Properties of some polysilane polymers: (n-PrSiMe) n , (i-PrSiMe) n,and (sec-BuSiMe) n

Three polysilane polymers, (n-PrSiMe) _n , (i-PrSiMe) _n , and (sec-BuSiMe) _n , were synthesized and characterized by DSC. UV spectroscopy, wide-angle X-ray diffraction, and optical microscopy, all at variable temperatures. The known thermochromic transition of (n-PrSiMe) _n at ～48 C is associated with a change from an orthorhombic to an isotropic phase. (i-PrSiMe) _n was examned as an insoluble and soluble (lowM _w) fraction, both existing mainly in an orthohombic lattice at room temperature. (sec-BuSiMe) _n has a mesophase structure at 25 C, undergoes a weak endothermic transition to a second (nematic) mesophase near 65 C, and becomes isotropic at ～160 C.     

(Z)6, (E)8-Heneicosadien-11-One: Synergistic Sex Pheromone Component of Douglas-Fir Tussock Moth, Orgyia pseudotsugata (McDunnough) (Lepidoptera: Lymantriidae)

Three candidate sex pheromone components, (Z)6,(Z)9-, (Z)6,(E)8-, and (Z)6,(E)9-heneicosadien-11-one (Z6Z9, Z6E8, and Z6E9) were identified in pheromone gland extracts of female Douglas-fir tussock moths (DFTM), Orgyia pseudotsugata (McDunnough). Their occurrence in subnanogram quantities in extracts and structural conversion during analytical procedures and bioassays complicated chemical identifications. Complete identification required comparative analyses of stereoselectively synthesized and female-produced dienones by coupled gas chromatographic–electroantennographic detection (GC-EAD), high-performance liquid chromatography (HPLC) and coupled GC–mass spectrometry (MS). Determination of the pheromone component was contingent upon an experimental design that minimized structural rearrangement of dienones before and during the field test. In a 40-min field experiment, acetonitrile solutions of each of the above dienones were carried on Dry Ice to traps and were syringed onto cotton release devices below trap lids. In combination with the previously known sex pheromone component of DFTM, (Z)6-heneicosen-11-one (Z6), Z6E8 was the only synergistic dienone and the mixture was highly attractive. Because Z6 by itself attracts seven species of tussock moths (two sympatric with DFTM), a blend of Z6 and Z6E8 may impart specificity to DFTM pheromone communication. In commercial lures, this binary blend may facilitate species-specific, sensitive monitoring and efficacious control by mating disruption of this important forest defoliator.     

Hybrid Metal (Gold)-Inorganic (Silica) Nanoparticles: Synthesis,Characterization, and Spin-Labeling

Water-soluble gold nanoparticles, capped with captopril, have been synthesized and characterized. Their average size is 2.3 nm, with a spherical shape. These gold nanoparticles can be easily labeled with stable free radicals (4-amino-tempo) by a coupling reaction performed in the presence of 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ). Both synthesized and spin-labeled gold nanoparticles can be incorporated into much bigger (100 nm) silica nanoparticles using the Stober method, thus forming hybrid metal (gold)-inorganic (silica) nanoparticles. These hybrid silica nanoparticles (containing or not spin-labeled gold nanoparticles) can be easily spin-labeled with another stable free radical (4-isocyanato-tempo), leading to the formation of a double spin-labeled material. In this way, some stable free radicals are attached on the gold surface while others are attached on the silica surface. Three types of EPR spectra were recorded and discussed for the hybrid gold-silica nanoparticles: (1) where the spin labels are attached to the embedded gold nanoparticles, (2) where the spin labels are attached to the silica nanoparticles, and (3) in the case of the double spin labeled material where both gold and silica nanoparticles are spin-labeled. Influence of different solvents on the EPR spectra is also discussed.     

Sex pheromone of the armyworm,Pseudaletia unipuncta (Haworth) (Lepidoptera: Noctuidae)

(Z)-11-Hexadecen-1-ol acetate (Z11–16Ac) free of theE isomer (<1%), hexadecan-1-ol acetate (16 Ac), and a hexadecen-1-ol [the (Z)-11 isomer based on the retention time on a Carbowax capillary column] were identified in extracts of the sex pheromone glands of adult virgin female armyworms,Pseudaletia unipuncta. Also, gas Chromatographic retention times on polar and nonpolar columns indicated the possible presence of (Z)-9-hexadecen-1-ol acetate (Z9–16Ac). The ratioZ11–16Ac/16Ac/Z11–16OH/Z9–16Ac was 10.150.130.02. Infield testsZ11–16 Ac was attractive alone, and the addition ofZ9–16Ac,Zll–16 OH, or 16 Ac singly or in combination in ratios found in the gland did not increase trap capture.Mention of a proprietary product does not constitute an endorsement of this product by the USDA.     

Pheromone differences between sibling taxaDiachrysia chrysitis (linnaeus, 1758) andD. tutti (Kostrowicki, 1961) (Lepidoptera: Noctuidae)

The noctuid sibling taxaDiachrysia chrysitis s. str. andD. tutti, of yet uncertain taxonomic status, have previously been shown to possess differences in morphology and to be attracted to different mixtures of the two presumed pheromone components (Z)-5-decenyl acetate and (Z)-7-decenyl acetate. TypicalD. tutti males (clearly broken forewing marking) are known to respond to a 2: 100 mixture of the two isomers, whereasD. chrysitis males (unbroken marking) are attracted to a 100: 10 mixture. We investigated female pheromone production and male electroantennographic (EAG) response inDiachrysia families raised in the laboratory from field-collected gravid females. Extracts of individual females from typicalD. tutti andD. chrysitis families were subjected to gas chromatography with simultaneous flame ionization and electroantennographic detection. All females produced mixtures of Z5- and Z7-10:OAc, but femaleD. chrysitis produced predominantly Z5-10:OAc and the antennae of their brothers responded more strongly to the Z5 peak than to the Z7-10:OAc peak, whereas the opposite was true forD. tutti families. The pheromone components were shown to be biosynthesized from hexadecanoic and tetradecanoic acid, respectively by Z11-desaturation followed by chain shortening, reduction, and acetylation. The EAG responses of males trapped with the typicalD. tutti andD. chrysitis blends, as well as with an intermediate blend, were investigated. Males trapped with theD. tutti mixture almost exclusively had a clearly broken wing marking and showed strongest EAG response to Z7-10:OAc. The intermediate blend and theD. chrysitis mixture gave more mixed catches, but with a prevalence of males with an unbroken (or almost unbroken) wing marking and with a higher mean response to Z5-10:OAc. Some males with typicalD. tutti EAG responses were attracted in the field to theD. chrysitis pheromone. In the flight tunnel someD. chrysitis males were attracted also to theD. tutti mixture. This indicates that cross attraction may take place between the two taxa under natural conditions.     

(6Z,9Z-3R,4S)-Epoxy-heptadecadiene: major sex pheromone component of the larch looper,Semiothisa sexmaculata (Packard) (Lepidoptera: Geometridae)

Gas chromatographic-electroantennographic analysis (GC-EAD) of female larch looper,Semiothisa sexmaculata (Packard), gland extracts revealed two EAD-active compounds. Retention index calculations, GC-mass spectroscopy in selected ion monitoring mode, and GC-EAD analysis of authentic standards identified the compounds as (3Z,6Z,9Z)-heptadecatriene (3Z,6Z,9Z-17H) and (6Z,9Z)-cis-3,4-epoxy-heptadecadiene (6Z,9Z-cis-3,4-epoxy-17H). Chirality determination of the monoepoxydiene in gland extracts was impeded by small quantities, but field experiments indicated that maleS. sexmaculata were most strongly attracted to enantiomerically enriched 6Z,9Z-3R,4S-epoxy-17H (69% ee), while maleS. neptaria (Guenée) responded well to various blends of theR,S- and S,R-epoxide enantiomers. Binary combinations of theR,S-epoxide enantiomer with 3Z,6Z,9Z-17H significantly inhibited response by maleS. sexmaculata, but strongly enhanced attraction of sympatric maleS. marmorata Ferguson. Enantiomerically enriched 6Z,9Z-3R,4S-epoxy-17H can be used as a trap bait to monitor populations of the larch-defoliatingS. sexmaculata. Whether 6Z,9Z-3R,4S-epoxy-17H serves as single component sex pheromone inS. sexmaculata or small amounts of 6Z,9Z-3S,4R-epoxy-17H synergize or suppress optimal attraction, will be tested as chirally pure monoepoxydienes become available.     

β-Phellandrene: kairomone for pine engraver,Ips pini (Say) (Coleoptera: Scolytidae)

The responses ofIps pini (Scolytidae) to multiple-funnel traps baited with the pheromone, ipsdienol, and various monoterpenes were determined in stands of lodgepole pine in southern and central British Columbia.Ips pini was attracted to both ipsdienol and -phellandrene, demonstrating that -phellandrene is a kairomone for this species.Lasconotus complex (Colydiidae) and aCorticeus sp. (Tenebrionidae) were attracted to both ipsdienol and -phellandrene. TheCorticeus sp. exhibited a synergistic response to the combination of ipsdienol and -phellandrene; the responses of the other two species to the combination were additive. The predators,Thanasimus undatulus, Enoclerus sphegeus, andE. lecontei (Cleridae), were attracted to ipsdienol-baited traps, whileMonochamus clamator (Cerambycidae) andDendroctonus ponderosae (Scolytidae) were attracted to -phellandrene. Attraction of all eight species increased with increasing release rates of ipsdienol and/or -phellandrene.     

Preparation,characterization, and properties of polylactide (PLA)–poly(ethylene glycol) (PEG) copolymers: A potential drug carrier

Polylactide (PLA)-poly(ethylene glycol) (PEG) copolymers were synthesized from polyethylene glycol and D ,L -lactide using low toxic stannous octoate as catalyst at 180°C by bulk polymerization. The copolymers were characterized by GPC, IR, and ¹³C-NMR. A full assignment NMR spectrum is presented. The physical, drug release, and biodegradable properties in vitro of PLA–PEG copolymers were investigated. The result indicates that the rates of drug release and biodegradation could be tailored by adjusting polymer composition. This amorphous material might be used as a drug carrier in medical applications.     

Multispecies trapping ofHelicoverpa (Heliothis) zea,Spodoptera frugiperda,Pseudaletia unipuncta,andAgrotis ipsilon (Lepidoptera: Noctuidae)

Multispecies sex pheromone trapping (trapping of more than one species in the same trap) for the bollworm,Helicoverpa (Heliothis) zea (Boddie); fall armyworm,Spodoptera frugiperda (J.E. Smith); armyworm,Pseudaletia unipuncta (Haworth); and the black cutworm,Agrotis ipsilon (Hufnagel) was evaluated. Baiting of individual traps with all possible combinations of the four species taken two at a time caused a reduction in the catches of at least one of any two species involved when compared to traps baited for only one species. These results demonstrated the species specificity of sex pheromones identified for these species. Although the effects were reduced in some cases, the interaction between species also was observed when adjacent traps were baited with the sex pheromone dispensers of the different species. These results indicate that the spacing between pheromone traps when more than one species are being trapped at the same site affects trap capture and should be evaluated further.This paper reports the results of research only. Mention of a commercial or proprietary product does not constitute an endorsement by the USDA.     

Sex pheromone of the mullein bug,Campylomma verbasci (Meyer) (Heteroptera: Miridae)

The first known sex pheromone for the family Miridae is reported for the mullein bug,Campylomma verbasci (Meyer) (Heteroptera: Miridae). Extracts of and Porapak Q-trapped volatiles from females were attractive to males in field bioassays. Butyl butyrate and hexyl butyrate were the predominant compounds in the females' volatiles, but these compounds previously had been found to be inactive when released alone or in combination. Butyl butyrate in combination with an isolated trace chemical, (E)-crotyl butyrate (which was inactive alone), rivaled the attraction elicited by five live females. When synthetic butyl butyrate and (E)-crotyl butyrate in a 16: 1 ratio were released at 91 or 183 g/day, they comprised an effective attractant for male bugs.     

Sex pheromone of tobacco stem borer,Scrobipalpa heliopa (Lower) (Lepidoptera: Gelechiidae)

The major volatile component in the extract of the female sex pheromone gland ofScrobipalpa heliopa was shown to be (E)-3-tridecen-1-ol acetate (V). The identification was based on mass spectral analyses, comparison of retention times with those of synthetic compounds on polar, nonpolar, and liquid crystal gas chromatographic columns and microchemical studies. The latter included hydrolysis and reacetylation, and mass spectral studies of the derivatives formed by epoxidation and methoxymercuration-demercuration. Analysis of gland extracts by gas chromatography linked to electroantennography showed this component to be the only one with significant biological activity, similar to that of the synthetic compound. (E)-3-Tridecenyl acetate (V) attracted male moths to traps in the field while addition of theZ isomer (III) reduced the numbers of moths caught.     

Sex pheromone of the avocado pest,Amorbia cuneana (Walsingham) (Lepidoptera: Tortricidae)

The major volatile components in the extract of the female sex pheromone gland ofAmorbia cuneana consisted of (E,E)- and (E,Z)-10,12-tetradecadien-1-ol acetates. The identification was based on electroantennogram bioassay of gas Chromatographic effluent from sex pheromone gland extract, relative retention times on polar and nonpolar gas chromatographic columns, chemical degradation (ozonolysis, saponification), mass spectrometry, chemical synthetic methods, and field tests. Based on mass spectrometry and retention times by capillary gas chromatography, traces of (E)-10-tetradecen-1-ol acetate and 1-tetradecanol acetate were also present in the extract. Traps baited with a combination of synthetic (E,E)- and (E,Z)-10,12-tetradecadien-1-ol acetates caught more males than did traps baited with females.This paper reports the results of research only. Mention of a commercial product in this paper does not constitute a recommendation by the U.S. Department of Agriculture.     

Sex pheromone of the cranberry girdler,Chrysoteuchia topiaria (Zeller) (Lepidoptera: Pyralidae)

Z-11-Hexadecen-1-al (Z11-16A1), free of theE isomer, was identified in extracts of femaleChrysoteuchia topiaria (Zeller) abdominal tips. In commercial grass seed fields, traps baited with synthetic Z11-16A1 were almost as attractive as female-baited traps. An alcohol, thought to be Z-11-hexadecen-1-ol on the basis of gas Chromatographic retention times, was also isolated from the extract.     

二二甲亚砜合硫氰酸镉（DSTC）晶体的合成、结构、表征与晶体生长

合成了金属有机配合物晶体二二甲亚砜合硫氰酸镉Cd(SCN) 2 (C2 H6 OS) 2 (简称DSTC)。用X射线四圆衍射方法确定了此化合物的晶体结构。用元素分析、红外光谱对其进行了化学表征。首次在DMSO/水的溶剂中 ,生长出尺寸为 3 5mm× 12mm× 11mm透明单晶。     

UV-activated hydrosilylation of (Me-Cp)Pt(Me)3: Enhanced photocatalytic activity,polymerization kinetics,and photolithography

Hydrosilylation is commonly known as a thermally induced addition reaction between unsaturated bonds and Si H bonds to synthesize or crosslink organosilanes and organosilicones, while it has emerged that it can also be activated under the coaction of UV irradiation and specific platinum catalyst. For higher photopolymerization conversion, excessive platinum catalyst is always required; however, this inevitably causes the significant increase of production cost and decrease of operation time. In this study, traces of trimethyl(methylcyclopentadienyl) platinum (IV) (Me-Cp)Pt(Me)₃ catalysts is combined with different photosensitizers (PSs) to efficiently promote the UV-activated hydrosilylation. Naphthalene is found to be the most applicable PS, because it improves the photopolymerization conversion from about 70 to 100% for the crosslinking of silicone rubbers. This UV-activated hydrosilylation is more likely to follow the first-order reaction kinetics, and its activation energy is 30.9 kJ mol⁻¹. The mechanical properties and thermostability of UV-crosslinked silicone rubbers are also enhanced with the incorporation of naphthalene. Moreover, this UV-activated hydrosilylation of silicone rubbers reveals a potential role to prepare complicated geometry shapes by photolithography. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48251.     

Synthesis,characterization and crystal structure of bis(acetylacetonato)dimethanolnickel(II): [Ni(acac)2(MeOH)2]

Bis(acetylacetonato)dimethanolnickel(II) was isolated as turquoise needle-like crystals by recrystallization of bis(acetylacetonato)nickel(II) from methanol solution and fully characterized by ¹H and ¹³C NMR, FT-IR spectroscopy, and single crystal X-ray diffraction. The X-ray structure analysis gives essentially a triclinic unit cell of bis(acetylacetonato)dimethanolnickel(II) containing one centrosymmetric molecule of the formula Ni[(O₂C₅H₇)₂(OHCH₃)₂]. The Ni(II) ion is located at the inversion centre of a tetragonally distorted octahedral coordination sphere. The equatorial plane of the tetragonally distorted octahedral coordination sphere includes four O-donor atoms of two acetylacetonato ligands and the axial positions are occupied by two oxygen atoms of two methanol ligands.     

Mn(II), Co(II) and Ni(II) complexes of 4-(2-thiazolylazo)resorcinol: Syntheses, characterization, catalase-like activity, thermal and electrochemical behaviour

Manganese(II), cobalt(II) and nickel(II) acetates react with the ligand, 4-(2-thiazolylazo)resorcinol, to form complexes of general formula [ML₂] for MCo(II), Ni(II) and [ML₂]·2H₂O for MMn(II). Each of the azo complexes was characterized using elemental analysis, electrolytic conductance, UV–visible spectroscopy and magnetic susceptibility. An octahedral structure is proposed for all complexes prepared, which molar conductance data revealed to be non-electrolytes. IR spectra reveal that the ligand is coordinated to the metal ions in a tridentate manner via the resorcinol OH, azo N and thiazole N groups as donor sites. The electrochemical behaviour of the ligand and its complexes were obtained by cyclic voltammetry. Thermal decomposition studies were undertaken to secure additional information on the structure of the investigated compounds. The manganese(II) complex catalysed the disproportionation of hydrogen peroxide in the presence of imidazole.     

Living metathesis polymerization of (p-n-butyl-o,o,m,m-tetrafluorophenyl)acetylene by MoOcl4-n-Bu4Sn-EtOH (1:1:1)

Summary Possibility of living metathesis polymerization by Mo catalysts was examined for (p-n-butyl-o,o,m,m-tetrafluorophenyl)acetylene, which has two fluorine atoms at both ortho positions. The MoOCl₄-n-Bu₄Sn-EtOH (1:1:1) catalyst yielded a polymer with narrow molecular weight distribution ( ), but the corresponding MoCl₅-based catalyst did not formed such a polymer. With the former catalyst, the number-average molecular weight of polymer increased in direct proportion to monomer conversion, while the molecular weight distribution remained narrow; this proves the livingness of the polymerization. The optimal conditions for the living polymerization were [n-Bu₄Sn]/[MoOCl₄]=∼1.0, [EtOH]/[MoOCl₄]=0.5–1.5, and temperature≤30 °C. n-Butyl acetate and acetone as well as EtOH were effective as third catalyst components.     

Developing Carrier Complexes for "Caged NO": RuCl(3)(NO)(H(2)O)(2) Complexes of Dipyridylamine, (dpaH), N,N,N'N'-Tetrakis (2-Pyridyl) Adipamide, (tpada), and (2-Pyridylmethyl) Iminodiacetate, (pida)

Delivery agents which can carry the {Ru(NO)}(6) chromophore ("caged NO") are desired for vasodilation and for photodynamic therapy of tumors. Toward these goals, complexes derived from [RuCl(3)(NO)(H(2)O)(2)]= (1) have been prepared using dipyridylamine (dpaH) as mono and bis adducts, [Ru(NO)Cl(3)(dpaH)] = (2) and [Ru(NO)Cl(dpaH)(2)]Cl(2) = (3). The dpaH ligands coordinate cis to the Ru(NO) axis.The mono derivative is a model for a potential DNA groove-spanning binuclear complex {[RuNO)Cl(3)](2)(tpada)} = (4) which has two DNA-coordinating Ru(II) centers, photo-labile {Ru(NO)}(6) sites, and a groove-spanning tether moiety.The binuclear assembly is prepared from the tethered dipyridylamine ligand N,N,N',N'-tetrakis(2-pyridylmethyl)adipamide (tpada) which has recently been shown to provide a binuclear carrier complex suited to transporting Ru(II) and Pd(II) agents. A related complex, [Ru(NO)Cl(pida)] = (5) with the {Ru(NO)}(6) moiety bound to (2-pyridylmethyl) iminodiacetate (pida(2-)) is also characterized as a potential "caged NO" carrier. Structural information concerning the placement of the pyridyl donor groups relative to the {Ru(NO)}(6) unit has been obtained from (1)H and (13)C NMR and infrared methods, noting that a pyridyl donor trans to NO+ causes "trans strengthening" of this ligand for [Ru(NO)Cl(pida)], whereas placement of pyridyl groups cis to NO+ causes a weakening of the N-O bond and a lower NO stretching frequency in the dpa-based complexes.     

Octa-O-bis-(R,R)-Tartarate Ditellurane (SAS) - a novel bioactive organotellurium(IV) compound: synthesis, characterization, and protease inhibitory activity

Octa-O-bis-(R,R)-Tartarate Ditellurane (SAS) is a new Te(IV) compound, comprised of two tellurium atoms, each liganded by four oxygen atoms from two carboxylates and two alkoxides of two tartaric acids. Unlike many other Te(IV) compounds, SAS was highly stable in aqueous solution. It interacted with thiols to form an unstable Te(SR)(4) product. The product of the interaction of SAS with cysteine was isolated and characterized by mass spectroscopy and elemental analysis. SAS selectively inactivated cysteine proteases, but it did not inactivate other families of proteolytic enzymes. It displayed selectivity towards the cysteine protease cathepsin B, a human enzyme of pharmaceutical interest, with a second order rate constant k(i)/K(i)=5900 M(-1) s(-1).