Synthesis, Properties, and Functionalization of Poly(ferrocenylsilane)s with Chloroalkyl Side Chains

A series of poly(ferrocenylsilane)s containing chloroalkyl side chains of increasing length is reported. By reacting fcLi₂· tmeda with Cl₂SiMeR, the corresponding [1]ferrocenophanes were prepared (2a, R=CH₂Cl; 2b, R=CH₂CH₂Cl; and 2c, R=CH₂CH₂CH₂Cl). Transition metal-catalyzed or thermal ring-opening polymerization (ROP) of these monomers yielded the polyferrocenes 3a, 3b, and 3c. The chlorine substituents of polymers 3a and 3b were unreactive toward nucleophilic substitution. In contast, polymer 3c could be reacted with 4-dimethylaminopyridine in DMF to afford the water-soluble poly(ferrocenylsilane) 4. This represents a new method for the preparation of water-soluble polyferrocenes.     

Enders’ SAMP‐Hydrazone as Traceless Auxiliary in the Asymmetric 1,4‐Addition of Cuprates to Enones

Conjugate additions of Gilman cyanocuprates to (S)‐N‐amino‐2‐(methoxymethyl)pyrrolidine (SAMP)‐hydrazones 4 , 5 derived from cyclic and acyclic α,β‐unsaturated ketones were investigated. A protocol utilizing copper(II) sulfate/ammonium chloride was evolved, which allowed cleavage of SAMP (S)‐ 1 under the hydrolysis and work‐up conditions, followed by recovery of the auxiliary with ethylenediaminetetraacetic acid (EDTA). The enantioselectivity of cuprate additions was dominated for cyclic SAMP‐hydrazones 4 by the cuprate alkyl substituent and the ring size, in the case of acyclic arylidene SAMP‐hydrazones 5 , however, by the nature of the aryl substituent. Electron‐donating substituents gave poor enantiomeric excesses, whereas electron‐withdrawing groups provided excellent ee values of 98–99%. The configuration of the new stereocenter was determined to be (R). Moreover, a reaction sequence was developed which integrates a tandem 1,4‐addition/methylation and traceless hydrolytic cleavage of the auxiliary (S)‐ 1 in a one‐pot reaction, resulting in enantiomerically pure methyl ketones 11 – 13 , each of them with>99% ee.     

Comparison of the Structures of Triacylglycerols from Native and Transgenic Medium-Chain Fatty Acid-Enriched Rape Seed Oil by Liquid Chromatography–Atmospheric Pressure Chemical Ionization Ion-Trap Mass Spectrometry (LC–APCI-ITMS)

The sn position of fatty acids in seed oil lipids affects physiological function in pharmaceutical and dietary applications. In this study the composition of acyl-chain substituents in the sn positions of glycerol backbones in triacylglycerols (TAG) have been compared. TAG from native and transgenic medium-chain fatty acid-enriched rape seed oil were analyzed by reversed-phase high performance liquid chromatography coupled with online atmospheric-pressure chemical ionization ion-trap mass spectrometry. The transformation of summer rape with thioesterase and 3-ketoacyl-[ACP]-synthase genes of Cuphea lanceolata led to increased expression of 1.5% (w/w) caprylic acid (8:0), 6.7% (w/w) capric acid (10:0), 0.9% (w/w) lauric acid (12:0), and 0.2% (w/w) myristic acid (14:0). In contrast, linoleic (18:2n6) and alpha-linolenic acid (18:3n3) levels decreased compared with the original seed oil. The TAG sn position distribution of fatty acids was also modified. The original oil included eleven unique TAG species whereas the transgenic oil contained sixty. Twenty species were common to both oils. The transgenic oil included trioctadecenoyl-glycerol (18:1/18:1/18:1) and trioctadecatrienoyl-glycerol (18:3/18:3/18:3) whereas the native oil included only the latter. The transgenic TAG were dominated by combinations of caprylic, capric, lauric, myrisitic, palmitic (16:0), stearic (18:0), oleic (18:1n9), linoleic, arachidic (20:0), behenic (22:0), and lignoceric acids (24:0), which accounted for 52% of the total fat. In the original TAG palmitic, stearic, oleic, and linoleic acids accounted for 50% of the total fat. Medium-chain triacylglycerols with capric and lauric acids combined with stearic, oleic, linoleic, alpha-linolenic, arachidic, and gondoic acids (20:1n9) accounted for 25% of the transgenic oil. The medium-chain fatty acids were mainly integrated into the sn-1/3 position combined with the essential linoleic and alpha-linolenic acids at the sn-2 position. Eight species contained caprylic, capric, and lauric acids in the sn-2 position. The appearance of new TAG in the transgenic oil illustrates the extensive effect of genetic modification on fat metabolism by transformed plants and offers interesting possibilities for improved enteral applications.     

Interaction Between Atmospheric CO<Subscript>2</Subscript> and Glucosinolates in Broccoli

Total and individual glucosinolate contents of broccoli cv Marathon were assessed at ambient CO₂ (430–480 ppm) and elevated atmospheric CO₂ (685–820 ppm) to determine the ecological relationship between changing atmospheric CO₂ concentrations and phytochemicals. Elevated atmospheric CO₂ concentration had a differing effect on individual glucosinolates and glucosinolate groups. Total glucosinolate content increased at elevated atmospheric CO₂ concentration as a result of a strong increase in both methylsulfinylalkyl glucosinolates glucoraphanin and glucoiberin. In contrast, indole glucosinolates simultaneously decreased, predominantly because of a reduction of glucobrassicin and 4-methoxy-glucobrassicin contents. We conclude that changes in N content and N/S ratios as well as alterations in photochemical processes at elevated atmospheric CO₂ concentration can influence total and individual glucosinolates contents of Brassicaceae, as demonstrated in the greenhouse, for broccoli.     

木窗表面处理——现代化生产过程中如何使木窗得到最好的表面处理

木窗,包括纯木窗,铝包木窗和木铝复合窗,作为一种相对新兴的窗型,近些年在国内发展迅速.而作为一种成熟产品,木窗在欧洲已经存在完整的生产和安装标准.我们可以借鉴国外的成熟技术加速自身完善.     

Psyllium, not pectin or guar gum, alters lipoprotein and biliary bile acid composition and fecal sterol excretion in the hamster

Different soluble dietary fibers known to alter cholesterol metabolism were fed to golden Syrian hamsters, and their specific impact on lipoproteins, biliary bile acid profile, and fecal sterol excretion was evaluated. Semipurified diets containing 20% fat; 0.12% cholesterol; and 8% of psyllium (PSY); high (hePE) and low (lePE) esterified pectin; or high (hvGG) and low (lvGG) viscous guar gum were fed for 5 wk. Compared to control, PSY caused a significant reduction in plasma cholesterol (2.9±0.5 vs. 5.5±0.5 mmol/L), whereas hePE, lePE, hvGG, or lvGG had no apparent effect on plasma lipids. Hepatic total and esterified cholesterol were substantially decreased with PSY, pectin and guar gum, whereby PSY produced the most pronounced effect. Distinctive changes existed in the bile acid profile related to the different fibers. In contrast to pectin and guar gum, PSY caused a significant increase in the cholate:chenodeoxycholate and the glycine:taurine conjugation ratio. Pectin and guar gum did not alter daily fecal neutral sterol excretion while PSY caused a 90% increase due to a higher fecal output. Daily fecal bile acid excretion and total fecal bile acid concentration were significantly increased by PSY, whereas hePE, lePE, hvGG, and lvGG revealed no or only minor effects. Taken together, the disparate hypocholesterolemic effects of PSY, pectin, and guar gum on cholesterol and bile acid metabolism in the hamster are possibly related to different physicochemical properties, e.g., viscosity and susceptibility to fermentation, affecting the fiber-mediated action in the intestine.     

Substrate-induced coagulation (SIC) of nano-disperse carbon black in non-aqueous media: a method of manufacturing highly conductive cathode materials for Li-ion batteries by self-assembly

Substrate-induced coagulation (SIC) is a coating process based on self-assembly for coating different surfaces with fine particulate materials. The particles are dispersed in a suitable solvent and the stability of the dispersion is adjusted by additives. When a surface, pre-treated with a flocculant e.g. a polyelectrolyte, is dipped into the dispersion, it induces coagulation resulting in the deposition of the particles on the surface. A non-aqueous SIC process for carbon coating is presented, which can be performed in polar, aprotic solvents such as N-Methyl-2-pyrrolidinone (NMP). Polyvinylalcohol (PVA) is used to condition the surface of substrates such as mica, copper-foil, silicon-wafers and lithiumcobalt oxide powder, a cathode material used for Li-ion batteries. The subsequent SIC carbon coating produces uniform layers on the substrates and causes the conductivity of lithiumcobalt oxide to increase drastically, while retaining a high percentage of active battery material.     

Influence of a Natural Plant Antioxidant on the Ageing Process of Ethylene-norbornene Copolymer (Topas)

In the field of polymer technology, a variety of mainly synthetic additives are used to stabilize the materials during processing. However, natural compounds of plant origin can be a green alternative to chemicals such as synthetic polyphenols. An analysis of the effect of hesperidin on the aging behavior of ethylene-norbornene copolymer was performed. The evaluation of changes in the tested samples was possible by applying the following tests: determination of the surface energy and OIT values, mechanical properties analysis, colour change measurements, FT-IR and TGA analyses. The obtained results proved that hesperidin can be effectively used as natural stabilizer for polymers. Furthermore, as a result of this compound addition to Topas-silica composites, their surface and physico-mechanical properties have been improved and the resistance to aging significantly increased. Additionally, hesperidin can act as a dye or colour indicator and only few scientific reports describe a possibility of using flavonoids to detect changes in products during their service life, e.g., in food packaging. In the available literature, there is no information about the potential use of hesperidin as a stabilizer for cycloolefin copolymers. Therefore, this approach may contribute not only to the current state of knowledge, but also presents an eco-friendly solution that can be a good alternative to synthetic stabilizers.