Reversible Ultra-Slow Crystal Growth of Mixed Lead Bismuth Perovskite Nanocrystals: The Presence of Dynamic Capping

An ultra-slow crystal growth over a period of 24 h of a newly synthesized CH₃NH₃Pb_1/2Bi_1/3I₃ perovskite (MPBI) nanocrystal in non-polar toluene medium is reported here. From several spectroscopic techniques as well as from TEM analysis we found that the size of nanocrystals changes continuously with time, in spite of being capped by the ligands. Using a single molecular spectroscopic technique, we also found that this size change is not due to the stacking of nanocrystals but due to crystal growth. The notable temperature dependence and reversible nature of the nanocrystals growth is explained by the dynamic nature of the capping. The observed temperature-dependent ultra-slow growth is believed to be a pragmatic step towards controlling the size of perovskite NC in a systematic manner.     

Copper nanoclusters conjugated silica nanoparticles modified on carbon paste as an electrochemical sensor for the determination of dopamine

An electrochemical sensor based on modification of carbon paste electrode by glutathione‐capped copper nanoclusters silica nanoparticles (CuNCs/SiO₂NPs) composite for determination of dopamine in the presence of ascorbic acid was presented. Transmission electron microscopy, scanning electron microscopy, energy dispersive X‐Ray analysis, X‐ray photoelectron spectroscopy, Fourier‐transform infrared spectroscopy, X‐ray diffraction and electrochemical impedance spectroscopy were used for characterization of the developed electrode. The electrochemical behavior of dopamine on CuNCs/SiO₂NPs/carbon paste electrode was investigated by cyclic voltammetry and differential pulse voltammetry. Dopamine was determined in the range of 10.0 – 900.0 μM, and the limit of detection was obtained as 0.43 μM. The electrochemical behaviors of the coexisting electroactive species, which often cause interference with the determination of dopamine, were investigated. The results show that the developed electrode does not show any interference with respect to coexisting species, even in the presence of ascorbic acid. The developed electrochemical sensor was further employed for the determination of dopamine in human blood plasma, with a good recovery.     

Effects of hydroxyl‐group end capping and branching on the physical properties of tailored polyethylene terephthalates

Polyethylene terephthalates (PETs) with well‐defined chemical structures were prepared by molecular design, and the effect of the chemical structure on the physical properties of PET was investigated. Hydroxyl‐group end‐capped PETs with η_inh = 0.4–0.6 dL/g exhibited a viscosity behavior similar to Bingham fluids, although other PETs with similar molecular weights (MWs) showed Newtonian flow behavior. This rheological feature was more noticeable for hydroxyl‐group end‐capped branched PETs. In addition, hydroxyl‐group end‐capped branched PETs became solidlike from 80 rad/s as the frequency was increased. On the other hand, hydroxyl end‐capped linear PETs showed a noticeable viscoelastic transition peak around 20 rad/s. High MW linear and branched PETs with η_inh ≥ 0.9 prepared by multistep synthesis showed non‐Newtonian fluid behavior. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1027–1035, 2001     

Nitroxide‐mediated Living Radical Polymerization of Styrene with Fluorescent Initiator

A fluorescence method was used for determination of marked chain ends in polystyrene samples prepared by 4‐substituted TEMPO type nitroxide‐mediated living free radical polymerization of styrene. 2,2,6,6‐Tetramethyl‐1‐(1‐phenylethoxy)‐piperidin‐4‐yl‐4‐pyren‐1‐ylbutanoate (PYNOR) was prepared and used as an unimolecular initiator bearing pyrene as a fluorescence mark on mediating nitroxide fragment. The bulk polymerization of styrene at 120°C, in the presence of new unimolecular initiator, was a typical nitroxide mediated living radical polymerization. For comparison, two different molar ratios of initiator and monomer (1∶400 and 1∶1000 initiator ‐ monomer [I:M]) were used for polymerization. When I:M=1∶400, the obtained polydispersity was 1.12 and maximum molecular weight 27,000 g/mol was obtained at 62% conversion. For ratio 1∶1000, slightly higher polydispersity was obtained ?1.26 and the molecular weight was 53,000 g/mol at 70% conversion. The content of the polystyrene chains bearing mediating nitroxide fragment was determined by fluorescence spectroscopy. The intensity of pyrene fluorescence decreased as the molar mass, and the conversion increased as well. The extent of the incorporation of chromophore at propagating chain end or “livingness” of polymerization decreased despite the fact that the polydispersity did not change. The extent of side reaction leading to broadening of polydispersity is suppressed due to the high viscosity of the system at higher conversion. A low extent of “livingness” will have a very negative effect on possible preparation of block copolymers.     

Target Syntheses of Two New Bivanadyl Capped Keggin Polyoxometalate Derivatives

Two new bivanadyl capped Keggin polyoxometalate-based inorganic–organic hybrid compounds, [M(2,2′-bipy)₂(H₂O)]₂[AsMo₁₂O₄₀(VO)₂]}(M = Co 1, Zn 2; bipy = bipyridine), have been synthesized under hydrothermal conditions by directly using Li₃[AsMo₁₂O₄₀] · nH₂O as starting materials. Single crystal X-ray analysis revealed that compounds 1 and 2 were isostructural, consisting of a neutral bivanadyl capped Keggin POMs bigrafted by [M(2,2′-bipy)₂(H₂O)]²⁺ fragments. Other characterizations by elemental analysis, IR spectra, XPS spectra, power X-ray diffraction and TG analysis were also described in the paper. The study of the electrochemical properties of compounds 1 and 2 exhibit similar redox behaviors, undergoing three two-electron reversible redox processes, and the electrocatalysis of 1 has also been studied in detail. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

D-Proline capped gold nanoclusters for turn-on detection of serum Raltitrexed

Using D-proline (D-Pro) as the reducing agent and capper, D-Pro@AuNCs was rapidly constructed. Its fluorescence could be quenched by AuNPs. Due to the electrostatic interaction between anticancer drug Raltitrexed (RTX) and AuNPs induced fluorescence "turn-on" principle, the resultant fluorescent probe exhibited good selectivity and sensitivity for detecting RTX in rat serums.     

3-巯基丙酸包裹的金纳米粒子自组装膜的制备及其层状周期性结构分析

制备了 3-巯基丙酸包裹的金钠米粒子水溶胶。在胺丙基三甲氧基硅烷覆盖的 Si或Si O2 基底上组装了上述金纳米粒子的单层膜和由 1 ,6-二巯基己烷联接的金纳米粒子多层膜。紫外 -可见吸收光谱和 X-射线衍射实验分析了多层膜的层状周期性结构     

一种二帽pseudo-Keggin结构簇合物[HN(C_2H_5)_3]_3[N(C_2H_5)_3]_2[Mo_8~ⅣMo_4~ⅤV_2~ⅣO_(38)(PO_4)]的水热合成、结构和性质研究

金属－氧簇合物因其结构多样性及在催化、材料和医药等方面的应用而引起人们的关注犤１犦。在众多金属－氧簇合物中，Keggin结构及金属取代Keggin结构金属－氧簇被大量报道，但由于很难获得高质量单晶，有关二帽Keggin结构的报道非常少，目前只有几例报道犤２～９犦。近年来，随着水热法应用到金属－氧簇的合成，陆续获得了一系列具有新颖结构的簇合物。１９９８年，通过水热法获得了第一个二帽pseudo－Keggin结构簇合物犤NH４犦４H犤PMo８VⅣ４VⅤ２O４２犦·２４H２O犤１０犦。我们用水热法以三乙胺做模板剂获得了一种全新的二帽pse…     

Effect of structure and concentration of polymer, metal ion and pH of the medium on the fluorescence characteristics of hyperbranched polyamines

A series of hyperbranched polyamines have been prepared by the reported method. All these polyamines exhibit fluorescence at about 350-650 nm with maximum intensity at about 450 nm. The study shows that the fluorescence intensity and the range of wavelength of fluorescence are strongly influenced by the structure of the hyperbranched polyamines. The effect of concentration of the polymer, pH of the medium and metal ion has also been investigated on the fluorescence characteristics of sulfone containing hyperbranched polyamine (Ps), as it shows the best result among the studied polymers. The results show that the intensity of fluorescence increases with the decrease of concentration (5-0.1 g/L in N,N′-dimethyl sulfoxide) of polymer and with the increase of pH (3.1-11.6) of the medium. The quenching of fluorescence increases with the increase of concentration of Cu²⁺ ions (0.01-0.04%). The hyperbranched polyamine (Ps) has also been end capped with benzoyl chloride and 4-hydroxybenzaldehyde to study the influence of end groups. The results showed that the structure of end capped compounds has prominent role to influence fluorescence characteristics of this hyperbranched polyamine.     

化学和电化学方法合成苯/胺封端苯胺四聚体

利用改进了MacDiarmid氧化偶联方法合成了苯／胺封端的苯胺四聚体，通过对循环伏安曲线的分析，给出二聚体经由电化学氧化－化学偶联成为四聚体的机理，利用基质辅助激光解吸质谱和红外光谱对产物进行了表征。