Influence of Polarity and Activation Energy in Microwave–Assisted Organic Synthesis (MAOS)

The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol⁻¹ and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.     

A paper-based resonance energy transfer nucleic acid hybridization assay using upconversion nanoparticles as donors and quantum dots as acceptors

Monodisperse aqueous upconverting nanoparticles (UCNPs) were covalently immobilized on aldehyde modified cellulose paper via reduction amination to develop a luminescence resonance energy transfer (LRET)-based nucleic acid hybridization assay. This first account of covalent immobilization of UCNPs on paper for a bioassay reports an optically responsive method that is sensitive, reproducible and robust. The immobilized UCNPs were decorated with oligonucleotide probes to capture HPRT1 housekeeping gene fragments, which in turn brought reporter conjugated quantum dots (QDs) in close proximity to the UCNPs for LRET. This sandwich assay could detect unlabeled oligonucleotide target, and had a limit of detection of 13 fmol and a dynamic range spanning nearly 3 orders of magnitude. The use of QDs, which are excellent LRET acceptors, demonstrated improved sensitivity, limit of detection, dynamic range and selectivity compared to similar assays that have used molecular fluorophores as acceptors. The selectivity of the assay was attributed to the decoration of the QDs with polyethylene glycol to eliminate non-specific adsorption. The kinetics of hybridization were determined to be diffusion limited and full signal development occurred within 3 min.     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.     

推广x重新标度模型的重标度参数经验公式

给出了推广x重新标度模型的重标度参数经验公式,其中建立了重标度参数与原子核的平均结合能之间的联系,由该公式可以得出A≥12的所有核的重标度参数值,利用这些参数值可以计算有关核过程并做出预言.     

在BEPC上建造γ束线站的分析

考虑电子的反冲并利用康普顿散射,研究了激光同步辐射光源(LSS)辐射的光子波长、光子能量。结果表明,对于不同的γ,LSS辐射的光子波长和能量有不同的近似公式。当γ<<λ1/4λe时,LSS辐射的光子波长λ2≈λ1/4γ2,能量(εc2≈4γ2εc1;当γ>>λ1/4λe时,LSS辐射的光子波长λ2≈λe/γ,能量cε2≈m0γc2;结果表明,LSS辐射的条件是种子激光的波长λ1大于电子的物质波波长λm;LSS辐射的极值波长是λ2m ax=h/m0γv,极值能量是cε2m ax=βeε;本文后半部分提出了利用北京正负电子对撞机的强流高亮度电子束与激光的康普顿背散射产生单色γ射线的建议。     

A Reliability Analysis of Calculated Results for Odd-Even and Odd-Odd Nuclei in Relativistic Mean-Field Theory

We calculate the binding energies of Ni, Cu, Xe, Cs, Pt, Au, Np, Pu isotope chains using two interaction parameter sets NL-3 and NL-Z, and compared the relative errors of the even-even nuclei with those of odd-even nuclei and odd-odd nuclei. We find that the errors of binding energy of odd-even and odd-odd nuclei are not bigger than the one of even-even nuclei. The result shows that comparing with even-even nuclei, there is no systematic error and approximation in the calculations of the binding energy of odd-even and odd-odd nuclei with relativistic mean-field theory. In addition, the result is explained theoretically.     

新颖外燃式湿空气燃气轮机循环及性能研究

本文首先提出一种新型的高效燃煤燃气轮机循环一外燃式湿空气透平循环动力系统。由于外燃的特点，作功工质为洁净湿空气，从而可以实现水的回收，是对常规ＨＡＴ循环的突破；另外洁净湿空气排放不受通常烟气露点限制，从而可回收利用湿空气降温时的低温凝结潜热，提高了加湿能力，从而提高系统性能。揭示了新型循环的基本规律；推导出具有湿化特点的约束方程和系统性能简明表达式，指明影响系统性能的关键因素。在透平初温为８５０℃的工况下，系统热效率高达４８．１１％。基于能量品位梯级利用原理和系统集成方法论，通过探索充分而合理利用中低温余热的有效途径，开拓洁净煤燃气轮机总能系统的新方向。