Time-Dependent Density Functional Theory Study on Hydrogen and Dihydrogen Bonding in Electronically Excited State of 2-Pyridone–Borane–Trimethylamine Cluster

In this work, the intermolecular dihydrogen and hydrogen bonding interactions in electronically excited states of a 2-pyridone (2PY)–borane–trimethylamine (BTMA) cluster have been theoretically studied using time-dependent density functional theory method. Our computational results show that the S₁ state of 2PY–BTMA cluster is a locally excited state, in which only 2PY moiety is electronically excited. The theoretical infrared (IR) spectra of the 2PY–BTMA cluster demonstrate that the N–H stretching vibrational mode is slightly blue-shifted upon the electronic excitation. Moreover, the computed IR spectrum of the 2PY–BTMA cluster exhibits no carbonyl character due to the extension of the C=O bond length in the S₁ state. However, the N–H bond is shortened slightly upon photoexcitation. At the same time, the H···H and H···O distances are obviously lengthened in the S₁ sate by comparison with those in ground state. In addition, the electron density of the carbonyl oxygen is diminished due to the electronic excitation. Consequently, the proton acceptor ability of carbonyl oxygen is decreased in the electronic excited state. As a result, it is demonstrated that the intermolecular dihydrogen and hydrogen bonds are significantly weakened in the electronically excited state.     

铌酸锂钠钾纳米粉体的溶胶-凝胶法合成及其相转变

采用化学络合法将Nb2O5转化为可溶性铌盐作为铌源, 用溶胶-凝胶法, 在500～650 ℃成功煅烧合成了平均晶粒尺寸为20～60 nm的纯钙钛矿相铌酸锂钠钾[(Li0.06Na0.47K0.47)NbO3]无铅压电陶瓷粉体. 研究了晶粒尺寸对铌酸锂钠钾纳米粉体相结构的影响. 结果表明, 基于纳米尺寸效应, 随着晶粒尺寸由60减小到20 nm, 铌酸锂钠钾粉体的相结构由正交相逐渐过渡到四方相, 而室温下四方相向立方相的转变将发生在20 nm以下.     

Synthesis of Terphenyl Derivatives by Pd‐Catalyzed Suzuki‐Miyaura Reaction of Dibromobenzene Using 2N2O‐Salen as a Ligand in Aqueous Solution

A simple and efficient catalytic system for Na₂PdCl₄ catalyzing the Suzuki‐Miyaura reaction of dibromobenzene and arylboronic acid has been developed by using 2N2O‐salen as a ligand in H₂O/EtOH (V:V=4:1) at 100°C. Using this method, the reactions of substrates containing sterically demanding ortho substituents (e.g. dibromobenzene and/or arylboronic acids) proceeded efficiently, with the corresponding terphenyl derivatives being produced in moderate to excellent yields. Furthermore, this method offers interesting features for the multi‐gram scale synthesis of terphenyl compound.     

One‐pot synthesis of polyfluoroterphenyls via palladium‐catalyzed Suzuki–Miyaura coupling of chlorobromobenzene and CH bond functionalization of perfluoroarenes

An efficient tandem route for the synthesis of polyfluoroterphenyl derivatives has been developed. The target compounds were obtained in moderate to good yields by a Pd(OAc)₂‐catalyzed three‐component coupling reaction involving palladium‐catalyzed direct C? H activation of perfluoroarenes. This in turn will set the stage for a wide application of this useful reaction for the synthesis of fluorinated liquid crystal compounds containing the privileged polyfluoroterphenyl structure. Copyright © 2014 John Wiley & Sons, Ltd.     

稀土-吡唑啉酮-2,6-吡啶二羧酸配合物的合成、表征及其性质研究

以稀土氯化物、1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮和2,6-吡啶二羧酸为原料,制备了一类新型稀土三元配合物,通过元素分析、红外光谱、紫外光谱、热重-差热分析、光电子能谱分析及X射线粉末衍射等手段对配合物进行了表征,确定了该类配合物的化学组成可能为:Na2[RE(PMBP)3(PDA)]·nH2O(RE=Sm3+,Y3+,Er3+,其中La配合物含有一分子配位水)。抗菌实验结果表明,三元配合物对大肠杆菌、金黄色葡萄球菌具一定的抑制作用,Na2[Er((PMBP)3(PDA)]·5H2O对大肠杆菌作用较好,而Na2[Sm(PMBP)3(PDA)]·5H2O对金黄色葡萄球菌作用较好。采用紫外光谱法和荧光光谱法初步研究了配合物与CT-DNA的作用方式,结果表明配合物是以插入模式与DNA结合的。同时配合物Na2[Sm(PMBP)3(PDA)]·5H2O具有荧光特性,可用作荧光探针等,在生物活性上具有一定的应用前景。     

Tris(2,2′-bipyridyl)cobalt(III)-doped silica nanoparticle DNA probe for the electrochemical detection of DNA hybridization

A new and sensitive electrochemical DNA hybridization detection assay, using tris(2,2′-bipyridyl)cobalt(III) [Co(bpy)₃³⁺]-doped silica nanoparticles as the oligonucleotide (ODN) labeling tag, and based on voltammetric detection of Co(bpy)₃³⁺ inside silica nanoparticles, is described. Electro-active Co(bpy)₃³⁺ is not possible for directly linking with DNA, it is doped into the silica nanoparticles in the process of nanoparticles synthesis for DNA labeling with trimethoxysilylpropydiethylenetriamine (DETA) and glutaraldehyde as linking agents. The Co(bpy)₃³⁺ labeled DNA probe is used to hybridize with target DNA immobilized on the surface of glassy carbon electrode. Only the complementary sequence DNA (cDNA) could form a double-stranded DNA (dsDNA) with the DNA probe labeled with Co(bpy)₃³⁺ and give an obvious electrochemical response. A three-base mismatch sequence and non-complementary sequence had negligible response. Due to the large number of Co(bpy)₃³⁺ molecules inside silica nanoparticles linked to oligonucleotide DNA probe, the assay showed a high sensitivity. It allows the detection at levels as low as 2.0×10⁻¹⁰ mol l⁻¹ of the target oligonucleotides.     

蛋黄-壳结构Fe3O4@SiO2@PMO磁性微球的制备及对漆酶的固定化

以蛋黄-壳结构的Fe₃O₄@SiO₂@PMO磁性微球作为载体, 采用交联法对漆酶进行固定, 考察了戊二醛浓度等对固定效果的影响, 并对固定后漆酶的活性进行了研究. 结果表明, 蛋黄-壳结构的磁性微球负载漆酶仅需6 h, 磁性微球对漆酶的固载量高达475 mg/g. 固定后漆酶的稳定性显著提高, 在pH=2.5~4.5的强酸性条件下, 固定后漆酶酶活仍可保持70%以上, 即使温度升高至60 ℃, 固定后漆酶的相对酶活仍保持65%以上. 这说明漆酶经所合成的材料固定后, 其耐酸和耐热能力都明显优于游离漆酶. 包覆的Fe₃O₄粒子使得材料很容易经磁铁分离法回收, 固定后漆酶经磁分离循环使用10次后仍然能保留85%的酶活, 具有良好的可操作性和稳定性, 有效降低了漆酶的使用成本.     

Heterogeneous Metal–Organic-Framework-Based Biohybrid Catalysts for Cascade Reactions in Organic Solvent

In cooperative catalysis, the combination of chemo- and biocatalysts to perform one-pot reactions is a powerful tool for the improvement of chemical synthesis. Herein, UiO-66-NH₂ was employed to stepwise immobilize Pd nanoparticles (NPs) and Candida antarctica lipase B (CalB) for the fabrication of biohybrid catalysts for cascade reactions. Distinct from traditional materials, UiO-66-NH₂ has a robust but tunable structure that can be utilized with a ligand exchange approach to adjust its hydrophobicity, resulting in excellent catalyst dispersity in diverse reaction media. These attractive properties contribute to the formation of MOF-based biohybrid catalysts with high activity and selectivity in the synthesis of benzyl hexanoate from benzaldehyde and ethyl hexanoate. With this proof-of-concept, we reasonably expect that future tailor-made MOFs can combine other catalysts, ranging from chemical to biological catalysts for applications in industry.     

A posteriori error estimates of constrained optimal control problem governed by convection diffusion equations

In this paper, we study a posteriori error estimates of the edge stabilization Galerkin method for the constrained optimal control problem governed by convection-dominated diffusion equations. The residual-type a posteriori error estimators yield both upper and lower bounds for control u measured in L ²-norm and for state y and costate p measured in energy norm. Two numerical examples are presented to illustrate the effectiveness of the error estimators provided in this paper.