基于咔唑-靛红双-硫代碳酰腙衍生物的NMR研究

采用多种核磁共振（NMR）技术（包括¹H NMR、¹³C NMR、¹H-¹H COSY、¹H-¹³C HSQC、¹H-¹³C HMBC），对基于咔唑-靛红双-硫代碳酰腙新型衍生物2，即1-[（3Z）-2-氧代吲哚-3-亚基]-5-[（9-己基-3-咔唑基）亚基]硫代碳酰腙的¹H和¹³C NMR信号进行了全归属，确定了其结构．     

Linearization of nonlinear filter generators and its application to cryptanalysis of stream ciphers

Nonlinear filter generators are commonly used as keystream generators in stream ciphers. A nonlinear filter generator utilizes a nonlinear filtering function to combine the outputs of a linear feedback shift register (LFSR) to improve the linear complexity of keystream sequences. However, the LFSR-based stream ciphers are still potentially vulnerable to algebraic attacks that recover the key from some keystream bits. Although the known algebraic attacks only require polynomial time complexity of computations, all have their own constraints. This paper uses the linearization of nonlinear filter generators to cryptanalyze LFSR-based stream ciphers. Such a method works for any nonlinear filter generators. Viewing a nonlinear filter generator as a Boolean network that evolves as an automaton through Boolean functions, we first give its linearization representation. Compared to the linearization representation in Limniotis et al. (2008), this representation requires lower spatial complexity of computations in most cases. Based on the representation, the key recoverability is analyzed via the observability of Boolean networks. An algorithm for key recovery is given as well. Compared to the exhaustive search to recover the key, using this linearization representation requires lower time complexity of computations, though it leads to exponential time complexity.     

On the Populations of Neon Levels in the Low Temperature Plasma of a Hollow Cathode Discharge

Atomic levels population measurements constitute an essential contribution to various aspects of plasma research: balance and cross-section of inelastic processes, admixtures effects on level excitation mechanism, purposeful optimisation of plasma parameters etc. Atomic level populations in the negative glow of a hollow cathode discharge are of utmost interest in view of the peculiarities of the spectral source: a rich spectrum consisting of gas lines, lines of the cathode material and also lines of the substances introduced in the discharge; intensive atomic and ionic lines of high excitation potentials; small spectral linewidth, convenient for analytical purposes.     

Synthesis and optical nondestructive evaluation of GaN nanorods on silicon surfaces with gold catalyst

Nanometric gallium-nitride rods were grown on a silicon (1 1 1) substrate through a chemical vapor deposition process with gold particles as the catalyst. Randomly distributed gallium-nitride rods of 20–200 nm in diameter and of various densities and lengths were formed under different deposition conditions. Characterization analyses, such as scanning electron microscopy and optical reflection spectroscopy, have been carried out on samples containing gallium-nitride rods different in size, shape, length and density. While the scanning electron microscopy shows directly the images of the sample surfaces, the optical spectroscopy provides a nondestructive evaluation of the sample surfaces, especially helpful for checking the uniformity of the samples.     

Electronic structure and peculiar bonding properties of NdNiMg5 from first principles

The newly found ternary compound NdNiMg₅ has been studied within DFT based methodologies. Results of cohesive energy, charge transfers, elastic constants and electron localized function mapping as well as electronic structure and bonding properties have been compared with those of isostructural binary NdNi. The calculation results have shown that Mg substructures interlayering NdNi – like slabs exhibit different magnitudes of charge transfers all within range of metallic behavior and the different Mg substructures selectively bind with Nd and Ni substructures. As a consequence an enhanced cohesion with respect to binary intermetallic NdNi is identified. The whole set of elastic constants and their combinations in orthorhombic symmetry confirm the mechanical stability of NdNiMg₅ with larger compressibility and less ductility (more brittleness) with respect substructures to NdNi. While in an intermetallic compound such as NdNi the bonding is ensured mainly by Nd–Ni interaction, in NdNiMg₅ Nd–Ni, Nd–Mg, Ni–Mg as well as Mg–Mg participate to the bonding and the extra electrons brought by Mg are found within bonding states thus illustrating furthermore the enhanced cohesion of the ternary versus the binary systems.     

Synthesis,spectral, DFT calculations and biological studies of solvatochromic copper(II)-ONS hydrazone derived from 2-aminochromone-3-carboxaldehyde

New ONS hydrazone ligand, 2-[(2-aminochromon-3-yl)methylidene]-N-phenylhydrazinecarbothioamide, HL , was synthesized and reacted with different salts of Cu (II) ion (OAc⁻, NO₃⁻, SO₄²⁻ and Cl⁻) in absence and presence of secondary ligands (L′); 8-hydroxyquinoline, 1,10-phenanthroline or SCN⁻; to form binary and ternary Cu(II)-chelates. The ligand and its Cu(II)-complexes were fully characterized by analytical, spectral, thermal, conductivity and magnetic susceptibility measurements. The metal chelates showed octahedral, square planar and /or distorted tetraherdal arrangements. Coats–Redfern equations used to calculate the kinetic parameters of the thermal decomposition stages (E_a, A, ΔH, ΔS and ΔG). The compounds exhibit luminescence property; promising interesting potential applications as photoactive materials. Lippert–Mataga, Bakhshiev, Kawski–Chamma–Viallet and microscopic solvent polarity parameter and E_T^N correlation methods were applied on the solvatochromic shifts of emission spectra to evaluate the ground (μ_g) and excited (μ_e) states dipole moments. Excited state dipole moment is larger than the ground state which may be attributed to π-π* transition. The coordinating anions play an important role on the position and intensity of emission band. The ligand and its metal complexes showed antimicrobial activity towards Gram–positive bacteria, Gram–negative bacteria, yeast and fungus. The molecular structural parameters of HL and its Cu(II)- complexes have been calculated on the basis of DFT engaged in the Gaussian 09 program at the B3LYP/6-31G(d,p) level; the theoretical data are correlated with the experimental data.     

Direct calculation of time varying Aharonov-Bohm effect

The Aharonov-Bohm effect (ABE) for steady magnetic fields is a well known phenomenon. However, if the current in the infinite solenoid that creates the magnetic field is time-dependent, that is in the presence of both magnetic and electric fields, there is no agreement whether the effect would be present. In this note, we try to investigate time varying ABE by a direct calculation in a set-up with a weak time dependent magnetic field. We find that the electric field arising out of the time-varying magnetic field in the path of the electrons does not enter the action integral but only changes the path of the electron from the source to the slits and then on to the detector. We find a frequency dependent AB phase shift. At low frequencies the result smoothly approaches the one for a constant field as the frequency tends towards zero. On the other hand, for high frequencies such that the AB-phase induced in the path of the wave packet oscillates rapidly, the net effect will be very small which is borne out by our results.     

基于回波平移序列的快速三维磁共振温度成像方法

高强度聚焦超声（HIFU）是一种无创的热消融疗法，为保证其安全性和有效性，需要一种精度高、速度快的测温方法在其治疗过程中对温度进行监控.基于质子共振频率位移（PRFS）的磁共振温度成像（MRT）对温度具有较高的灵敏度，且与温度具有良好的线性关系，因此常被用于引导HIFU治疗.然而在实际应用中，HIFU治疗的最大隐患在于可能造成表皮灼伤，并且灼伤区域可能与焦点区域相隔较远.因此MRT的监控范围十分重要.本文基于三维回波平移成像序列，结合可控混叠的空间并行成像技术，实现了时间分辨率为3 s的快速三维温度成像.为了验证该方法的精度，本文首先设计了仿体降温实验，利用光纤温度计验证回波平移序列测温的准确度和精确度.然后在室温条件下扫描离体猪肉组织，对比加速前后的MRT的测温精确度.在HIFU加热条件下扫描离体猪肉组织，对比加速前后的MRT的测温准确度.结果显示，本文提出的方法可以在3 s内完成三维温度精准测量，对于HIFU治疗的安全监控具有重要意义.     

立体化学在有机化学中的重要地位——中国化学奥林匹克竞赛理论试题分析

分析2015-2017年中国化学奥林匹克竞赛（初赛、决赛）理论部分试题，发现有机化学试题中立体化学相关内容备受命题者的青睐，凸显了立体化学在有机化学中的重要地位。     

Improved Method for the Total Synthesis of Azaperone and Investigation of Its Electrochemical Behavior in Aqueous Solution

Azaperone, with anti-anxiety and anti-aggressive activities used in veterinary medicine, is a member of the butyrophenone class. It is ordinarily utilized for a wide range of indications, such as sedation, obstetrics, and anesthesia. In this research, an improved synthetic route is presented for azaperone using a phase-transfer catalyst(PTC). In general, it was synthesized as a dopamine antagonist in four steps. The bis(2-chloroethyl) amine intermediate is easily obtained after the conversion of the alcohol groups into the chloride leaving group using thionyl chloride(95% yields). The alkylation of commercially available 2-amino pyridine in the presence of PTC was then carried out, giving 1-(pyridin-2-yl) piperazine with 75% yield. 1-(Pyridin-2-yl) piperazine was finally alkylated using 4-chloro-1-(4-fluorophenyl) butan-1-one to achieve azaperone with 60% yield. The butyrophenone intermediate was obtained via the Friedel-Crafts reaction of fluorobenzene with 4-chlorobutyryl chloride in the presence of AlCl₃. High efficiency, gentle reaction conditions, and fast and simple procedure are the advantages of this method. Also, the electrochemical oxidation behaviour of azaperone was investigated using cyclic and differential pulse voltammetry techniques. Cyclic voltammetric studies indicated an irreversible process for azaperone electro-oxidation with a peak potential of 0.78 V in a phosphate buffer solution(pH=7.0) vs. Ag/AgCl(saturated KCl) electrode. The value of the peak current vs. the azaperone concentration was enhanced linearly in the range of 10―70 μmol/L, and the detection limit was found to be 3.33 μmol/L.