A novel and efficient synthesis of pyrazolo[3,4-d]pyrimidine derivatives and the study of their anti-bacterial activity

In this work 4-amino-6-aryl-2-phenyl pyrimidine-5-carbonitrile derivatives were synthesized through a one-pot,three-component reaction of an aldehyde,malononitrile and benzamidine hydrochloride,in the presence of magnetic nano Fe₃O₄ particles as a catalyst under solvent-free conditions.3-Amino-6-aryl- 2-phenylpyrazolo[3,4-d]pyrimidine derivatives were prepared through an efficient and environmentally friendly reaction between 4-amino-6-aryl-2-phenylpyrimidine-5-carbonitrile derivatives and hydrazine hydrate and their antibacterial activity has been evaluated.     

Two-dimensional correlation spectroscopic studies on coordination between carbonyl group of butanone and metalions

Two dimensional asynchronous spectra were used to characterize coordination between carbonyl group of butanone and metal ions by using an approach proposed in our recent paper.Spectral variation of n-π~*transition band of carbonyl group is used to probe the coordination even if metal ions does not possess any characteristic peak in spectra.Experimental results indicate that Ca~(2+) and Al~(3+) show considerable ability to coordinate with the carbonyl group of butanone and bring about spectral variation of the n-π~*transition band,which is manifested by cross peaks in 2D asynchronous spectra.     

Microwave-assisted,facile, rapid and solvent-free one pot two-component synthesis of some special acylals

A facile,rapid and solvent-free method for the conversion of acids and dihalomethane to the corresponding methylene diesters(acylals) using microwave as activators or assistor,is reported.This method is particularly powerful for the diesterification of carboxylic acids,which afford methylene diesters in good to excellent yields(up to >99%).When the intermediate is trapped,a "double successive S_N2 reactions" mechanism is proved.     

SnO2 hollow nanospheres assembled by single layer nanocrystals as anode material for high performance Li ion batteries

SnO₂ hollow nanospheres were successfully synthesized via a facile one-step solvothermal method.Characterizations show that the as-prepared SnO₂ spheres are of hollow structure with a diameter at around 50 nm,and especially,the shell of the spheres is assembled by single layer SnO₂ nanocrystals.The surface area of the material reaches up to 202.5 m²/g.As an anode material for Li ion batteries,the sample exhibited improved electrochemical performance compared with commercial SnO₂ particles.After cycled at high current rate of 0.5 C,1 C and 0.5 C for 20 cycles,respectively,the electrode can maintain a capacity of 509 mAh/g.The suitable shell thickness/diameter ratio endows the good structural stability of the material during cycling,which promises the excellent cycling performance of the electrode.The large surface area and the ultra thin shell ensure the high rate performance of the material.     

Cp2ZrCl2-catalyzed synthesis of 2-aminovinyl benzimidazoles under microwave conditions

A microwave-assisted general method for the synthesis of 2-aminovinyl benzimidazoles has been developed.Treatment of the 1,2-phenylenediamines and N-arylated/N,N-dialkylated 3-aminoacroleins with bis(cyclopentadienyl)zirconium(IV) dichloride(Cp2Zr Cl2) as the catalyst under microwave irradiation for 3–5 min followed by in situ Mn O2 oxidation afforded thirteen 2-aminovinyl benzimidazoles in good yields.     

Alumina-supported heteropoly acid: An effi cient catalyst for the synthesis of azaarene substituted 3-hydroxy-2-oxindole derivatives via C(sp3)H bond functionalization

A method of C(sp3)-H bond functionalization of methyl azaarenes catalyzed by alumina-supported heteropoly acid and addition to isatins was developed. This transformation could be used for the synthesis of biologically important 3-hydroxy-2-oxindole derivatives in good to excellent yields and the catalyst could be reused for six times without significant decrease in activity.     

Gel-incorporated PbS and PbI2 single-crystals

Gel-incorporated single-crystals provide unique combinational properties of long-range order and composite structures, which is desired for semiconducting and conducting materials. However, the reported gel-incorporated single-crystals are limited to insulating crystals. Here, we examine crystals of two typical semiconductors, lead sulfide (PbS) and lead iodide (PbI2), grown from both silica gels and agarose gels. In all the four crystal-gel pairs, single-crystals of the cubic phase of PbS and the hexagonal phase of PbI2 were obtained according to the X-ray diffraction analysis. Dissolution of the gel-grown crystals exposed insoluble materials with the shape similar to the original crystals, indicative of gelincorporation inside the crystals. As such, this work creates a facile strategy to construct 3D heterostructures inside semiconducting single-crystals without destroying their long-range order.     

PEGylated WS2 nanosheets for X-ray computed tomography imaging and photothermal therapy

WS2 nanosheets were prepared by the solvent-thermal method in the presence of n-butyl lithium, then the exfoliation under the condition of ultrasound. The formed WS2 nanosheets were conjugated with thiol-modified polyethylene glycol (PEG-SH) to improve the biocompatibility. The nanosheets (WS2-PEG) were able to inhibit the growth of a model HeLa cancer cell line in vitro due to the high photothermal conversion efficiency of 35% irradiated by an 808 nm laser (1 W/cm2). As a proof of concept, WS2-PEG nanosheets with the better X-ray attenuation property than the clinical computed tomography (CT) contrast agent (Iohexol) could be performed for CT imaging of the lymph vessel.     

Jahn-Teller畸变后D2h C60--的电子结构和光谱

用INDO系列方法对C60自由基负离子进行了几何构型优化,得到D2h对称性的构型,表明C60--确实发生了Jahn-Teller畸变,导致单键变短,双键变长,形成15种键,9种不等同碳原子,其额外负电荷主要分布在赤道附近。以此构型为基础,计算了C60--的电子光谱,与实验值吻合,在对光谱进行理论指认的同时讨论了光谱红移的原因。     

用Xα方法对CH4在Ni(Ⅲ)表面吸附解离反应的理论研究

用Ｘ_α方法对ＣＨ_４在Ｎｉ（Ⅲ）表面吸附解离反应的理论研究马晨生,马理,杨忠志（吉林大学理论化学研究所,长春,１３００２３）关键词ＣＨ_４／Ｎｉ（Ⅲ）吸附体系,原子簇模型,ＣＨ_４／Ｍｉ_７,ＭＳ－Ｘ_α－ＳＣＦ方法甲烷在Ｎｉ表面的催化重整反应在工业和国...     

Interactions between pyridinium and Nd3+

In this paper,2D asynchronous spectra generated by using the DAOSD approach was utilized to probe interactions between Nd~(3+) and pyridinium dissolved in aqueous solution.A series of cross peaks in the resultant 2D asynchronous spectrum confirms the occurrence of intermolecular interaction between Nd~(3+)and pyridinium.However,no coordination occurs between Nd~(3+) and pyridinium.Interaction between πelectron from aromatic system and/electron from lanthanide ions account for the appearance of cross peaks in 2D asynchronous spectra.Because of the interaction,the emission spectrum of pyridinium exhibits a significant change when neodymium perchlorate was introduced into the system.     

Highly effi cient and regioselective thiocyanation of aromatic amines,anisols and activated phenols with H2O2/NH4SCN catalyzed by nanomagnetic Fe3O4

A new method employing magnetic nanoparticles Fe3O4 as a catalyst and H2O2 as a green oxidant is developed for the oxidative thiocyanation of aromatic amines, anisols and activated phenols with high yields under mild reaction conditions. The catalyst could be easily recovered from the reaction mixture using an external magnet and reused in several reaction cycles without loss of activity.     

~1H–~(15)N HMBC spectra of C_(18)-diterpenoid alkaloids

The normally underused 1H–15N HMBC spectra of thirteen C18-diterpenoid alkaloids have been determined for the first time. As a result, the significant effects of the substituents of nitrogen atoms, the conformations of A ring, and protonation, on the nitrogen-15 chemical shifts are demonstrated.     

Fe(NO3)3·9H2O-catalyzed aerobic oxidation of sulfi des to sulfoxides under mild conditions with the aid of trifl uoroethanol

Selective oxidation of sulfides to sulfoxides was successfully performed by employing readily available Fe(NO3)3·9H2O as the active catalyst with oxygen as the oxidant in 2,2,2-trifluoroethanol (TFE) without the formation of sulfones. Nitrate anion could play a crucial role in promoting the reaction due to the oxidation capacity under acidic media. High yields of sulfoxides were exclusively obtained from the corresponding sulfides. Furthermore, both aromatic and aliphatic sulfides gave moderate to high yields of sulfoxides with this protocol.     

Chemical compositions and effects on chemiluminescence of AMs in vitro of chalk dusts

The aim of this study was to investigate the chemical compositions of chalk dust and examine the adverse effects of fine chalk particle matters (PM2.5) on rat alveolar macrophages (AMs) in vitro. Morphologies and element concentrations of chalk particles were analyzed using quantitative energydispersive electron probe X-ray microanalysis (ED-EPMA). The oxidative response of AMs exposed to chalk PM2.5 was measured by luminol-dependent chemiluminescence (CL). The results showed that (1) Chalk dust was mainly composed of gypsum (CaSO4), calcite (CaCO3)/dolomite (CaMg(CO3)2), and organic adhesives; (2) Fine chalk particles induced the AM production of CL, which was inhibited by about 90% by diphenyleneiodonium chloride (DPI). Based on these results, we showed that cytotoxicity of chalk PM2.5 may be related to the reactive oxygen species (ROS) generation.     

Selective hydrogenation of unprotected indole to indoline over N-doped carbon supported palladium catalyst

Mesoporous N-doped carbon supported palladium catalyst Pd@CN0.132 was able to efficiently catalyze unprotected indole to indoline under mild conditions.In the aqueous system,a selectivity of 100% and conversion of 96% was achieved under 313 K and atmospheric hydrogen gas.     

Rationalization of regioselectivity of electrophilic substitution reaction for cyclic compounds in terms of Dpb values

Accepted theories predict that substitution reactions are controlled by the electronic nature of the attacked site for electrophilic aromatic substitution. Here it is shown that in addition the bond strength of the broken bond may also influence the regioselectivity of the substitution reaction, and that the Dpb is a good indicator of the strength of a chemical bond. The Dpb denotes the depth of the potential acting on one electron in amolecule at the bond center (bc). In this letter, the values of Dpb along the C-H and N-H bonds have been investigated, and it is demonstrated that for aromatic compounds, the regioselectivity of the electrophilic substitution can well be rationalized in terms of Dpb values.     

Suzuki–Miyaura cross-coupling reactions in water using in situ generated palladium(II)–phosphazane complexes

The phosphazane derivatives(L1–3) were readily obtained by reaction of different ratios of PCl3 and PhNH2. The L1–3 derivatives were found to be efficient ligands in the palladium-catalyzed Suzuki C–C coupling reactions in water. It was determined that with the use of L1–3 /Pd(OAc)2 system as a catalyst, aryl halides undergo Suzuki cross-couplings with arylboronic acids to give the desired products in moderate to excellent yields.     

共存牺牲剂对染料敏化TiO_2纳米晶体系电子传输的影响

采用卟啉染料敏化TiO2纳米晶在可见光条件下(λ390 nm)进行水分解制氢.考察了不同牺牲剂———甲醇(MeOH)、三乙醇胺(TEOA)及其混合物对体系析氢效率的影响.通过荧光猝灭及光电化学性能分析发现,激发态染料与TiO2之间的电子转移极大地受到添加的牺牲剂的影响,而体系的pH值对其影响不大.     

Rare earth metal triflates catalyzed electrophilic nitration using N2O5

A mild,efficient and eco-friendly process for the electrophilic nitration is described using N₂O₅ as a green nitrating agent in the presence of rare earth metal triflates[RE（OTf）₃]under mild conditions.