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1.
The thiol‐ene reaction between trans‐limonene oxide (trans‐LO) and ethane‐1,2‐dithiol in the presence of triethylborane affords a bio‐based bis‐functional epoxide (bis‐trans‐LO). The crosslinking reaction of bis‐trans‐LO with branched polyethyleneimine (BPEI; Mn = 600; BPEI600) at a feed ratio of bis‐trans‐LO/BPEI600 = 57/43 (wt/wt) yields the corresponding network polymer with Td10 (10% thermal decomposition temperature) of 304.7 °C in 98% yield. In contrast, negligible amounts of network polymer are obtained by the reaction of bis‐LO (bis‐functional epoxide derived from cis and trans‐LO) and BPEI600 regardless of the feed ratio. The mechanical strengths as measured by direct tensile tests of the network polymers derived from bis‐trans‐LO and BPEI600,1800 (Mn = 600 and 1800) were approximately 16 and 11 times higher than that of bis‐LO and BPEI1800, respectively. The tensile shear strengths of the metal‐to‐metal adhesive bonds induced by bis‐trans‐LO and BPEI600,1800 were 9.5 and 14.1 MPa, respectively. DMA revealed that the storage modulus of the network polymer derived from bis‐trans‐LO and BPEI1800 in the rubber region was higher than that of the material prepared from bis‐LO and BPEI1800, indicating higher crosslink density of the bis‐trans‐LO/BPEI1800 system. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2466–2473  相似文献   
2.
Total synthesis of cordiaquinone K, a new antifungal and larvicidal meroterpenoid, is reported. The absolute configuration of cordiaquinone K was confirmed by the synthesis.  相似文献   
3.
Time-of-Flight (TOF) neutron diffraction measurements have been carried out on aqueous 8 mol% sodium acetate solutions in D2O. Scattering cross sections that were observed for sample solutions involving 12C/13C and H/D isotopically substituted acetate ions were used to derive the first-order difference functions, ΔH(Q) and ΔC(Q), and corresponding distribution functions, G H(r;r) and G C(r;r), which describe the environmental structure around the methyl and the carboxyl groups within the acetate ion, respectively. Structural parameters concerning the first hydration shell of the carboxyl group within the acetate ion were obtained through the least squares fit to the observed intermolecular difference function, ΔC inter(Q). The nearest neighbor C O...D W1 (CO: carboxyl carbon atom, DW1: water deuterium atom) distance, r(C O...D W1 ), and the angle, ∠ C O ...D W1 -O W (O W : water oxygen atom), were determined to be 2.63(1) Å and 120(1)°, respectively. The coordination number, n(C O ...D W1 ), was obtained to be 4.0(1). These results are consistent with the hydration structure in which water molecules in the first hydration shell of the carboxyl group are hydrogen-bonded with oxygen atoms of the carboxyl group.  相似文献   
4.
The change in the conformation of the flexible O-CH2-CH2-CH2-O segment of poly(trimethylene terephthalate) (PTT) monofilament caused by drawing was investigated by means of the gamma-gauche effect on the 13C solid-state NMR chemical shift of the internal methylene carbon, combined with the NMR relaxations. The conformation around the O-CH2 and CH2-O bonds for as-spun fiber was trans/trans. On drawing, followed by heat treatment, the conformation changed to gauche/gauche. The ratio of gauche/gauche to trans/trans for the drawn PTT fiber was determined quantitatively.  相似文献   
5.
The external chiral ligand-controlled asymmetric conjugate addition reaction of lithium amides with alpha,beta-unsaturated esters provided beta-amino esters in high yields and high enantioselectivities.  相似文献   
6.
The reaction of lithium ester enolate with enones provides a challenge for chemoselectivity, that is, discrimination between a conjugate addition and a 1,2-addition. Asymmetric conjugate addition of a lithium enolate of alpha-trimethylsilanylacetate to acyclic and cyclic alpha,beta-unsaturated ketones was mediated by an external chiral ligand to give the corresponding 1,4-adducts in good enantioselectivity of 74% and good chemoselectivity.  相似文献   
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8.
Paramagnetic NMR and optical studies of the oxidized forms of mesophile Pseudomonas aeruginosa cytochrome c(551) and its quintuple mutant (F7A/V13M/F34Y/E43Y/V78I), and thermophile Hydrogenobacter thermophilus cytochrome c(552) demonstrated that the amino acid side chain packings in the protein interior influence the coordination bond between the heme iron and the axial methionine in the proteins. The strength of heme axial coordinations was found to correlate with the overall protein thermostability.  相似文献   
9.
H2 generation during mechanochemical treatment of kaolinite by dry grinding was examined by X-ray diffraction analysis, Fourier transform infrared spectroscopy, and BET surface area measurement. The H2 concentration in the mill pot, measured by gas chromatography, increased with grinding time up to a maximum concentration of 156 ppm (0.35 micromol) after 600 min. This H2 generation is considered to occur as a result of three processes: (1) structural destruction characterized by the delamination and loss of hydroxyl groups as a result of dry grinding, (2) transformation of liberated hydroxyls into water molecules by mechanochemical effects such as prototropy, and (3) H2 generation through reaction between surface water molecules and mechanoradicals created by the rupture of Si-O or Al-O-Si bonds. Although the surface area plateaued after 240 min grinding, the H2 concentration continued to increase, indicating that surface mechanoradicals are created during this later grinding stage. Thus, H2 generation can be used as an indicator of mechanoradical formation during mechanochemical treatment.  相似文献   
10.
The concentrations of l ‐tryptophan (Trp) and the metabolite l ‐kynurenine (KYN) can be used to evaluate the in‐vivo activity of indoleamine 2,3‐dioxygenase (IDO) and tryptophan 2,3‐dioxygenase (TDO). As such, a novel method involving derivatization of l ‐Trp and l ‐KYN with (R)‐4‐(3‐isothiocyanatopyrrolidin‐1‐yl)‐7‐(N,N‐dimethylaminosulfonyl)‐2,1,3‐benzoxadiazole (DBD‐PyNCS) and separation by high‐performance liquid chromatography (HPLC) with tandem mass spectrometric (MS/MS) detection on a triazole‐bonded column (Cosmosil HILIC®) was developed to determine their concentrations. The optimized mobile phase, CH3CN/10 mm ammonium formate in H2O (pH 5.0) (90:10, v/v) eluted isocratically, resulted in satisfactory separation and MS/MS detection of the analytes. The detection limits of l ‐Trp and l ‐KYN were approximately 50 and 4.0 pm , respectively. The column temperature affected the retention behaviour of the Trp and KYN derivatives, with increased column temperatures leading to increased capacity factors; positive enthalpy changes were revealed by van't Hoff plot analyses. Using the proposed LC‐MS/MS method, l ‐Trp and l ‐KYN were successfully determined in 10 μL human serum using 1‐methyl‐l ‐Trp as an internal standard. The precision and recovery of l ‐Trp were in the ranges 2.85–9.29 and 95.8–113%, respectively, while those of l ‐KYN were 2.51–16.0 and 80.8–98.2%, respectively. The proposed LC‐MS/MS method will be useful for evaluating the in vivo activity of IDO or TDO. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   
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