液晶态分子在分析化学中的应用进展

评述了液晶态分子在分析化学中的应用进展，包括其超分子的分子识别作用，液晶在色谱，光谱探针，核磁共振谱等分析化学领域中的应用。     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 11. Synthesis and total assignment of the 1H and 13C NMR spectra of isomeric benzothienonaphthoquinolines using multiple inverse detected two-dimensional NMR methods

Two novel heterocyclic ring systems, namely, [1]benzothieno[2,3-c]naphtho[1,2-f]quinoline and [1]benzothieno[2,3-c]naphtho[2,1-g]quinoline have been synthesized and characterized by inverse detected two-dimensional nmr methods. Unequivocal total assignments of the proton and carbon nmr spectra were made through the concerted utilization of HMQC (Heteronuclear Multiple Quantum Correlation) and a combination of HMBC (Heteronuclear Multiple Bond Correlation) and HMQC-TOCSY (HMQC with proton TOtal Correlation Spectroscopy).     

The formation of mesoporous TiO2 spheres via a facile chemical process

The mesoporous TiO(2) solid and hollow spheres have been synthesized via a controllable and simple chemical route. Structural characterization indicates that these TiO(2) mesoporous spheres after calcined at 500 degrees C have an obvious mesoporous structure with the diameters of 200-300 nm for solid spheres and 200-500 nm for hollow spheres. The average pore sizes and BET surface areas of the mesoporous TiO(2) solid and hollow spheres are 6.8, 7.0 nm and 162, 90 m(2)/g, respectively. Optical adsorption investigation shows that TiO(2) solid and hollow spheres possess a direct band gap structure with the optical band gap of 3.68 and 3.75 eV, respectively. A possible formation mechanism for TiO(2) solid and hollow spheres is discussed.     

A direct quantitative analysis method for monitoring biogenic volatile organic compounds released from leaves of Pelargonium hortorum in situ

A direct quantitative method is presented that is based upon the use of multiple headspace solid phase microextraction (HS-SPME) to monitor biogenic volatile organic compounds (BVOCs) released from a living leaf of Pelargonium hortorum in situ. Seventeen BVOCs were detected by GC-MS after a single SPME extraction using a CAR/DVB/PDMS fibre. An internal standard was employed to determine the absolute amounts of seven terpenoid compounds released from a P. hortorum leaf. The quantitative analysis was performed over two days, with extraction preformed for 20 min every 3 h. The amount of volatiles extracted varied with the time of day, with two maxima recorded at 14:00 (day 1) and 17:00 (day 2), corresponding to 236 and 277 ng of the seven terpenoids recorded, respectively. These results indicate that multiple HS-SPME in combination with an internal standard is a simple, quick, and quantitative technique for analysising BVOC emissions from a live plant sample.     

Dexmedetomidine promotes the progression of hepatocellular carcinoma through hepatic stellate cell activation

Dexmedetomidine (DEX) is an anesthetic that is widely used in the clinic, and it has been reported to exhibit paradoxical effects in the progression of multiple solid tumors. In this study, we sought to explore the mechanism by which DEX regulates hepatocellular carcinoma (HCC) progression underlying liver fibrosis. We determined the effects of DEX on tumor progression in an orthotopic HCC mouse model of fibrotic liver. A coculture system and a subcutaneous xenograft model involving coimplantation of mouse hepatoma cells (H22) and primary activated hepatic stellate cells (aHSCs) were used to study the effects of DEX on HCC progression. We found that in the preclinical mouse model of liver fibrosis, DEX treatment significantly shortened median survival time and promoted tumor growth, intrahepatic metastasis and pulmonary metastasis. The DEX receptor (ADRA2A) was mainly expressed in aHSCs but was barely detected in HCC cells. DEX dramatically reinforced HCC malignant behaviors in the presence of aHSCs in both the coculture system and the coimplantation mouse model, but DEX alone exerted no significant effects on the malignancy of HCC. Mechanistically, DEX induced IL-6 secretion from aHSCs and promoted HCC progression via STAT3 activation. Our findings provide evidence that the clinical application of DEX may cause undesirable side effects in HCC patients with liver fibrosis.Subject terms: Cancer microenvironment, Cell growth     

Catalytic oxidation of alcohols with polymer-supported ruthenium complex under mild conditions

Polymer-supported ruthenium-containing complex PS–Phen–Ru was synthesized (where PS = chloromethyl polystyrene resin, Phen = 1,10-phenanthroline) and was characterized by FT-IR, ICP, and XPS. The supported complex was used to catalyze the oxidation of primary aliphatic alcohols as well as aromatic alcohols in the presence of iodosylbenzene. The oxidations were carried out in acetonitrile solution, affording the corresponding aldehydes or ketones in high substrate conversion and high selectivities under mild reaction conditions. The catalyst can be easily prepared and can be recycled.     

The assemble,grow and lift-off (AGLO) strategy to construct complex gold nanostructures with pre-designed morphologies

The construction of metallic nanostructures with customizable morphologies and complex shapes has been an essential pursuit in nanoscience. DNA nanotechnology has enabled the fabrication of increasingly complex DNA nanostructures with unprecedented specificity, programmability and sub-nanometer precision, which makes it an ideal approach to rationally organize metallic nanostructures. Here we report an Assemble, Grow and Lift-Off (AGLO) strategy to construct robust standalone gold nanostructures with pre-designed customizable shapes in solution, using only a simple 2D DNA origami sheet as a versatile transient template. Gold nanoparticle (AuNP) seeds were firstly assembled onto the pre-designed binding sites of the DNA origami template and then additional gold was slowly deposited onto the AuNP seeds. The growing seed surfaces eventually merge with adjacent seeds to generate one continuous gold nanostructure in a pre-designed shape, which can then be lifted off the origami template. Diverse customized patterns of templated AuNP seeds were successfully transformed into corresponding gold nanostructures with the target structure transformation percentage over 80%. Moreover, the AGLO strategy can be incorporated with a magnetic bead separation platform to enable the easy recycling of the excess AuNP seeds and DNA components.

The AGLO strategy generates complex gold nanostructures with user-designed morphologies in solution, using only a simple 2D DNA origami sheet as a versatile transient template. The products are robust and stable as standalone gold nanostructures.     

Propane fuel cells using phosphoric-acid-doped polybenzimidazole membranes

Propane fuel cells using H(3)PO(4)-doped polybenzimidazole polymer membranes produce low and unsustainable current densities at temperatures up to 250 degrees C under anhydrous conditions. Stable intermediate species blocked the surface of noble metal anode catalysts, and the intermediate species could not react further into desorbable final products. In contrast, when water was introduced by light humidification (S(r) 0.08%) of the propane stream, sustainable and higher current densities were achieved. Water participated in the reaction sequence to form surface-bound hydrocarbon and then oxygen-containing intermediates and thereby generated CO and CO(2) as the only carbon-containing products.     

Micro-Determination of Protein Containing SH– and –S–S– Groups Based on the Polarographic wave of an Electroactive Derivative

This paper presents a new simple and sensitive method for the micro-determination of protein containing SH– and –S–S– groups based on the single sweep polarographic wave of an electroactive derivative. In 0.04molL^–1 Na₃PO₄ and 0.2% ascorbic acid solution, protein is heated in a boiling water bath for 15min, the reaction product giving a sensitive reduction wave at –0.70V (vs. SCE). The wave height is linearly proportional to the concentration of protein. The calibration curves of bovine serum albumin (BSA), human serum albumin (HSA), ovalbumin (OVA) and lysozyme (Lyso) are constructed under the optimal conditions. For BSA and HSA, the linear ranges and detection limits are 0.05–24mgL^–1 and 0.02mgL^–1, respectively. The method has been applied to the determination of protein in human serum samples with satisfactory results. The mechanism of the polarographic wave was also studied, and the results show that S^2– ion is released from the protein molecule during the derivatization reaction, the wave being attributed to the reduction of HgS.     

Spectrophotometric determination of microamounts of scandium with o-chlorophenylfluorone and cetyltrimethylammonium bromide

The reaction of scandium(III) with o-chlorophenylfluorone (o-CIPF) in the presence of cetyltrimethylammonium bromide (CTMAB) has been studied. In an acetate buffer at pH 4.4, a red-purple complex is obtained, with maximum absorption at 569 nm and a molar absorptivity of 1.31 x 10(5)1.mole(-1).cm(-1). The composition of the complex is found to be 1:2:2 Sc-o-CIPF-CTMAB. Beer's law is obeyed over the range 0-12 mug/25 ml scandium. The proposed method has been used for determination of trace scandium in tungsten ores after its prior separation by solvent extraction.