Studies on the interactions between anionic surfactants and polyvinylpyrrolidone: Surface tension measurement, 13C NMR and ESR

 The interaction between anionic surfactants and polyvinylpyrrolidone (PVP) are investigated using ¹³C NMR, ESR spectroscopy and surface tension measurements at the air/water interface. The behavior of single-chained surfactant, sodium dodecyl sulphonate (AS), is compared with that of the double-chained surfactant, sodium bis(2-ethylhexyl) phosphate (NaDEHP). The results showed that a surfactant–polymer complex of “necklace and head structure” is formed in AS aqueous solutions in the presence of PVP due to the hydrophobic interaction between PVP and AS. The AS micelles nucleate on the polymer hydrophobic sites, and the mobility of the AS head groups is not affected. But, for NaDEHP surfactant, it was found that PVP is little effective in influencing the monomer–micelle equilibrium and no surfactant– polymer complex formed in the NaDEHP aqueous solution. Received: 8 May 1996 Accepted: 14 August 1997     

New Stephaoxocane Alkaloids from Stephania longa

Three new stephaoxocane‐type alkaloids, stephalonganines A–C ( 1 – 3 ), together with the known eletefine ( 4 ), were isolated from the whole plant of Stephania longa. Their structures were fully characterized spectroscopically, and the absolute configurations of the new alkaloids were assigned by comparison of their circular‐dichroism (CD) data with those of 1,2‐dihydrostephaoxocanine ( 5 ), in combination with 2D‐NMR experiments.     

Analysis of bufadienolides in the Chinese drug ChanSu by high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry

The qualitative analysis of bufadienolides in the Chinese drug ChanSu was performed using high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS). Bufadienolides are the major bioactive constituents of ChanSu, which is used to treat heart failure and cancer in traditional Chinese medicine. The APCI-MS fragmentation behavior of bufadienolides was studied. For bufadienolides with only hydroxyl substituents, the fragmentation was characterized by successive eliminations of H(2)O and CO molecules, and the profile of MS/MS product ions was correlated with the number of hydroxyl groups. If a C-16 acetoxyl group was present, the fragmentation of [M+H](+) ions was triggered by initial loss of 60 Da (HOAc). The elimination of CO was significant for bufadienolides with a 19-formyl group, and the 19-hydroxyl group could be characterized by the loss of 30 Da (HCHO). These fragmentation rules were applied to the identification of bufadienolides in a methanolic extract of ChanSu, which was separated on a C(18) column with gradient elution. A total of 35 bufadienolides were identified, including four new constituents. The method established here facilitated the convenient and rapid quality control of ChanSu crude drug and its pharmaceutical preparations.     

水汽对TiO_2上CO光催化氧化反应的影响

在室温、杀菌灯照射下 ,对“氧化的”TiO2 催化剂上CO光催化氧化反应进行了研究 ,发现当原料气中加入分压为 3.36kPa水汽时 ,光催化氧化CO的活性明显降低 .这可能是由于杀菌灯照射下TiO2 表面生成的O-(a) 或O(a) 与H2 O反应生成·OH ,降低了表面的O-(a) 和O(a) 的浓度 ,而生成的·OH不能使CO氧化 ,从而降低了氧化CO的能力     

Synthesis and magnetic properties of poly(p‐phthaloyl‐disacetylaceton‐ethylenediimine) metal complexes

Macrocyclic Schiff‐base ligand, bisacetylaceton‐ethylenediimine (BAE) and its transition metal complexes M(BAE) (M = Cu²⁺, Ni²⁺) were synthesized. The complexes having characteristics of aromatic systems and well‐defined one‐dimensional structures, reacted with p‐phthaloyl chloride, to obtain polymer complexes. The complexes were characterized by elemental analysis, inductively coupled plasma (ICP), FT‐IR, and thermal analysis and show good thermal stability. ESR spectra analysis discovered that there are free radicals in the chain of polymers, indicating that a weak magnetic spin‐exchange interaction operates between the metal ions and free radicals. It is found that, as the bridging p‐phthaloyl group is able to propagate the magnetic exchange interaction, the polymer complexes show paramagnetic properties by measurement of temperature dependence of the magnetic property, and obey Curie–Weiss law. Copyright © 2001 John Wiley & Sons, Ltd.     

LyP-1 peptide-functionalized gold nanoprisms for SERRS imaging and tumor growth suppressing by PTT induced-hyperthermia

The gold nanoprisms (GNPs) have exhibited special plasmonic properties for biomedical applications because of their unique shapes and dimensions. Based on their optical performance, the NIR dye IR780 not only enabled the GNPs-based nanosystem as SERRS nanoparticles for Raman-encoded molecular imaging, but also enhanced the plasmonic photothermal property by laser irradiation. Meanwhile, the GNPs/IR780-Lyp-1 by introduction of tumor-homing peptide segment LyP-1, which presents high affinity to p32 protein, demonstrated the increased enrichment in tumor region and enhanced photothermal therapy efficacy.     

Rapid—In—situ Determination of Chromium （VI） in Water Using Modified Diphenylcarbazine with Citrate

In recent years, the determination of Cr (VI) has attracted great attention because of its toxicity to human, plants and animals1-5. Usually, in the industrial waste water, the concentration of Cr (VI) is relatively high and should be determined frequently. So, an accurate, quick, and convenient method for the measurement of Cr (VI) in environmental water, as well as in river, lake, sea and tap water, is of great importance. The method for determination of Cr (VI) by diphenylcarbazine …     

DFT法研究离子液中EMIM~ 催化丁烯双键异构反应机理(II)

用密度泛函理论(DFT)在B3LYP/6鄄31G(d,p)的计算水平上研究了离子液中1鄄乙基鄄3鄄甲基咪唑阳离子(EMIM )的4鄄H和5鄄H原子催化丁烯双键异构反应的可能途径,优化了反应体系的平衡态和过渡态的几何构型,分析了反应过程中键参数的变化,通过振动分析对平衡态和过渡态进行了验证.计算结果表明,离子液中的EMIM 首先通过4鄄H和5鄄H原子吸附丁烯,进而催化丁烯的双键异构反应,EMIM 的4鄄H和5鄄H催化1鄄丁烯异构为2鄄丁烯的正反应活化能分别为204.2和207.3kJ·mol-1,逆反应活化能约为220.9和223.8kJ·mol-1,反应为基元反应.     

Novel metal-linked face-to-face porphyrazine dimer

We report the synthesis and physical studies of a novel porphyrazine (pz) dimer [1[Ni,Cu]]2, which has Ni(II) ions incorporated into the pz cores and is linked by two Cu(II) ions coordinated to bis(picolinamide) chelates attached to the pz periphery. [1[Ni,Cu]]2 was prepared from precursor pz 2 with a selenodiazole ring fused to the pz core. This ring was deprotected to form the diamino-pz 3, which reacted with 2 mol of picolinoyl chloride hydrochloride to form pz 1[2H,2H], with peripheral bis(picolinamide) chelates; this was metalated to form [1[Ni,Cu]]2. The crystal structures of 1[2H,2H] and [1[Ni,Cu]]2 are presented. The latter is a dimer in which parallel, face-to-face pz's with an average separation of 3.30 angstroms are linked through the peripheral picolinamide ligands by a pair of peripheral Cu(II) ions. Each Cu(II) is coordinated with distorted square-planar geometry by a picolinamide from each pz. In this report, we focus on the interaction of these two peripheral Cu(II) ions. We discuss the preparation and magnetic properties of the pz dimer complex [1[Ni,Cu]]2 with two Cu(II) ions in the peripheral chelate but a diamagnetic metal ion Ni(II) in the pz core. Although [1[Ni,Cu]]2 contains two Cu(II) ions (S = 1/2), we could detect no electron paramagnetic resonance signal, which suggests very strong antiferromagnetic exchange between those two Cu(II) ions. Temperature-dependent magnetic susceptibility measurement gives an exchange splitting between the S = 0 ground state and the excited triplet state of delta = 660 cm(-1).     

Longistylumphyllines A–C,Three New Alkaloids from Daphniphyllum longistylum

Three new alkaloids, longistylumphyllines A–C (1–3), together with the six known alkaloids deoxycalyciphylline B, deoxyisocalyciphylline B, methyl homosecodaphniphyllate, daphnicyclidin A, daphnicyclidin B, and daphnicyclidin F, were isolated from the stems and leaves of Daphniphyllum longistylum. Their structures and relative configuration were elucidated on the basis of spectroscopic data, especially 1D and 2D NMR techniques.