artificial spider silk (Fig. 19.23), which is one of the strongest fibers known. 

Figure 5.31 LC-electrospray-MS-MS spectrum of the column eluate at around 22 min in the analysis of the peptide mixture from the tryptic digest of glycoprotein TIME-EA4 from silkworm diapause eggs. Reprinted from Bioorg. Med. Chem., 10, Kurahashi, T., Miyazaki, A., Murakami, Y., Suwan, S., Franz, T., Isobe, M., Tani, M. and Kai, H., Determination of a sugar chain and its linkage site on a glycoprotein TIME-EA4 from silkworm diapause eggs by means of LC-ESI-Q-TOF-MS and MS/MS , 1703-1710, Copyright (2002), with permission from Elsevier Science.

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