Special odd-even effect of degree of oligomerization on properties of cyclic oligoesters

We demonstrate here seven pure cyclic samples,which belongs to two series of oligoesters,cyclic oligo(trimethylene terephthalate)s(COTTs) and cyclic oligo(butylene terephthalate)s(COBTs),showing odd-even effect of degree of oligomerization(repeating units number) on properties.The pentamer of COTT and trimer of COBT show much lower melting temperature,and the trimer of COTT and trimer of COBT show significant lower refractive index,which can be ascribed to the low packing density of cyclic oligoesters with odd number of degree of oligomerization.Our results reveal the discrete property change as a function of cyclic size of oligomers,which can be used to design materials with special properties.     

Direct electron transfer of glucose oxidase and dual hydrogen peroxide and glucose detection based on water-dispersible carbon nanotubes derivative

A water-dispersible multi-walled carbon nanotubes (MWCNTs) derivative, MWCNTs-1-one-dihydroxypyridine (MWCNTs-Py) was synthesis via Friedel–Crafts chemical acylation. Raman spectra demonstrated the conjugated level of MWCNTs-Py was retained after this chemical modification. MWCNTs-Py showed dual hydrogen peroxide (H₂O₂) and glucose detections without mutual interference by adjusting pH value. It was sensitive to H₂O₂ in acidic solution and displayed the high performances of sensitivity, linear range, response time and stability; meanwhile it did not respond to H₂O₂ in neutral solution. In addition, this positively charged MWCNTs-Py could adsorb glucose oxidase (GOD) by electrostatic attraction. MWCNTs-Py-GOD/GC electrode showed the direct electron transfer (DET) of GOD with a pair of well-defined redox peaks, attesting the bioactivity of GOD was retained due to the non-destroyed immobilization. The high surface coverage of active GOD (3.5 × 10⁻⁹ mol cm⁻²) resulted in exhibiting a good electrocatalytic activity toward glucose. This glucose sensor showed high sensitivity (68.1 μA mM⁻¹ cm⁻²) in a linear range from 3 μM to 7 mM in neutral buffer solution. The proposed sensor could distinguish H₂O₂ and glucose, thus owning high selectivity and reliability.     

烧结脱硫石膏的钙相分析

建立烧结脱硫石膏的钙相分析方法。根据石灰石浆脱硫工艺的特点,利用脱硫石膏中硫酸钙和亚硫酸钙等钙相的不同特征,用EDTA容量法测定总钙,并用ICP法、红外仪器方法测得硫酸钙、亚硫酸钙、碳酸钙等的含量,再利用差减法计算氧化钙的含量。测定结果的相对标准偏差小于1.5%(n=6),硫酸钙、亚硫酸钙、碳酸钙及氧化钙的加标回收率在97%~100%之间。该方法操作简单、快速,可用于烧结脱硫工艺中烧结脱硫石膏钙相的日常检测,实现对脱硫工艺中各阶段反应产物的准确定量。     

Self‐Guided Supramolecular Cargo‐Loaded Nanomotors with Chemotactic Behavior towards Cells

Delivery vehicles that are able to actively seek and precisely locate targeted tissues using concentration gradients of signaling molecules have hardly been explored. The directed movement toward specific cell types of cargo‐loaded polymeric nanomotors along a hydrogen peroxide concentration gradient (chemotaxis) is reported. Through self‐assembly, bowl‐shaped poly(ethylene glycol)‐b‐polystyrene nanomotors, or stomatocytes, were formed with platinum nanoparticles entrapped in the cavity while a model drug was encapsulated in the inner compartment. Directional movement of the stomatocytes in the presence of a fuel gradient (chemotaxis) was first demonstrated in both static and dynamic systems using glass channels and a microfluidic flow. The highly efficient response of these motors was subsequently shown by their directional and autonomous movement towards hydrogen peroxide secreting neutrophil cells.     

Silver‐Catalyzed Cross‐Coupling of Isocyanides and Active Methylene Compounds by a Radical Process

Isocyanides are versatile building blocks, and have been extensively exploited in C? H functionalization reactions. However, transition‐metal‐catalyzed direct C? H functionalization reactions with isocyanides suffer from over‐insertion of isocyanides. Reported herein is a radical coupling/isomerization strategy for the cross‐coupling of isocyanides with active methylene compounds through silver‐catalysis. The method solves the over‐insertion issue and affords a variety of otherwise difficult to synthesize β‐aminoenones and tricarbonylmethanes under base‐ and ligand‐free conditions. This report presents a new fundamental C? C bond‐forming reaction of two basic chemicals.     

Characterization and simultaneous quantification of biological aporphine alkaloids in Litsea cubeba by HPLC with hybrid ion trap time‐of‐flight mass spectrometry and HPLC with diode array detection

The root and rhizome of Litsea cubeba (Lour) Pers., named ‘Dou‐chi‐jiang’ in Chinese, has been traditionally used for treatment of cardiovascular and cerebrovascular diseases, rheumatic arthralgia, and other diseases in China. Aporphine alkaloids are its characteristic ingredients and responsible for its bioactivities, especially anti‐inflammatory and analgesic effects. A sensitive and reliable high‐performance liquid chromatography with diode array detection‐tandem mass spectrometry method was developed for characterization and simultaneous determination of biological aporphine alkaloids in ‘Dou‐chi‐jiang’. The optimized chromatographic conditions were performed on an Eclipse XDB C₁₈ column with a gradient of acetonitrile/water containing 0.1% formic acid as the mass spectrometry mobile phase and acetonitrile/water containing 0.2% diethylamine (pH 3.10, adjusted by acetic acid) as the liquid chromatography mobile phase. The fragmentation pathways by loss of CO, ·CH₃, ·NH₃, and ·NH₂CH₃ were detected as characteristic for aporphine alkaloids. Based on these characteristics, total 12 analogues were identified. The quantification method was validated in terms of linearity, precision, and accuracy for six major aporphine alkaloids, which was successfully applied for simultaneous determination in ten batches of samples. The established method is simple, rapid, and specific for characterization and quantitation of aporphine alkaloids in ‘Dou‐chi‐jiang’ and other traditional Chinese medicines rich in this kind of ingredient.     

Strategy for the Construction of Diverse Poly-NHC-Derived Assemblies and Their Photoinduced Transformations

A series of supramolecular assemblies of types [Ag₈( L )₄](PF₆)₈ and [Ag₄( L )₂](PF₆)₄, obtained from the tetraphenylethylene (TPE) bridged tetrakis(1,2,4-triazolium) salts H₄-L(PF₆)₄ and Ag^I ions, is described. The assembly type obtained dependends on the N-wingtip substituents of H₄-L(PF₆)₄. Changes in the lengths of the N4-wingtip substituents enables controlled formation of assemblies with either [Ag₄( L )₂](PF₆)₄ or [Ag₈( L )₄](PF₆)₈ stoichiometry. The molecular structures of selected [Ag₈( L )₄](PF₆)₈ and [Ag₄( L )₂](PF₆)₄ assemblies were determined by X-ray diffraction analyses. While H₄- L (PF₆)₄ does not exhibit fluorescence in solution, their tetra-NHC (NHC=N-heterocyclic carbene) assemblies do upon NHC–metal coordination. Upon irradiation, all assemblies undergo a light-induced, supramolecule-to-supramolecule structural transformation by an oxidative photocyclization involving phenyl groups of the TPE core, resulting in a significant change of the luminescence properties.     

Challenges in the theoretical investigations of lipid membrane configurations

We report some key results in the theoretical investigations of configurations of lipid membranes and present several challenges in this field,which involve(i)the exact solutions to the shape equation of lipid vesicles,(ii)the exact solutions to the governing equations of open lipid membranes,(iii)the neck condition of two-phase vesicles in the budding state,(iv) the nonlocal theory of membrane elasticity,and(v)the relationship between the symmetry and the magnitude of the free energy.     

Characteristics and mechanism of nano‐polycrystalline La2O3 thin‐film resistance switching memory

We investigated the characteristics and the mechanism of Pt/La₂O₃/Pt resistance switching memory with a set of measurements. The La₂O₃ films were determined as nano‐poly‐crystalline (diameter of the nanocrystals 5–10 nm) by XRD and HRTEM analysis. The Pt/La₂O₃/Pt device exhibited excellent resistive switching properties, including low switching voltage (<2 V), large low/high resistance ratio (>10⁸), and good cycling endurance property. The conduction mecha‐ nisms of the Pt/La₂O₃/Pt device were revealed with current–voltage characteristics, which are different in the low and high resistance states. Furthermore, XPS analysis and temperature‐dependent resistance measurement in the low resistance state showed that the conducting filaments in the Pt/La₂O₃/Pt device are mainly affected by oxygen defects rather than metallic La. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experiment on smooth,circular cylinders in cross-flow in the critical Reynolds number regime

Experiments were conducted for 2D circular cylinders at Reynolds numbers in the range of 1.73 × 10⁵–5.86 × 10⁵. In the experiment, two circular cylinder models made of acrylic and stainless steel, respectively, were employed, which have similar dimensions but different surface roughness. Particular attention was paid to the unsteady flow behaviors inferred by the signals obtained from the pressure taps on the cylinder models and by a hot-wire probe in the near-wake region. At Reynolds numbers pertaining to the initial transition from the subcritical to the critical regimes, pronounced pressure fluctuations were measured on the surfaces of both cylinder models, which were attributed to the excursion of unsteady flow separation over a large circumferential region. At the Reynolds numbers almost reaching the one-bubble state, it was noted that the development of separation bubble might switch from one side to the other with time. Wavelet analysis of the pressure signals measured simultaneously at θ = ±90° further revealed that when no separation bubble was developed, the instantaneous vortex-shedding frequencies could be clearly resolved, about 0.2, in terms of the Strouhal number. The results of oil-film flow visualization on the stainless steel cylinder of the one-bubble and two-bubble states showed that the flow reattachment region downstream of a separation bubble appeared not uniform along the span of the model. Thus, the three dimensionality was quite evident.