Synthesis of crescent shaped heterocycle-fused aromatics via Garratt-Braverman cyclization and their DNA-binding studies

Three crescent shaped heterocycle-fused phenanthrene based systems 1–3 have been synthesized starting from benzene (or substituted benzene) 1,2-bis-propargyl alcohols. Bis-alkylation with propargylic bromides provided the key intermediate, the bis-propargyl bis-ethers. In spite of the possibility of many competing reactions, the latter underwent facile double Garratt-Braverman cyclization to provide compounds 1–3 in near quantitative yield, in a striking reaction involving the formation of four C–C bonds in a single step. Compounds 1–3 showed binding interaction with DNA, predominantly, via groove binding along with partial intercalation (combilexins). Molecular docking study supported the proposed binding modes.     

A fluorescent chemosensor for Cu2+ ions and its application in cell imaging

A new on-off fluorescent probe 1 for Cu²⁺ based on Schiff base compound was designed and synthesized by one-step reaction. The single probe 1 exhibited strong green fluorescence emission. A fluorescence quenching effect and faint color change were observed as soon as the Cu²⁺ was added to the probe system in H₂O/EtOH (v/v = 8:2, HEPES buffer, 0.05 M, pH = 7.4) solution. Other common metal cations did not cause the changes in the fluorescence and color of the probe 1. The optical properties were studied by the fluorescence emission and UV–Vis spectra. Meanwhile, the geometry optimizations of probe 1 and the [1-Cu²⁺] coordination complexes were also carried out by DFT using the Gaussian 09 program, in which the B3LYP function was used. Based on experimental measurement and theoretical analysis, we can know that the combination ratio of the probe and Cu²⁺ is 2:1 and the limit of detection (LOD) is as low as 5.3 × 10^?9 M Besides, the probe 1 was also used to analyze the Cu²⁺ in living cells.     

内积在溶液浓度测定中的应用

提出内积的溶液浓度测定方法。该方法计算已知浓度溶液透光率曲线与0号溶液（浓度最低的溶液）透光率曲线的内积ρ,确定溶液的ρ-C曲线,然后测定未知溶液的透光率曲线,计算其与0号溶液透光率曲线的内积,并利用已建立好的ρ-C曲线进行插值以估计溶液浓度。由于该方法利用了透光率曲线的全部信息,因此对溶液浓度的估计精度较高。对K2Cr2O7溶液浓度的测定实验结果表明,该方法对溶液浓度的估计相对误差小于1.00%。     

Biphenyl-type sensing system in proton-rich environment by fluorescence and quantum-chemical calculations

Biphenyl derivative N-allyl-N′-(4′-nitro[1,1′-biphenyl]-4-yl)thiourea (BP1) was synthesized as a functional fluorescent sensor for protons and their photophysical properties were studied. The influence of environment protonation on photophysical properties of the biphenyls in solutions was investigated using UV absorption, steady-state and time-resolved fluorescence spectroscopy. Semi-empirical and DFT calculations and optimization of the molecular structure of the biphenyl derivatives in vacuum, in polar solvents and in a proton-rich environment were conducted using the HyperChem, Amsol and Gaussian3 software package. Fluorescence quenching with addition of acidic acid was observed and the Stern-Volmer quenching rate constant was about 3.0×10⁹ M⁻¹ s⁻¹. Intermolecular hydrogen bonds formations by the protons with the sulphur being substituted to the biphenyls generate charge movement and strong increase (×5) of the dipole moment of the fluorophore.     

Influence of pressure on the relative population of the two lowest vibrational levels of the C <Superscript>3</Superscript> Π<Subscript>u</Subscript> state of nitrogen for electron beam excitation

Continuous and pulsed 12 keV electron beams were used to excite nitrogen within a gas cell at pressures ranging from 10 to 1400 hPa. The pressure dependence of the ratio of photon fluxes for emission from vibrational levels v'=0 and 1 of the C ³Π _u state has been studied. The results confirm the presence of a collisional excitation mechanism populating v'=0, 1 in addition to electron impact excitation. Rate constants of (1.27 ±0.04)×10^-11 cm³s^-1 [ v'=0] and (2.68 ±0.08)×10^-11 cm³s^-1 [ v'=1] were measured for C ³Π _u quenching by ground state nitrogen. For electron beam conditions relative excitation efficiencies of 1:0.59:0.22 for vibrational levels 0, 1 and 2 were calculated. The recorded flux ratios are compared with the predictions given by a vibrational relaxation model.     

Optical Thin-Film Sensors for the Determination of Aqueous Halide Ions

Fourteen thin-film optical sensors in which halide-sensitive fluorophores are immobilized in a thin copolymer film (50 m, dry) have been developed and characterized. The sensor films use rhodamine, 6-methoxyquinoline, and harmane dyes which have been functionalized and bound to a hydrophilic copolymer. The sensor films are reversibly capable of determining aqueous bromide and iodide with 4 and 2% accuracy, respectively, at concentrations of around 10^–3 mol dm^–3, and are more sensitive than previous plastic sensor fabrications. The 90% response time to molar iodide is 30–60 s. A combination of sensor films allows the simultaneous determination of both I^– and Br^– in a mixed-halide solution. The interference of several ions, including pseudo-halides, on the sensor films has been studied.     

Interaction of dispersed phase with concentration polarization

The effect of a dispersed phase in reducing the concentration polarization in a membrane tube has been studied. The presence of a dispersed phase seems to have an effect in controlling the size of eddy formation and the rate of energy dissipation in the fluid medium. The role of eddy length and the energy dissipation rate on the mass transfer coefficient is discussed. Theoretical results obtained for the mass transfer coefficient and for the concentration polarization in the case of gelatin ultrafiltration are compared with the existing experimental results. The theoretical predictions seem to be in good agreement with the experimentally observed results.     

NH4Cl作助熔剂合成CaS：Ce的光谱特性及其浓度效应

以ＮＨ４Ｃｌ作助溶剂，碳还原硫酸钙的方法合成了ＣａＳ：Ｃｅ。在紫外光激发下，ＣａＳ：Ｃｅ中存在着Ｃｅ＾３＋的＾２Ｄ－＾２Ｆ５／２（５００ｎｍ）和＾２Ｄ－＾２Ｆ７／２（５５０ｎｍ）跃迁发射，但在蓝色光激发下，只有波峰为５３２ｎｍ半宽度为９２ｎｍ的宽带发射。当Ｃｅ＾３＋的浓度为０．０７５ｍｏｌ％时，＾２Ｄ－＾２Ｆ５／２跃迁发射强度与＾２Ｄ－＾２Ｆ７／２跃迁发射强度相等，而５３２ｎｍ发射猝灭。     

以二乙氨基乙基交联葡聚糖凝胶为基质的铝荧光传感层

本文基于Ａｌ＾３＋离子对电价键固定在二乙氨基乙基交联葡聚糖凝胶上的水杨基荧光 酮的可逆荧光淬灭作用，研制了测定Ａｌ＾３＋离子浓度的荧光传感层。     

巯基棉富集─火焰原子吸收分光光度法测定水中的微量铁

本文详细考查了巯基棉富集Ｆｅ（Ⅲ）的条件，发现微量铁（Ⅲ）在ｐＨ值为５－８的条件下能为巯基棉定量吸附．１ｍｏｌ／Ｌ盐酸５ｍＬ能将巯基棉吸附的Ｆｅ（Ⅲ）定量洗脱，０．１ｇ巯基棉的饱和吸附量为９０μｇ，样品分析测定结果的相对标准偏差小于３．４％，９８．４％－９８．８％。