2]Catenane assembly from calix[4]arene crown ethers [In Process Citation

A variety of novel calix[4]arene-incorporating crown ethers with or without intramolecular hydrogen bonding have been prepared by two efficient methods and utilized as donor rings to assemble calix[4]arene [2]catenanes based on pi-stacking interaction between hydroquinone and bipyridinium units. Treatment of calix[4]arene crown ethers 4, 10a, or 10b, whose cone conformation was fixed by intramolecular hydrogen bonding within the calix[4]arene moiety, with dicationic salt 15 x 2PF6 and dibromide 16 afforded the corresponding [2]catenanes 17a x 4PF6, 17b x 4PF6, and 17c x 4PF6 in 20%, 53%, and 55% yields, respectively, whereas from the reactions of 15 x 2PF6 and dibromide 16 in the presence of conformationally flexible 11 or 12 with a cone conformation kept by two propyl groups, [2]catenanes 18 x 4PF6 and 19 x 4PF6 were obtained in 12% and 6% yields. [2]Catenanes 21a x 4Cl, 21b x 4Cl, and 21c x 4Cl, incorporating calix[4]arene in both the donor and acceptor rings, were also successfully assembled from 10a or 10b, 16, and dicationic salts 20a x 2PF6 or 20b x 2PF6. The dynamic 1H NMR and absorption spectra of the [2]catenanes have been investigated, which revealed a strongest donor-acceptor interaction in 17a x 4PF6 and that the cone [2]catenanes 17a-c x 4PF6 can isomerize to the partial cone isomer at high temperature. The difference of the dynamic properties of these catenanes was discussed. The results demonstrate that catenation is one new general method to change the conformational distributions of calix[4]arenes.     

迁移管的电场强度对真空紫外电离-离子迁移谱仪性能的影响

离子迁移管是离子迁移谱仪的核心部分,它用来产生均匀的电场,以使不同迁移率的离子进行分离。本研究以丙酮为例,详细研究了本课题组所研制的真空紫外电离源-离子迁移谱仪中迁移管的电场参数对离子的灵敏度和分辨率的影响,发现电压的增大灵敏度增大,但是分辨率存在一个最佳的电压,这些结果可用于迁移谱的优化设计。     

The Synthesis of Some New N‐[1‐(2,5‐Dichlorophenyl)‐5‐Methyl‐1,2,3‐Triazol‐4‐yl]‐Carbamic Acid Ester Derivatives

The synthesis of some new N‐[1‐(2,5‐dichlorophenyl)‐5‐methyl‐1,2,3‐triazol‐4‐yl]‐carbamic acid ester derivatives are reported in this paper. The yielded products 6a‐l were confirmed by Elemental analyses, NMR, MS, and IR spectra.     

Formation enthalpies of rare earth titanate pyrochlores

High-temperature oxide melt solution calorimetry and Rietveld refinements of powder X-ray diffraction data were used to investigate the structure (Fd3m; Z=8) and energetics of a series of RE₂Ti₂O₇ (RE=Sm-Lu) compounds with the pyrochlore structure as well as La₂Ti₂O₇ with a layered perovskite-type structure. All of the RE-titanates were found to be stable in enthalpy with respect to their oxides. In the pyrochlore series, Lu₂Ti₂O₇ was least stable in enthalpy (ΔHf-ox at 298 K=−56.0±4.0 kJ/mol); the most stable materials were Gd-, Eu-, and Sm₂Ti₂O₇ with ΔHf-ox at 298 K=−113.4±2.7, −106.1±4.2, −115.4±4.2 kJ/mol, respectively. In general, as the radius ratio of the A- to B-site cations, R_A/R_B, decreases, the pyrochlore structure becomes less stable. The trend of ionic radius of the RE³⁺ cation vs. ΔHf-ox at 298 K is non-linear and approximately parallels the increasing “resistance” to ion-beam-induced amorphization as R_A/R_B decreases.     

Benzolignanoid and Polyphenols from Origanum Vulgare

A new dihydrobenzodioxane derivative, origalignanol ( 10 ), together with nine polyphenolic compounds, salvianolic acid A ( 1 ), salvianolic acid C ( 2 ), lithospermic acid ( 3 ), apigenin 7‐O‐β‐D‐glucuronide ( 4 ), apigenin 7‐O‐β‐D‐(6″‐methyl)glucuronide ( 5 ), luteolin, ( 6 ), luteolin 7‐O‐β‐D‐glucopyranoside ( 7 ), luteolin 7‐O‐β‐D‐glucuronide ( 8 ), and luteolin 7‐O‐β‐D‐xylopyranoside ( 9 ), were isolated from the aqueous ethanolic extract of the aerial parts of Origanum vulgare for the first time. The structure of new compound 10 was determined on the basis of spectroscopic methods. Compound 5 is probably an artifact formed during the isolation. Compounds 1, 2 and 3 showed strong DPPH radical scavenging activity with an EC₅₀ of 7.2 ± 0.4, 9.6 ± 0.9, and 9.5 ± 0.7 μM, respectively, and protected rat hepatocytes from CCl₄‐damage at 100 μM.     

Native agarose gel electrophoresis and electroelution: A fast and cost‐effective method to separate the small and large hepatitis B capsids

Hepatitis B core antigen (HBcAg) expressed in Escherichia coli is able to self‐assemble into large and small capsids comprising 240 (triangulation number T = 4) and 180 (triangulation number T = 3) subunits, respectively. Conventionally, sucrose density gradient ultracentrifugation and SEC have been used to separate these capsids. However, good separation of the large and small particles with these methods is never achieved. In the present study, we employed a simple, fast, and cost‐effective method to separate the T = 3 and T = 4 HBcAg capsids by using native agarose gel electrophoresis followed by an electroelution method (NAGE‐EE). This is a direct, fast, and economic method for isolating the large and small HBcAg particles homogenously based on the hydrodynamic radius of the spherical particles. Dynamic light scattering analysis demonstrated that the T = 3 and T = 4 HBcAg capsids prepared using the NAGE‐EE method are monodisperse with polydispersity values of ～15% and ～13%, respectively. ELISA proved that the antigenicity of the capsids was not affected in the purification process. Overall, NAGE‐EE produced T = 3 and T = 4 capsids with a purity above 90%, and the recovery was 34% and 50%, respectively (total recovery of HBcAg is ～84%), and the operation time is 15 and 4 times lesser than that of the sucrose density gradient ultracentrifugation and SEC, respectively.     

A simple and efficient algorithm for fused lasso signal approximator with convex loss function

We consider the augmented Lagrangian method (ALM) as a solver for the fused lasso signal approximator (FLSA) problem. The ALM is a dual method in which squares of the constraint functions are added as penalties to the Lagrangian. In order to apply this method to FLSA, two types of auxiliary variables are introduced to transform the original unconstrained minimization problem into a linearly constrained minimization problem. Each updating in this iterative algorithm consists of just a simple one-dimensional convex programming problem, with closed form solution in many cases. While the existing literature mostly focused on the quadratic loss function, our algorithm can be easily implemented for general convex loss. We also provide some convergence analysis of the algorithm. Finally, the method is illustrated with some simulation datasets.     

Oscillatory interaction between two like‐charged nanoparticles induced by polyelectrolyte brush–solvent interface

We use two‐dimensional (2D) self‐consistent field theory to study the effective interactions between two like‐charged cylindrical nanoparticles mediated by an oppositely weakly charged polyelectrolyte brush in a solvent solution. In a poor solvent, where a sharp brush–solvent interface forms, an oscillatory interaction is observed when two nanoparticles are both located at the brush–solvent interface. This oscillatory interaction depends on the penetration depths of the particles and their geometric orientations with respect to the substrate. When the particles are both immersed in the brush and/or the particles are oriented vertically or diagonally with large angles to the substrate, the oscillatory behavior disappears. We interpret our findings by analyzing in detail the contributions to the free energy from electrostatic interaction, nonelectrostatic interaction, and entropies, separately. Briefly, the deformations of the interface and the ion layers formed in the vicinity of the interface are responsible for this oscillatory behavior. In a good solvent, where the narrow brush–solvent interface vanishes, the effective particle–particle interactions behave like that for both particles immersed into the brush with poor solvent. They are found to be repulsive. The influences of the particle size, grafting density, and amount of charges and ions are also briefly discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1458–1468     

Synthesis,crystal structures and DNA/human serum albumin binding of ternary Cu(II) complexes containing amino acids and 6‐(pyrazin‐2‐yl)‐1,3,5‐triazine‐2,4‐diamino

Two water‐soluble 6‐(pyrazin‐2‐yl)‐1,3,5‐triazine‐2,4‐diamino (pzta)‐based Cu(II) complexes, namely [Cu(l ‐Val)(pzta)(H₂O)]ClO₄ ( 1 ) and [Cu(l ‐Thr)(pzta)(H₂O)]ClO₄ ( 2 ) (l ‐Val: l ‐valinate; l ‐Thr: l ‐threoninate), were synthesized and characterized using elemental analyses, molar conductance measurements, spectroscopic methods and single‐crystal X‐ray diffraction. The results indicated that the molecular structures of the complexes are five‐coordinated and show a distorted square‐pyramidal geometry, in which the central copper ions are coordinated to N,N atoms of pzta and N,O atoms of amino acids. The interactions of the complexes with DNA were investigated using electronic absorption, competitive fluorescence titration, circular dichroism and viscosity measurements. These studies confirmed that the complexes bind to DNA through a groove binding mode with certain affinities (K_b = 4.71 × 10³ and 1.98 × 10³ M^?1 for 1 and 2 , respectively). The human serum albumin (HSA) binding properties of the complexes were also evaluated using fluorescence and synchronous fluorescence spectroscopies, indicating that the complexes could quench the intrinsic fluorescence of HSA in a static quenching process. The relevant thermodynamic parameters revealed the involvement of van der Waals forces and hydrogen bonds in the formation of complex–HSA systems. Finally, molecular docking technology was also used to further verify the interactions of the complexes with DNA/HSA.     

A Resettable Keypad Lock with Visible Readout Based on Closed Bipolar Electrochemistry and Electrochromic Poly(3‐methylthiophene) Films

A closed bipolar electrode (BPE) system was developed with electrochromic poly(3‐methylthiophene) (PMT) films electropolymerized on the ITO/rGO electrode as one pole of BPE in the reporting reservoir and the bare ITO electrode as another pole of BPE in the analyte reservoir, in which rGO represents reduced graphene oxide. Under a suitable driving voltage (V_tot), the electrochemical reduction/oxidation of electroactive probes, such as H₂O₂/glutathione (Glu), in the analyte reservoir could induce the reversible color change of PMT films in the reporting reservoir between blue and red. Based on this, a keypad lock with H₂O₂, Glu, and V_tot=?3.0 V as the three inputs and the color change of PMT films as the visible output was established. This system was easily operated and did not need to synthesize the complex compounds or DNA molecules. The security system was easy to reset and could be used repeatedly.