Theoretical study on the mechanism of cycloaddition reaction between dimethyl germylidene and formaldehyde

The cycloaddition mechanism of the reaction between singlet dimethyl germylidene and formaldehyde has been investigated with MP2/6-31G* method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. The energies of the different conformations are calculated with CCSD (T)//MP2/6-31G* method. From the potential energy profile, we predict that the cycloaddition reaction between singlet dimethyl germylidene and formaldehyde has two dominant reaction pathways. First dominant reaction pathway consists of three steps: (1) the two reactants (R1, R2) firstly form an intermediate INT1a through a barrier-free exothermic reaction of 43.0 kJ/mol; (2) INT1a then isomerizes to a four-membered ring compound P1 via a transition state TS1a with an energy barrier of 24.5 kJ/mol; (3) P1 further reacts with formaldehyde(R2) to form a germanic heterocyclic compound INT3, which is also a barrier-free exothermic reaction of 52.7 kJ/mol; Second dominant reaction pathway is as following: (1) the two reactants (R1, R2) firstly form a planar four-membered ring intermediate INT1b through a barrier-free exothermic reaction of 50.8 kJ/mol; (2) INT1b then isomerizes to a twist four-membered ring intermediate INT1.1b via a transition state TS1b with an energy barrier of 4.3 kJ/mol; (3) INT1.1b further reacts with formaldehyde(R2) to form an intermediate INT4, which is also a barrier-free exothermic reaction of 46.9 kJ/mol; (4) INT4 isomerizes to a germanic bis-heterocyclic product P4 via a transition state TS4 with an energy barrier of 54.1 kJ/mol.     

The d metal-sulfosalicylate complexes: Herring-bone, ladder and double-stranded chain frameworks with green luminescences

Assembly of 5-sulfosalicylic acid (H₃L) and d¹⁰ transition metal ions (Cd^II, Ag^I) with the neutral N-donor ligands produces five new complexes: [Cd₂(HL)₂(4,4′-bipy)₃]_n·2nH₂O (1), {[Cd₂(μ₂-HCO₂)₂(4,4′-bipy)₂(H₂O)₄][Cd(HL)₂(4,4′-bipy)(H₂O)₂]}_n (2), {[Cd(4,4′-bipy)(H₂O)₄][HL]·H₂O}_n (3), [Cd(HL)(dpp)₂(H₂O)]_n·4nH₂O (4), {[Ag(4,4′-bipy)][Hhbs]}_n (5) (4,4′-bipy=4,4′-bipyridine, dpp=1,3-di(pyridin-4-yl)propane, H₂hbs=4-hydroxybenzenesulfonic acid, the decarboxylation product of H₃L). Complex 1 adopts a 5-connected 3D bilayer topology. Complex 2 has the herring-bone and ladder chain, which are extended to a 3D network via hydrogen bonding. In 3–4 complexes, 3 is a 3D supermolecular structure formed by polymeric chains and 2D network of HL²⁻, while 4 gives the double-stranded chains. In 5, ladder arrays are stacked with the 2D networks of Hhbs⁻ anions in an –ABAB– sequence. Complexes 1–4 display green luminescences in solid state at room temperature, while emission spectra of 3 and 4 show obvious blue-shifts at low temperature.     

From Molecular Fragments to Crystals: A UV Raman Spectroscopic Study on the Mechanism of Fe‐ZSM‐5 Synthesis

The nucleation process of iron‐exchanged zeolite Fe‐ZSM‐5, from the assembly of distorted tetrahedrally coordinated iron species and silicate rings in the precursor to the final Fe‐ZSM‐5 crystals, as well as variations in the coordination environment of iron, were studied by UV resonance Raman spectroscopy and complementary techniques.

     

抽运-检测型非线性磁光旋转铷原子磁力仪的研究

报道了一种抽运-检测型的非线性磁光旋转铷原子磁力仪.其原理是线偏振光通过处于外磁场环境中被极化的原子介质后,由于原子对线偏振光中左、右圆偏成分不同的吸收和色散,导致光的偏振方向会产生与磁场相关的转动.分析了该磁力仪的工作原理,并测试了它对不同磁场大小的响应.测试结果表明,磁力仪测量范围为100—100000 nT,极限灵敏度为0.2 p T/Hz~(1/2),磁场分辨率为0.1 p T.进一步研究了不同磁场下原子系综极化态的横向弛豫时间,讨论了原子磁力仪高磁场采样率的获得方法.本文的原子磁力仪在5000—100000 n T的磁场测量范围内磁场采样率可实现1—1000 Hz范围内可调,能够测量低频的微弱交变磁场.本文的研究内容为大磁场测量范围、高灵敏度、高磁场采样率的原子磁力仪研制提供了重要参考.     

重组嗜热β-葡萄糖苷酶转化稀有人参皂苷Rd和CK

利用高效液相色谱(HPLC)法, 对重组嗜热β-葡萄糖苷酶(Fpglu1)转化稀有人参皂苷(Rd和CK)进行研究, 并表征了其催化动力学参数. 利用同源模建和分子动力学模拟等生物信息学技术, 探究了Fpglu1转化人参皂苷的结构基础及其相互作用. 结果表明, Fpglu1能够水解人参总皂苷生成稀有皂苷Rd和CK, 其催化人参皂苷Rb₁, Rb₂和Rc的K_m值分别为0.318, 1.840和5.269 mmol/L; 酶的转换数(k_cat)值分别为144.191, 0.572和0.011 s^-1. 当转化时间分别为6和102 h时, Rd和CK的产率达到最大, 分别为60%和93%. 通过对该酶的结构预测及皂苷分子的对接研究发现, 底物位于由疏水性氨基酸构成的底物口袋中, 氨基酸残基Glu194和Glu367是参与催化作用的关键, 且实验测得的酶促反应动力学参数(K_m)与对接的相互作用能量值存在线性关系.     

Thermal decomposition of the solid phase of nitromethane: ab initio molecular dynamics simulations

The Car-Parrinello molecular dynamics simulations were employed to investigate thermal decomposition of the solid nitromethane. It is found that it undergoes chemical decomposition at about 2200?K under ambient pressure. The initiation of reactions involves both proton transfer and commonly known C-N bond cleavage. About 75 species and 100 elementary reactions were observed with the final products being H2O, CO2, N2, and CNCNC. It represents the first complete simulation of solid-phase explosive reactions reported to date, which is of far-reaching implication for design and development of new energetic materials.     

二氯亚锗基卡宾与甲醛生成锗杂双环化合物反应的从头算研究

用CCSD(T)//MP2/6-31G^*方法研究了单重态二氯亚锗基卡宾(Cl₂Ge=C:)与甲醛生成锗杂双环化合物的环加成反应机理,根据该反应的势能面可以预言,该反应有两条相互竞争的主反应通道．该反应所呈现的反应规律为：二氯亚锗基卡宾中C原子的2p空轨道因从氧端插入甲醛的π轨道而造成了中间体的形成;在中间体和两反应物之间,因二氯亚锗基卡宾和甲醛中的两成键π轨道发生了[2+2]环加成作用,从而分别生成了Ge-O对位的和Ge-O顺位的两四元环化合物;由于四元环化合物中卡宾C原子的不饱和性,进一步与甲醛作用,从而生成了两锗杂双环化合物．     

Directly LD-pumped passively Q-switched YVO<Subscript>4</Subscript>-Nd:YVO<Subscript>4</Subscript> laser at 1.34 μm with a V<Superscript>3+</Superscript>: YAG saturable absorber

The performance of a directly LD-pumped passively Q-switched YVO₄-Nd:YVO₄ laser at 1.34 μm with a V³⁺:YAG saturable absorber was demonstrated for the first time to the best of our knowledge. The average output power of 580 mW was obtained at the pump power of 8.8 W, corresponding to the optical conversion efficiency of 6.6% and slope efficiency of 11%. The minimum pulse width was 280 ns with the pulse repetition rate of 230 kHz, which was attained with a T = 5.6% output coupler at the pump power of 8.8 W.     

Nanoscratch study of Zn1−xMnxO heteroepitaxial layers

We investigated the nanotribological properties of Zn_1−xMn_xO epilayers (0 ≤ x ≤ 0.16) grown by molecular beam epitaxy (MBE) on sapphire substrates. The surface roughness and friction coefficient (μ) were analyzed by means of atomic force microscopy (AFM) and hysitron triboscope nanoindenter techniques.The nanoscratch system gave the μ value of the films ranging from 0.17 to 0.07 and the penetration depth value ranging 294-200 nm when the Mn content was increased from x = 0 to 0.16. The results strongly indicate that the scratch wear depth under constant load shows that higher Mn content leads to Zn_1−xMn_xO epilayers with higher shear resistance, which enhances the Mn-O bond. These findings reveal that the role of Mn content on the growth of Zn_1−xMn_xO epilayers can be identified by their nanotribological behavior.     

High Performance Thermally Activated Delayed Fluorescence Sensitized Organic Light‐Emitting Diodes

Recently, organic light‐emitting diodes (OLEDs) employing thermally activated delayed fluorescence (TADF) materials have aroused huge attention in both academia and industry. Compared with fluorescent and phosphorescent materials, TADF materials can theoretically capture 100 % excitons without incorporating noble metals, making them effective emitters and hosts for OLEDs simultaneously. Here, in this review, our recent works on mechanisms and materials of high performance TADF‐sensitized phosphorescent (TSP) OLEDs, TADF‐sensitized fluorescent (TSF) OLEDs and TADF‐sensitized TADF (TST) OLEDs are summarized. Finally, we propose the outlook for the further development and application of TADF‐sensitized OLEDs.