Preparation of novel structural nanosized Y2O3 powders and their catalytic activity on the decomposition of NH4ClO4

For the first time, novel structural nanosized Y₂O₃ powders were successfully synthesized by the n-butanol soft-template method. X-ray diffraction, transmission electron microscopy, scanning electron microscopy and Raman spectroscopy were used to characterize the products. The results indicate that these products (calcined at 700°C) were comprised of many Y₂O₃ nanomembranes, and the nanomembranes could change into nanorods when calcined at 1000°C. Interestingly, differential thermal analysis studies suggested that the nanosized Y₂O₃ crystals had intense catalytic activity on the thermal decomposition of ammonium perchlorate.     

DNA sequencing and genotyping in miniaturized electrophoresis systems

Advances in microchannel electrophoretic separation systems for DNA analyses have had important impacts on biological and biomedical sciences, as exemplified by the successes of the Human Genome Project (HGP). As we enter a new era in genomic science, further technological innovations promise to provide other far-reaching benefits, many of which will require continual increases in sequencing and genotyping efficiency and throughput, as well as major decreases in the cost per analysis. Since the high-resolution size- and/or conformation-based electrophoretic separation of DNA is the most critical step in many genetic analyses, continual advances in the development of materials and methods for microchannel electrophoretic separations will be needed to meet the massive demand for high-quality, low-cost genomic data. In particular, the development (and commercialization) of miniaturized genotyping platforms is needed to support and enable the future breakthroughs of biomedical science. In this review, we briefly discuss the major sequencing and genotyping techniques in which high-throughput and high-resolution electrophoretic separations of DNA play a significant role. We review recent advances in the development of technology for capillary electrophoresis (CE), including capillary array electrophoresis (CAE) systems. Most of these CE/CAE innovations are equally applicable to implementation on microfabricated electrophoresis chips. Major effort is devoted to discussing various key elements needed for the development of integrated and practical microfluidic sequencing and genotyping platforms, including chip substrate selection, microchannel design and fabrication, microchannel surface modification, sample preparation, analyte detection, DNA sieving matrices, and device integration. Finally, we identify some of the remaining challenges, and some of the possible routes to further advances in high-throughput DNA sequencing and genotyping technologies.     

Determining the folding and unfolding rate constants of nucleic acids by biosensor. Application to telomere G-quadruplex

Nucleic acid molecules may fold into secondary structures, and the formation of such structures is involved in many biological processes and technical applications. The folding and unfolding rate constants define the kinetics of conformation interconversion and the stability of these structures and is important in realizing their functions. We developed a method to determine these kinetic parameters using an optical biosensor based on surface plasmon resonance. The folding and unfolding of a nucleic acid is coupled with a hybridization reaction by immobilization of the target nucleic acid on a sensor chip surface and injection of a complementary probe nucleic acid over the sensor chip surface. By monitoring the time course of duplex formation, both the folding and unfolding rate constants for the target nucleic acid and the association and dissociation rate constants for the target-probe duplex can all be derived from the same measurement. We applied this method to determine the folding and unfolding rate constants of the G-quadruplex of human telomere sequence (TTAGGG)(4) and its association and dissociation rate constants with the complementary strand (CCCTAA)(4). The results show that both the folding and unfolding occur on the time scale of minutes at physiological concentration of K(+). We speculate that this property might be important for telomere elongation. A complete set of the kinetic parameters for both of the structures allows us to study the competition between the formation of the quadruplex and the duplex. Calculations indicate that the formation of both the quadruplex and the duplex is strand concentration-dependent, and the quadruplex can be efficiently formed at low strand concentration. This property may provide the basis for the formation of the quadruplex in vivo in the presence of a complementary strand.     

Identification and quantification of 13 components in Angelica sinensis (Danggui) by gas chromatography-mass spectrometry coupled with pressurized liquid extraction

Angelica sinensis (Danggui in Chinese), a well-known traditional Chinese medicine, is also used as a health food product for women's care in Europe and America. Therefore, the demand for Danggui is enormous throughout the world. Due to the shortage of Angelica sinensis, Angelica acutiloba and Angelica gigas are commonly used as the substitutes of Danggui in the market of southeast Asia. However, the three common Angelica roots showed variation in their genetic and chemical composition. Up to date, it is thought that ferulic acid, ligustilide and other phthalides such as butylidenephthalide are the biologically active components of Danggui. In this paper, the contents of 13 compounds including ferulic acid, Z-ligustilide, E-ligustilide, Z-butylidenephthalide, E-butylidenephthalide, 3-butylphthalide, 3-butylidene-4-hydroxyphthalide, senkyunolide A, 6,7-epoxyligustilide, senkyunolide F, senkyunolide H, senkyunolide I, and 6,7-dihydroxyligustilide were determined or estimated by using gas chromatography-mass spectrometry (GC-MS) coupled with pressurized liquid extraction (PLE). The results showed that GC-MS coupled with PLE offered a simple, rapid and high sensitive method to analysis of components in Angelica root. And the contents of investigated compounds in Angelica sinensis, Angelica acutiloba and Angelica gigas, which are used as Danggui in China, Japan and Korea, respectively, were highly variant. It is thought that interaction of multiple chemical compounds contributes to the therapeutic effects of Chinese medicines. However, the overall clinical efficacy of these different Danggui has not been determined. Therefore, comparison of chemical components and pharmacological activities of different Angelica root is helpful to elucidate the mechanism of therapeutic effects of Danggui.     

Synthesis and photovoltaic properties of alternating conjugated polymers derived from indolo[3,2-<Emphasis Type="Italic">b</Emphasis>]carbazole and thiophene/thieno[3,2-<Emphasis Type="Italic">b</Emphasis>]thiophene-cored benzoselenadiazole

Two alternating narrow band gap (NBG) copolymers derived from 5,11-di(N-9-heptadecanyl)-indolo[3,2-b]carbazole (ICZ) and 4,7-di(thien-2-yl)-2′,1′,3′-benzoselenadiazole (DSeBT) or 4,7-di(thieno[3,2-b]thien-2-yl)-2′,1′,3′-benzoselenadiazole (DTSeBT), were synthesized and named PICZ-DSeBT and PICZ-DTSeBT, respectively. The PICZ-DSeBT shows good solubility in common organic solvent, and the PICZ-DTSeBT is soluble in hot o-dichlorobenzene (ODCB) and not good soluble in chloroform, toluene etc. The chemical structure, molecular weight and fundamental physical properties of the copolymers were characterized by ¹H NMR, gel permeation chromatography (GPC), cyclic voltammetry (CV), thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) etc. Potential application of the copolymers to be employed as electron donor material and PC61BM ([6,6]-phenyl-C₆₁ butyric acid methyl ester) for photovoltaic solar cells (PSCs), were investigated. PSCs based on the blends of PICZ-DSeBT/PC₆₁BM (w: w; 1: 2) or PICZ-DTSeBT/PC₆₁BM (w: w; 1: 2) with devices configuration as ITO/PEDOT: PSS/blend/Al, show the power conversion efficiencies (PCEs) of 1.06% and 1.52%, with the open circuit voltage (V _oc) of 0.75 V and 0.70 V, short circuit current densities (J _sc) of 3.45 mA/cm² and 5.30 mA/cm² under an AM1.5 simulator (100 mW/cm²) and the photocurrent response on-set wavelength extending up to 760 nm and 800 nm, respectively. It indicates that the NBG copolymers are viable electron donor materials for PSCs.     

Factors that regulate the conformation of m-benziporphodimethene complexes: agostic metal-arene interaction, hydrogen bonding, and η2,π coordination

Group 12 and silver(I) tetramethyl‐m‐benziporphodimethene (TMBPDM) complexes with phenyl, methylbenzoate, or nitrophenyl groups as meso substituents were synthesized and fully characterized. The dimeric silver(I) complex displays an unusual η²,π coordination from the β‐pyrrolic C?C bond to the silver ion. All of the complexes displayed a close contact between the metal ion and the inner C(22)? H(22) on the m‐phenylene ring. The downfield chemical shifts of H(22) and large coupling constants between Cd^II and H(22) strongly support the presence of an agostic interaction between the metal ion and inner C(22)–H(22). Crystal structures revealed that the syn form is the predominant conformation for TMBPDM complexes. This is distinctively different from the exclusive anti conformation observed in m‐benziporphyrin and tetraphenyl‐m‐benziporphodimethene (TPBPDM) complexes. Evidently, intramolecular hydrogen‐bonding interactions between axial chloride and methyl groups stabilize syn conformations. Unlike the merely syn conformation observed in the solid‐state structures of TMBPDM complexes that contain an axial chloride, in solution these complexes display highly solvent‐ and temperature‐dependent syn/anti ratio changes. The observation of dynamic ¹H NMR spectroscopic scrambling between syn and anti conformations from the titration of chloride ion into the solution of the TMBPDM complex suggests that axial ligand exchange is a likely pathway for the conversion between syn and anti forms. Theoretical calculations revealed that intermolecular hydrogen‐bonding interactions between the axial chloride and CHCl₃ stabilizes the anti conformation, which explains the increased ratio for the anti form when dichloromethane or chloroform was used as the solvent.     

A Study of the Interaction Between Cucurbit[8]uril and Alkyl‐Substituted 4‐Pyrrolidinopyridinium Salts

The interaction between cucuribit[8]uril (Q[8]) and a series of 4‐pyrrolidinopyridinium salts bearing aliphatic substituents at the pyridinium nitrogen, namely 4‐(C₄H₈N)C₅H₅NRBr, where R=Et (g1), n‐butyl (g2), n‐pentyl (g3), n‐hexyl (g4), n‐octyl (g5), n‐dodecyl (g6), has been studied in aqueous solution by ¹H NMR spectroscopy, electronic absorption spectroscopy, isothermal titration calorimetry and mass spectrometry. Single crystal X‐ray diffraction revealed the structure of the host–guest complexes for g1, g2, g3, and g5. In each case, the Q[8] contains two guest molecules in a centrosymmetric dimer. The orientation of the guest molecule changes as the alkyl chain increases in length. Interestingly, in the solid state, the inclusion complexes identified are different from those observed in solution, and furthermore, in the case of g3, Q[8] exhibits two different interactions with the guest. In solution, the length of the alkyl chain plays a significant role in determining the type of host–guest interaction present.     

Electrochemiluminescent sensing of dopamine using CdTe quantum dots capped with thioglycolic acid and supported with carbon nanotubes

We have synthesized water-dispersible CdTe quantum dots (QDs) capped with thioglycolic acid. Their quantum yield is higher than 54%. A sensitive electrochemiluminescence (ECL) method was established based on the modification of the composite of the QDs, carbon nanotubes and chitosan on indium tin oxide glass. The sensor displays efficient and stable anodic ECL which is quenched by dopamine. A respective sensor was designed that responds to dopamine linearly in the range of 50?pM to 10?nM, and the detection limit is 24?pM. Dopamine was determined with this sensor in spiked cerebro-spinal fluid with average recoveries of 95.7%.

A highly sensitive and selective fluorescent probe for Fe3+ containing two rhodamine B and thiocarbonyl moieties and its application to live cell imaging

A novel turn-on rhodamine B-based fluorescent chemosensor (RBCS) was designed and synthesized by reacting N-(rhodamine B)lactam-1,2-ethylenediamine and carbon disulfide. Upon addition of Fe³⁺ in EtOH/H₂O solution (2:1, v/v, HEPES buffer, 0.6?mM, pH 7.20), the RBCS displayed a significant fluorescence enhancement at 582?nm and a dramatic color change from colorless to pink, which can be detected by the naked eye. Significantly, the RBCS exhibited a highly selective and sensitive ability toward Fe³⁺. The detection limit of the probe was 2.05?×?10^?7?M. Job's plot indicated the formation of 1:1 complex between the RBCS and Fe³⁺. Moreover, the practical use of the RBCS is demonstrated by its application in the detection of Fe³⁺ in HeLa cells.     

Ti-ZSM-11的红外光谱研究

随着杂原子分子筛研究领域的开拓与发展，近年来，对钛硅沸石的研究逐渐增多．Ti－ZSM－11（TS－2）型分子筛是由Reddy，Ratanasarny等[1]首先合成的．钛硅沸石的表征与其它杂原子分子筛相比较为复杂，对杂原子Ti是否进入了骨架还没有一个直接的证据，且争议较多．在红外光谱的研究中，对960cm－1－980cm－1区间的特征吸收的归属也存在着很大的分歧[2－4]．钛硅沸石在H2O2对有机化合物的选择氧化领域有极其优良的催化性能[1]，因此，对它的开发有广泛的应用前景．本文以动态和静态相结合的水热晶化法合成了Ti－ZSM－11型分子筛．IR光…