[2＋2] Photocycloaddition of [60] Fullerene with Podophyllotoxin Derivative Containing Cyclohexadienone Group

Photochemical [2 2] cycloaddition of C60 with podophyllotoxin derivative containing a cyclohexadienone group in o-dichlorobenzene afforded an isomeric mixture of adducts and a pure adduct of C60-fused podophyllotoxin derivatives. The structures of the products were characterized by MS, NMR and IR spectra.     

Synthesis of β-Cyclodextrin-[60]fullerene Conjugate and Its DNA Cleavage Performance

A water soluble β-cyclodextrin (β-CD) functionalized [60]fullerene (C60-CD) was synthesized.The C60-CD-induced generation of reactive oxygen species (ROS),and DNA-cleavage ability and cytotoxicity of C60-CD were studied upon visible light irradiation,demonstrating that the compound is very promising in the applications of photodynamic therapy.The histological analyses demonstrate that C60-CD has no acute or subacute toxicity to living body.     

GAS-PHASE ION-MOLECULE REACTIONS OF BUCKMINSTERFULLERENE(C_(60))WITH Si(CH_3)_n CL_(4-n)(n=2,3)IN MASS SPECTROMETER

Reactions of C60 with Si(CH_3)_nCl_(4-n) (n=2,3)in the ion sourceof the mass spectrometer have been studied.The corresponding adductions[C60Si(CH_3)_mCl3_(-m)]~+(m=1,2,3),[C60SiCl]~+ and[C60CH_3]~+ wereobserved and their possible structures were discussed.The resultsindicated that C60 is very reactive to electrophiles in the gas phase.     

ESR spectra studies of Cu(Ⅱ) 2,4-dihydroxybenzaldehyde tyrosine complex

A novel Schiff base derived from 2,4-dihydroxybenzaldehyde and tyrosine and its copper(Ⅱ)complex have been synthesized and characterized.The composition of the complex is K[CuL] H2O,where L=H11C16NO5.ESR spectra of the copper(Ⅱ)complex were investigated at different temperatures and in various solvents.The second order effect and the relaxation effect were observed in the solution spectrum at room temperature,which was satisfactorily explained by spin Hamiltonian.The bonding parameters of copper(Ⅱ)complex were calculated using spectral parameters from ESR spectra at low temperature.Its bonding characterization and stability were disscussed.The result shows that the in-plane a-bond and the in-plane π-bond in the complex all play an important role.     

Combined Transient Spectra and Semiempirical Calculation of [60]Fullerenes Attached with Piperidinodithiocarboxylate and 7-Chloro-phenazine

[60]Fullerenes attached with piperidinodithiocarboxylate dyad （1） and 7-chloro-1,2,3,4-tetrahydrophenazine （2） were efficiently synthesized through Diels-Atder cycloaddition with dienes. The physical properties of the triplet states of these compounds, in which strong electron acceptor moieties were covalently attached to C60 cores, were investigated by nanosecond laser flash photolysis. The excited triplet states in benzonitrite have been evaluated by observing the transient absorption bands in the near-IR region. The HOMO and LUMO were calculated by semiempirical methods AM1, which could predict the intramolecular photoinduced electron transfer in 1 and 2, and the nanosecond transient absorption spectra observed experimentally in solution were in excellent agreement with the calculated ones.     

Effect of 1-butyl-3-methylimidazolium tetrafluoroborate on the formation rate of CO2 hydrate

The effect of the addition of 1-butyl-3-methylimidazolium tetrafluoroborate （[C4mim][BF4]） on the formation rates of CO2 hydrates was investigate. The isothermal and isobaric methods were used to measure the formation rates of CO2 hydrates. As compared to those of pure water, the data of phase equilibrium changed greatly. The effects of pressure, temperature, and the concentration of [C4mim][BF4] aqueous solution on the formation rates of CO2 hydrates were investigated. With a constant concentration of [C4mim][BF4], the rate of gas consumption was enhanced with the lowering of experimental temperature. However, a decrease in pressure exerted an opposite effect on the rate of gas consumption. Moreover, the addition of [C4mim][BF4] raised the equilibrium pressure of hydrate formation at the same temperature.     

Mass Spectrometric Studies on Metal-hexafluorobenzene Anionic Complexes（M=Ag, Au, Pd, Pt, Pb and Bi）

The anionic products from the reactions between metal(M=Ag, Au, Pd, Pt, Pb and Bi) vapour produced by laser ablation and hexafluorobenzene seeded in carrier gas(Ar) were studied by means of a homemade reflectron time-of-flight mass spectrometry(RTOF-MS). Experimental results show that the dominant products were [MmC6F6]-complexes for the reactions of Ag, Au, Pd and Pt with C6F6, while the dominant products were [MmC6F5]-complexes for the reactions of Pb and Bi with C6F6. The formation mechanisms of the prod...     

Syntheses of Aladan and [Ald~6](?)oloatin C and Study on Their Fluorescent Properties

Aladan{β-[6'-(N,N-dimethyl)amino-2'-naphthoyl]alanine}and aladan-containing cyclodecapeptide[Ald~6]-loloatin C were synthesized.The properties of their fluorescent behaviours both in aqueous buffer and micelles cre-ated by sodium dodecylsulfate(SDS)and dodecylphosphorylcholine(DPC)were further investigated.It was foundthat in either of micelle systems,[Ald~6]loloatin C possesses red-shift emission maximum wavelength and higherquantum yield.This property could be useful in the research of peptide-cell membrane interaction.     

Ionic liquid assisted synthesis of flowerlike Cu2O micro-nanocrystals

Novel flowerlike Cu2O micro-nanocrystals were prepared by a greener reductive reaction of cupric acetate monohydrate with ethylene glycol in aqueous solutions of [C8mim]X (X = Cl , Br , BF4 , PF6 ) and [Cnmim][BF4] (n = 4, 6, 8). The obtained microstructures of Cu2O were characterized by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) and Fourier Transform Infrared (FT-IR). The effects of cations, anions and concentration of the ionic liquids on the morphology of Cu2O were examined in some details. The results suggest that the formation of flowerlike Cu2O was governed by a [C8mim][BF4] controlled reductive reaction mechanism. As one of their applications, the Cu2O nanoparticles were used for the photocatalytic degradation of methylene blue in aqueous solution, and high photocatalytic activity was observed.     

Syntheses of Aladan and [Ald^6]loloatin C and Study on Their Fluorescent Properties

Aladan {β-[6＇-（N,N-dimethyl）amino-2＇-naphthoyl]alanine} and aladan-containing cyclodecapeptide [Ald^6]loloatin C were synthesized. The properties of their fluorescent behaviours both in aqueous buffer and micelles created by sodium dodecylsulfate （SDS） and dodecylphosphorylcholine （DPC） were further investigated. It was found that in either of micelle systems, [Ald^6]loloatin C possesses red-shift emission maximum wavelength and higher quantum yield. This property could be useful in the research of peptide-cell membrane interaction.     

Synthesis and characterization of novel ternary deep eutectic solvents简

A series of room-temperature ternary deep eutectic solvents(TDESs) were prepared from imidazolium halides, zinc halides and amides. The [BMIM]Cl–ZnCl2 –acetamide(1:1:1) system shows the lowest freezing point( 60 8C) and lowest density in the series. The viscosity and conductivity of TDESs have an exponential relationship with temperature and can be fitted by Arrhenius equation.     

Identification of the starting reaction position in the hydrogenation of (N-ethyl)carbazole over Raney-Ni

Hydrogenation of carbazole and N-ethylcarbazole over Raney-Ni catalyst were realized in the temperature range of 393-503 K. 4[H] adduct dominated the hydrogenation products and the formation of 2[H] adduct was the rate-limiting step during the period, in which the conversion of carbazole was less than 40%. The hydrogenation process followed pseudo-first-order kinetics and the hydrogenation activation energies of carbazole and N-ethylcarbazole were 90 k J/mol and 115 k J/mol, respectively. The reaction starting position as well as the pathway of the hydrogenation of(N-ethyl)carbazole were investigated by comparing the kinetic characteristics of hydrogen uptake of carbazole and Nethylcarbazole. The results showed that the reaction was a stepwise hydrogenation process and the first H2 was added to the C1 = C10 double bond in the hydrogenation.     

Synthesis of water-soluble C_(60) derivatives and their scavenging free radical activity

Four piperazine-appended [60] fuilerenes (1a-1d) were synthesized and characterized. Their activities of scavenging radical were studied via UV-Vis and EPR. The results indicate that light irradiation is of advantage to increase the activity of scavenging radical.     

Theoretical Studies on Electronic Spectra and Second-order Nonlinear Optical Properties of N-methyl-2-(2′-thiophene)-pyrrolo[3,4]C_(60)

Since C60 was synthesized, the theoretical predications and experimental observations about the structures and properties of C60 derivatives1~5 were attracted great interest. Many new types of C60 derivatives, which have potential application in material and biological science6,7, have been synthesized via different reactions. Liu11 et al. successfully prepared a series of N-methyl-pyrrolo[3,4]C60 derivatives and their optical and electro chemical properties were determined. But, up to now, …     

Studies on the syntheses and properties of boronoalkoxy calix [ 4 ] arenes

New boronoalkoxycalix[4]arenes were synthesized by allylation, alkylation, hydroboration and hydrolysis of 25,26,27,28-tetrahydroxycalix[4]arene, and identified by elemental analysis, IR, 1H NMR, 13C NMR, 11B NMR, MS and UV spectra. The data of UV and fluorescence spectra showed that tctrapropoxycalix-[4]arene triboronic acid could coordinate significantly with monosaccharides.     

STUDIES ON THE POLYPYRROLE/POLYELECTROLYTE MOLECULAR COMPOSITES

The potyelectrolyte of propane sulfonate(PS) grafted PPTA copolymers——PPTA-PS, PPTA[O]-PS, PPTA[C]-PS were prepared and used as electrolyte in the process of electrochemical polymerization of pyrrole to form the molecular composite polypyrrole (PPY)/Polyelectrolyte.The preparation and liquid crystalline property of three kinds of polyelectrolyte, the electrical conductivity, mechanical properties, SEM and thermoproperties of PPY/polyelectrolyte are presented in detail.     

SKELETON VIBRATIONS AND FORCE FIELD OF TWO ISOMOR-PHIC TRINUCLEAR μ_3-OXOFORMATO COMPLEXES OF IRON AND CHROMIUM

<正> The IR and Raman spectra for two isomorphic trinuclear μ3-oxo-formato complexes of iron and chromium were measured in the range 2000-110 cm-1.The assignments on the vibrations of the bridging and terminal coordinated formic ligands were made from the results of substitution reaction of the latter.A simplified model and a simplified general valence force field were used in normal coordinate analysis.The calculated frequencies agree well with the observed values,with a mean deviation of 1.1% for [Fe3O17C] and 0.9% for [Cr3O17C],confirming our assignments of their vibrational spectra.Two sets of the force constants have been calculated.In terms of the relationship among the vibrational frequencies,structure and some properties of the compounds,the rationality and reliability of the results were discussed.     

新型取代硅桥联茂稀土化合物的合成及在纳米级氢化钠助催化剂作用下高活性催化甲基丙烯酸甲酯聚合的研究

The synthesis and characterization of four new silicon-linked lanthanocene complexes with pendant phenyl groups on cyclopentadiene were reported. Based on the data of elemental analyses, MS and IR, the complexes were presumed to be unsolvated and dimeric complexes [Me2Si(C5H3CMe2C6H5)2LnC1]2 [Ln=Er (1), Gd (2), Sm (3), Dy (4)]. In conjunction with AlEt3 or sodium hydride as the co-catalyst, these complexes could efficiently catalyze the polymerization of methyl methacrylate (MMA). When the nanometric sodium hydride was used as a co-catalyst, the complexes were highly effective for the polymerization of MMA. At low temperature and in short time, in [MeESi(C5H3CMe2C6H5)2LnC1]2/NaH (nanometric) system, the polymer was obtained in more than 80% yield and the molecular weight was greater than 105. The activity reached that of organolanthanide hydride as a single-component catalyst. In ]MeESi(C5H3CMe2C6H5)2ErC1]2/Nail (nanometric) system, the effects of the molar ratio of MMA/catalyst and catalyst/co-catalyst, and the temperature on polymerization were studied.     

Synthesis, Crystal Structure and Characterization of α-（1-Benzimidazolyl） -hypnone Cobalt（Ⅱ） Complex： [CoCl （ C7H5N2CH2COPh）4] Br

The crystal structure of [CoCl ( C7H5N2CH2COPh)4] Br has been determined by means of X-ray crystallography. The molecular structure consists of a discrete [CoCl ( C7H5N2CH2COPh)4] ^ cation and one Br^- anion, in the [CoCl ( C7H5N2CH2COPh)4]^ cation, the coordination geometry of the central Co atom is square-pyramidal with four tertiary N atoms of benzimidazole from four α-( benzimidazol-1-yl) -hypnone ligands in the basal position and one chloride anion in the apical position. In the solid state, [CoCl ( C7H5N2CH2COPh)4]^ and Br^- anion possess intermolecular and intramolecular interactions, which stabilize the crystal structure. The characterization of the title compound were also carried out by using elemeutal analysis, FTIR, UV spectrometries and TG-DSC.     

Synthesis and thermal properties of novel calix[4]arene derivatives containing 1,2,3-triazole moiety via K2CO3-catalyzed 1,3-dipolar cycloaddition reaction

Two calix[4]arene derivatives containing 1,2,3-triazole moiety were synthesized via K2CO3-catalyzed1,3-dipolar cycloaddition reaction between calix[4]arene-based azide and active methylene compounds in good yields.The structures of the two compounds synthesized herein were fully confirmed by 1HNMR,,（13）C NMR,and MS（ESI）.The thermal analysis showed that the mass losses of the synthesized compounds 4 and 5 containing 1,2,3-triazole groups are similar to each other.