1-氯-1,1-二硝基-2-(N-氯脒基)乙烷的合成、表征和晶体结构

采用高锰酸钾/盐酸体系氧化氨基的方法获得了1-氯-1,1-二硝基-2-(N-氯脒基)乙烷,收率为70%,用核磁、红外、质谱、元素分析等方法对该产物进行了结构表征。以二氯甲烷为溶剂制备出了其单晶,用X射线单晶衍射仪测定了晶体结构。结果表明,该化合物的分子式为C2H2C l2N4O4,相对分子质量为216.98,该晶体为正交晶系,属Pbcn空间群,晶体学参数为:a=0.9940(17)nm,b=1.0628(19)nm,c=1.4487(3)nm,V=1.5304(5)nm3,Z=8,D c=1.883 g.cm-3,F(000)=864,R1=0.0325,ωR2=0.0784。该化合物的熔点为90℃,起始分解温度为136.6℃,较1,1-二氨基-2,2-二硝基乙烯(FO X-7)有大幅度下降,表明其热稳定性较FO X-7差。

Collecting performances of N-dodecylethylene-diamine and its adsorption mechanism on mineral surface

The collecting performances of N-dodecylethylene-diamine （ND） to quartz and hematite were studied via single mineral flotation. Experimental results show that ND has stronger collecting ability to quartz than hematite. Different floatability of quartz and hematite was presented in the existence of depressant. Compared with lauryl amine, ND has stronger collecting performances to quartz. Satisfied separation result of artificially mixed sample was acquired with iron grade of concentrate of 59.92% and iron recovery of 88.85% when pulp pH value was 7.27 with 41.7 mg/L collector and 3.33 mg/L starch. Polar group properties calculation results indicated that ND has stronger collecting capability and better selectivity than lauryl amine. Measurement results of zeta-potentials and infrared spectrum showed that hydrogen bonding adsorption and electrostatic adsorption occur between the surface of ND and quartz.

ESTIMATION OF ACTIVATED ENERGY OF DESORPTION OF n-HEXANE ON ACTIVATED CARBONS BY TPD TECHNIQUE

In this paper, six kinds of activated carbons such as Ag+-activated carbon, Cu2+- activated carbon, Fe3+- activated carbon, activated carbon, Ba2+- activated carbon and Ca2+- activated carbon were prepared. The model for estimating activated energy of desorption was established. Temperature-programmed desorption (TPD) experiments were conducted to measure the TPD curves of n-hexanol and then estimate the activation energy for desorption of n-hexanol on the activated carbons. Results showed that the activation energy for the desorption of n-hexanol on the Ag+- activated carbon, the Cu2+- activated carbon and the Fe3+- activated carbon were higher than those of n-hexanol on the activated carbon, the Ca2+- activated carbon and the Ba2+- activated carbon.

Synthesis and Crystal Structure of Bis-{N-[2-(6-ethylpyridyl)]-salicylideneiminato} Cobalt(Ⅱ)

The title complex 1, C28H26CoN4O2, crystallizes in the triclinic system, space group P with a = 9.506(3), b = 9.506(3), c = 14.837(5) ? a = 106.397(5), b = 106.012(5), g = 91.889(6), V = 1217.7(7) 3, Z = 2, Dc =1.390 g/cm3, Mr = 509.46, F(000) = 530, m(MoKa) = 0.738 mm-1, the final R = 0.0359 and wR = 0.0951 for 4275 observed reflections with I > 2s(I). The complex adopts a distorted tetrahedral coordination sphere around the cobalt atom.

Kinetics of Copolymerization of Acrylonitrile with N-Vinylpyrrolidone in H_2O/Dimethyl Sulphoxide Mixture

Kinetics of copolymerization of acrylonitrile(AN) with N-vinylpyrrolidone(NVP) initiated by azodi-isobutyronitrile(AIBN) was investigated in H2O/dimethyl sulphoxide(DMSO) mixture between 50℃ and 70℃ under N2 atmosphere. The rate of copolymerization and particle size were measured respectively. The kinetic equation of copolymerization system is obtained as Rpat 60℃. The overall activation energy for copolymerization system was computed as 87.3kJ.mol-1. Effect of additives of hydroquinone and dioxane on copolymerization was discussed. The polymerization is retarded by hydroquinone and accelerated by dioxane, which confirms the free radical copolymerization of AN with NVP.

Synthesis and Characterization of Poly(N-Vinyl-2-Pyrrolidone/Itaconic Acid) Hydrogel

With N-vinyl-2-pyrrolidone (NVP) and itaconic acid(IA), poly(N-vinyl-2-pyrrolidone/itaconic acid)[P(NVP/IA)] hydrogel was synthesized by free radical solution polymerization. The structure of this (P(NVP/IA)) was characterized by IR. Effects of concentration of itaconic acid, amount of cross-link agent, N,N′-methylene-bis-acrylamide, reaction temperature, and time on properties of swelling ratio(SR) of the hydrogel were investigated.The results show that the best swelling property of the hydrogel is obtained at 50 ℃ and 1.5 h. pH sensitivity increases as the concentration of itaconic acid in the hydrogel system increases. Swelling ratio of the hydrogel decreases as the amount of cross-link agent increases.

Spectroscopic Investigated Interaction between Silver Nanocomposites Based of Poly-N-Vinylpyrrolidone and Doxorubicin for Drug Delivering

It is investigated to synthesis of Ag nanoparticles by presence the synthetic polymer poly-N-vinylpyrrolidone. It was determined with X-ray analyses that the size ofnanoparticles changed between 18-42 nm. Then, the authors studied sorption process of doxorubicine by silver nanocomposites and investigated chemical interaction between antibiotic and poly-N-vinyplyrrolidone with UV-VIS （ultraviolet visible） and FT-IR （Fourier transform infrared） spectroscopy. It is shown that formation of the nanoparticles doxorubicin complex mainly occurs in the 190-208 nm wavelengths on polymers 〉C=O functional groups. Also, the four main absorbing peaks of doxorubicin--234, 253, 288 and 495 nm undergo chemists shift （A2 = 12-15 nm）. When increases to pH = 7-8, the size of Ag-doxorubicin particles decreases. It is determined that the 410 nm absorption peak of Ag nanoparticles undergo 409-418 nm interval and the 3,500, 1,600, 1,645 and 1,190 sm^-1 absorption lines of PVPr （polymer poly-N-vinylpyrrolidone） slightly altered.

Relationship between the Composition of Polymer of n-Alkyl Substituted Acrylate and Vinyl Amine and Their Performance on Pour Point Depression

Polymer of n-alkyl substituted acrylate （PA） with the alkyl side chains C16- 30 were synthesized. Their crystallinity, solubility and effect on pour point depression were studied. Results showed that only carbon atoms located far away from polar groups of PAL pour point depressants participated in crystallization. When the number of carbon atoms that participated in crystallization is about three fourths of the average carbon number of wax in crude, the effect of PA is the best. The molecular weight distribution of PA pour point depressant has little influence on the effect of pour point depression, and the average molecular weight of PA in the range of （ 1.5- 2.2）× 10^4 shows the best effect. The introduction of polar groups into the molecule of PA can improve its performance. However, a too high content of polar groups in PA would cause deterioration, and even lead to loss of PA＇s performance for pour point depression.

1-氯-1,1-二硝基-2-(N-氯脒基)乙烷的波谱解析

在酸性条件下,用高锰酸钾氧化1,1-二氨基-2,2-二硝基乙烯(FOX-7)时,得到一种非预期的新化合物。通过元素分析、红外、核磁和质谱等波谱分析数据,鉴定样品的结构为1-氯-1,1-二硝基-2-(N-氯脒基)乙烷,并对其裂解途径进行了推断。

Controlled Synthesis of PCL/PVP Copolymer by RAFT Method and Its HydrophUic Block-Dependent MiceUar Behaviors

A range of poly（ε-caprolactone）/poly（N-vinyl-2-pyrrolidone） amphiphilic block copolymers with well-defined hydrophilic chain length were synthesized by the living/controlled reversible addition fragmentation chain transfer polymerization method. The composition and struc- ture of the targeted resultants were characterized with 1H NMR, 13C NMR, FT-IR spec- troscopy and gel permeation chromatography. The various block copolymers were success- fully employed to fabricate the spherical micelle with core-shell morphological structure. The poly（N-vinyl-2-pyrrolidone） block-dependent characteristics of the copolymeric micelles were investigated by fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. The solubilization of the hydrophobic ibuprofen as a model drug in the micelle solution was also explored. It was found that the drug loading contents are related to the micellar morphology structure determined by hydrophilic chain length in the copolymer.

细胞内Ca2+对可释放囊泡库的影响

目的:探讨细胞内Ca^2+对可释放囊泡库的影响.方法:取体外培养成熟的新生鼠大脑皮层神经元细胞,分别对正常细胞、去除细胞外Ca^2+的细胞、同时去除细胞内外Ca^2+的细胞,记录微小型兴奋性突触后电流(mEPSCs)和微小型抑制性突触后电流(mIPSCs),观察兴奋性和抑制性突触可释放囊泡库(RRP)大小,研究细胞外和细胞内Ca^2+对细胞胞吐的不同影响.结果:去除神经元细胞外Ca^2+和细胞内Ca^2+均对mEPSCs和mIPSCs的电流频率有抑制作用,细胞外Ca^2+对RRP大小并无显著影响,而去除细胞内Ca^2+可引起细胞内RRP的显著降低.结论:细胞内Ca^2+可影响RRP的维持.

Ebulliometric Method Based on Error Analysis Equation

Ebulliometric method based on the error analysis equation is presented for systems with the large phase equilibrium constant. Application is given for the determination and calculation of binary vapor-liquid equilibrium data for the ethanol+n-hexane system. It is also given the comparison results between the ebulliometric method based on the error analysis equation and the quasi-static method.

Synthesis and Structure of a Novel Macrocyclic Ligand( C_(22) H_(29) N_3 O_3 Br_2)

The title compound, 1,12,15 triaza 3,4:9,10 dibenzo 5,8 dioxacyclopentadecane N acetic lactam (C 22 H 29 N 3O 3Br 2, M r =543.29) has been synthesized and characterized by analytical data, IR and 1HNMR spectra. The compound crystallizes in the trigonal system, space group R 3 with a = 35.194(1), c = 10.397(1) , γ=120°, V=11152.6(1) 3, Z=18, D c =1.456 gcm -3 , F(000)=4968, μ =3.3 mm -1 . Mo Kα radiation ( λ = 0.71073), R = 0.0145 for 3094 observed reflections 〔 I>2σ(I )〕 of 3392 independent reflections. The result shows that monofunction reaction for polyaza macrocycle were protonized. 1H NMR spectra of the ligand showed two sets of multiplets due to the two phenyl rings of the ligand in different environments.

Halogen adsorbates on polymer-stabilized gold clusters: Mass spectrometric detection and effects on catalysis

The mass spectrometry of gold clusters stabilized by poly（N‐vinyl‐2‐pyrrolidone） （Au：PVP） re‐vealed the presence of Cl adsorbates derived from synthetic precursors, mainly on the Au34 and Au43 clusters. Changes in the amount of Cl adsorbates on the Au clusters did not affect the catalytic prop‐erties for the aerobic oxidation of benzyl alcohol, suggesting that the Cl atoms were only weakly bound to the Au clusters. In contrast, the replacement of Cl with Br on the Au34 and Au43 clusters significantly suppressed activity, without any influence on the electronic structure. This result indi‐cated that the Br atoms were strongly bound to the Au clusters and sterically blocked their active sites. The substantial reduction of the catalytic activity by the Br adsorbates suggested that the Au34 and Au43 clusters made a major contribution to the catalytic activity of the Au：PVP.

Synthesis and Properties of Novel Surface Active Maleic Monomer Containing Phosphate Group

A novel surface active monomer （surfmer） containing poly（ethylene glycol） chain and terminated phosphate group was synthesized. The copolymerization of synthesized surfmer with NVP （N-vinylpyrrolidone） and with NVP and VEP （5-tert-butylperoxy-5-methyl-2-hexene-3-yne monomer） led to formation of corresponding surface-active copolymers. The capability of application of resulted copolymers as surface active macroinitiators of emulsion polymerization of styrene and as components of polymeric scaffolds was investigated.

Structure Studies on New Types of Macrocyclic Compounds Part Ⅵ. Crystal Structure of Copper(Ⅱ) Complex of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-N', N'-diaceticacid

The crystal structure of copper(Ⅱ) complex with a new 14-membered tetraazamacrocyclic ligand 5,5,7,12,12,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane-N'N'-diacetic acid,[CuC16N4H34(CH2COO)(CH2COOH)]·ClO4·0. 5HCIO4·1. 5H2O was determined. Crystallographic data: Mr = 639.22,orthorhombic, space group Pcnb with a=11.743(4),b=16.446(2),c=29.611 (4) A,Z=8,V=5726(3) A3, Dc=1.482 g·cm-3, F(000)=1344,μ=9. 64 cm-1,R=0.063,and Rw=0.067 for 2386 reflections with I≥3σ(I). The structure shows an unusual configuration in which two carboxyl groups were bonded to two neighboring nitrogen atoms of the macrocycle, N1 and N4, and six methyl substituents occur on one side of the macrocycle, while two carboxyl groups on the other side, and central copper(Ⅱ) ion forms a five-coordinated geometry.

N-vinyl pyrrolidone promoted aqueous-phase dehydrogenation of formic acid over PVP-stabilized Ru nanoclusters

In this work, we fabricated the poly（N-vinyl-2-pyrrolidone） （PVP）-stabilized ruthenium（0） nanoclusters by reduction of RuC13 using different reducing agents, and studied their catalytic activity in hydrogen generation from the decomposition of formic acid. It was demonstrated that N-vinyl-2-pyrrolidone （NVP）, which is a monomer of PVP, could promote the reaction by coordination with Ru nanoparticles. The Ru nanoparticles catalyst reduced by sodium borohydride （NaBH4） exhibited highest catalytic activity for the decomposition of formic acid into H2 and CO2. The turnover of numenber （TOF） value could reach 26113 h-1 at 80 ℃. We believe that the effective catalysts have potential of application in hydrogen storage by formic acid.

One-step preparation of vinyl-functionalized material surfaces:a versatile platform for surface modification

A simple approach has been developed to functionalize various substrates, such as gold and polyvinylchloride, with dopamine methacrylamide—a molecule with adhesive properties that mimic those of mussels—to produce a versatile and general platform for subsequent surface modification. With active double bonds on the surface, various polymers, such as poly([2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide(PMEDSAH) and poly(N-vinylpyrrolidone)(PVP), can be grafted by conventional radical polymerization. Double bond surface functionalization and subsequent polymer grafting have been verified by static water contact angle, Fourier transform infrared–attenuated total reflectance(FTIR-ATR) spectroscopy and X-ray photoelectron spectroscopy(XPS) measurements. Protein adsorption assays showed that the polymermodified substrates have good protein-resistant properties. Considering the advantages of facility, versatility and substrate- independence, this method should be useful in designing functional interfaces for bioengineering applications.