Dependence of electronic and optical properties of multilayer SiC and GeC on stacking sequence and external electric field

The electronic and optical properties of different stacked multilayer SiC and GeC are investigated with and without external electric field (EEF). The band gaps of multilayer SiC and GeC are found smaller than that of monolayer SiC and GeC due to the interlayer coupling effect. When EEF is applied, the direct band gaps (ΔK–M) of multilayer SiC and direct band gaps (ΔK–K) of multilayer GeC all turn to indirect band gaps (ΔK–G) as the band at the G point drops dramatically toward zero. The imaginary part ε₂(ω)s of multilayer SiC and GeC show that new absorption peaks between 2–5 eV appear when the polarized direction is perpendicular to the layer plane, and new absorption peaks in infrared region appear as the EEF is higher than a certain point when the polarized direction is parallel to the layer plane. Our calculations reveal that different stacking sequences and EEF can provide a wide tunable band structures and optical properties for multilayer SiC and GeC.     

Cloning and expression of L-asparaginase gene in Escherichia coli

The L-asparaginase (ASN) from Escherichia coli AS1.357 was cloned as a DNA fragment generated using polymerase chain reaction technology and primers derived from conserved regions of published ASN gene sequences. Recombinant plasmid pASN containing ASN gene and expression vector pBV220 was transformed in different E. coli host strains. The activity and expression level of ASN in the engineering strains could reach 228 IU/mL of culture fluid and about 50% of the total soluble cell protein respectively, more than 40-fold the enzyme activity of the wild strain. The recombinant plasmid in E. coli AS1.357 remained stable after 72h of cultivation and 5h of heat induction without selective pressure. The ASN gene of E. coli AS1.357 was sequenced and had high homology compared to the reported data.     

Size‐guided multi‐seed heuristic method for geometry optimization of clusters: Application to benzene clusters

Since searching for the global minimum on the potential energy surface of a cluster is very difficult, many geometry optimization methods have been proposed, in which initial geometries are randomly generated and subsequently improved with different algorithms. In this study, a size‐guided multi‐seed heuristic method is developed and applied to benzene clusters. It produces initial configurations of the cluster with n molecules from the lowest‐energy configurations of the cluster with n − 1 molecules (seeds). The initial geometries are further optimized with the geometrical perturbations previously used for molecular clusters. These steps are repeated until the size n satisfies a predefined one. The method locates putative global minima of benzene clusters with up to 65 molecules. The performance of the method is discussed using the computational cost, rates to locate the global minima, and energies of initial geometries. © 2018 Wiley Periodicals, Inc.     

基于微流控芯片的72重单核苷酸多态性族群推断系统的构建

建立了常染色体单核苷酸多态性（SNPs）复合检测芯片体系,用于未知个体的族群来源推断。基于前期筛选的74-SNPs组合,采用竞争性等位基因特异性聚合酶链式反应（PCR）的原理构建SNPs的扩增体系,在微流控芯片的每个反应孔内完成一个SNP的检测,通过高通量PCR微流控芯片实现了其中72个SNPs的同步检测。芯片的扩增由平板PCR仪完成,反应孔的荧光信号通过激光共聚焦扫描仪检测,最终通过提取的荧光值进行结果分析。使用该芯片检测获得52份样本的SNPs分型,分型结果的准确率为100%。以57个人群的3628个样本为参考人群数据库,进行20份样本的族群来源推断,推断结果与样本的实际来源一致。本研究建立的常染色体72个SNPs微流控芯片体系可以有效地进行SNP多态性分析检测,基于参考数据库,20份检测样本族群推断的准确性为100%。     

Synthesis and characterization of fully aromatic thermotropic liquid‐crystalline copolyesters containing m‐hydroxybenzoic acid units

A series of fully aromatic copolyesters based on p‐acetoxybenzoic acid (p‐ABA), hydroquinone diacetate (HQDA), terephthalic acid (TPA), and m‐acetoxybenzoic acid (m‐ABA) were prepared by a modified melt‐polycondensation reaction. The copolyesters were characterized by DSC, thermogravimetric analysis, ¹H NMR, polarized optical microscopy, X‐ray diffraction, and intrinsic viscosity measurements. The copolyesters exhibited nematic liquid‐crystalline phases in a broad temperature range of about 150 °C, when the content of linear (p‐ABA, HQDA, and TPA) units was over 67 mol %. DSC analysis of the anisotropic copolyesters revealed broad endotherms associated with the nematic phases, and the melting or flow temperatures were found to be in the processable region. The flow temperatures and crystal‐to‐nematic and nematic‐to‐isotropic transitions depend on the type of linear monomer units, and these transitions increased as the content of the p‐ABA units increased, as compared to the HQDA/TPA units. When the content of the p‐ABA units increased, as compared to other linear units (HQDA and TPA), the intrinsic viscosity and degree of crystallinity of the copolyesters also increased, implying a higher reactivity for p‐ABA in the p‐ABA/HQDA/TPA/m‐ABA polymer system. The aromatic region in the ¹H NMR spectra of the copolyesters containing equal molar compositions of p‐ABA, HQDA, and TPA units were sensitive to the sequence distribution of aromatic rings. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3263–3277, 2001     

Thermodynamic molecular switch in sequence‐specific hydrophobic interactions

This communication will demonstrate the existence of a thermodynamic molecular switch in the pairwise, sequence‐specific hydrophobic interaction of Ile–Ile, Leu–Ile, Val–Leu, or Ala–Leu over the temperature range of 273–333 K reported by Nemethy and Scheraga in 1962. Based on Chun's development of the Planck–Benzinger methodology, the change in inherent chemical bond energy at 0 K, ΔH°(T₀), is 3.0 kcal mol^?1 for Ile–Ile, 2.4 for Leu–Ile, 1.8 for Val–Leu, and 1.2 kcal mol^?1 for Ala–Leu. The value of ΔH°(T₀) decreases as the length of the hydrophobic side chain decreases. It is clear that the strength and stability of the hydrophobic interaction is determined by the packing density of the side chains, with Ala–Leu being the most stable. At 〈T_m〉, the thermal agitation energy, $\int^{T}_{0}\Delta Cp^{\circ}(T)\,dT$, is about five times greater than ΔH°(T₀) in each case. Additionally, the thermal agitation energy for the same series, evaluated at 〈T_m〉, decreases in the same order, that is, as the length of the side chain decreases. This pairwise, sequence‐specific hydrophobic interaction is highly similar in its thermodynamic behavior to that of other biological systems, except that the negative Gibbs free energy change minimum at 〈T_s〉 occurs at a considerably higher temperature, 355 K compared to about 300 K. The melting temperature, 〈T_m〉, is also high, 470 K compared to 343 K in a biological system. The implication is that the negative Gibbs free energy minimum at a well‐defined 〈T_s〉 has it origin in the hydrophobic interactions, which are highly dependent on details of molecular structure. In addition to the four specific dipeptide interactions described, we have shown in our unpublished work the existence of a thermodynamic molecular switch in the interactions of 32 dipeptides wherein a change of sign in ΔCp°(T)_reaction leads to a true negative minimum in the Gibbs free energy of reaction, and hence, a maximum in the related K_eq. Indeed, all interacting biological systems that we have thus far examined using the Planck–Benzinger approach point to the universality of thermodynamic molecular switches. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Modification of silica gel with diethylamino group by novel reaction and its characterization

1,3,5,7-Tetramethylcyclotetrasiloxane (H₄) was deposited on silica gel at 80°C by utilizing a chemical vapor deposition (CVD) method, where it was catalytically polymerized to form a surface coating of polymethylsiloxane (PMS). Treated silica gel (PMS-Si) increased in weight up to a plateau level, and there was no further increase with increasing reaction time. The film of PMS was partially cross linked; typical values of crosslinking ratio and film thickness were 2% and 0.6 nm, respectively. An anionic ion exchanger containing diethylamino groups was synthesized from PMS-Si by hydrosilylation of allyl glycidyl ether followed by treatment with diethylamine. Its structure was confirmed by¹³C and²⁹Si CP/MAS NMR spectroscopy and FT-IR spectrophotometry. Characterization of silica gel (DEA-Si) modified with diethylamino group was evaluated by a packing of the column for liquid chromatography. As a mixture of five nucleotides was completely separated, it was recognized that DEA-Si was operated by ion exchange action. Because the surface of the silica gel was covered with hydrophobic PMS, the peak heights and retention times did not change after washing of the column with alkaline solution.     

Mild conversion of propargylic alcohols to α,β-unsaturated enones in ionic liquids (ILs); a new ‘metal free’ life for the Rupe rearrangement

A mild and selective transition metal free protocol for the conversion of propargylic alcohols to cyclic and acyclic α,β-unsaturated enones via the Rupe rearrangement is reported. The method utilizes the Brønsted acidic ionic liquid [BMIM-SO₃H][OTf] as catalyst and [BMIM][PF₆] as solvent and offers the potential for recycling and reuse of the IL solvent. The feasibility to synthesize bicyclic fused cyclopentenone derivatives via a Rupe → Aldol → Nazarov sequence utilizing this protocol has also been demonstrated.     

滴加顺序对制备酯加氢催化剂Cu-Zn-Al-Ba的影响

采用共沉淀法以不同的滴加混合顺序制备了新型高效无铬Cu-Zn-Al-Ba催化剂,通过XRD、SEM、BET、H₂-TPR和TG等表征方式进行了分析,对其前驱体、焙烧后和还原后催化剂物相进行分析研究,探究了相同条件下不同滴加混合顺序对催化剂结构与催化性能的影响,同时考察了催化剂对C12~C18脂肪酸甲酯加氢制醇的催化性能以及重复利用性。结果表明,以混合盐溶液滴加沉淀剂所制备的无铬Cu-Zn-Al-Ba催化剂R-cat具有较好的酯加氢催化活性和稳定性。在230℃,3MPa氢压的反应条件下,R-cat催化C12~C18脂肪酸甲酯加氢制醇的收率和选择性都高于90%,催化剂重复利用5次,仍保持较高的催化活性。     

NMR analysis of the microstructure of poly(methyl acrylate-co-N-vinylcarbazole)

The microstructure of a series of high conversion copolymers of methyl acrylate (MA) and N-vinylcarbazole (NVC) was characterized by NMR. ¹H- and ¹³C-NMR spectra were assigned by comparison to the homopolymers and by using heteronuclear shift correlation spectroscopy. MA-centered triad distributions were obtained from the carbonyl carbon. Distributions of NVC sequences were determined from aromatic carbons 1 and 8a, and aromatic proton 1 These experimentally determined sequence distributions were compared to those calculated from reactivity ratios approximated from the copolymer compositions. Agreement was very good for low NVC content copolymers. Three signals were particularly useful in providing rapid assessment of the distribution of NVC units within low NVC content copolymers: proton 1 and carbon 1 of NVC and the carbonyl carbon of MA. © 1992 John Wiley & Sons, Inc.