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.     

The Construction of DNA Logic Gates Restricted to Certain Live Cells Based on the Structure Programmability and Aptamer-Cell Affinity of G-Quadruplexes

DNA computation is considered a fascinating alternative to silicon-based computers; it has evoked substantial attention and made rapid advances. Besides realizing versatile functions, implementing spatiotemporal control of logic operations, especially at the cellular level, is also of great significance to the development of DNA computation. However, developing simple and efficient methods to restrict DNA logic gates performing in live cells is still a challenge. In this work, a series of DNA logic gates was designed by taking full advantage of the diversity and programmability of the G-quadruplex (G4) structure. More importantly, by further using the high affinity and specific endocytosis of cells to aptamer G4, an INHIBIT logic gate has been realized whose operational site is precisely restricted to specific live cells. The design strategy might have great potential in the field of molecular computation and smart bio-applications.     

Enantioselective Sulfoxidation Catalyzed by a Bisguanidinium Diphosphatobisperoxotungstate Ion Pair

The first enantioselective tungstate‐catalyzed oxidation reaction is presented. High enantioselectivities were achieved for a variety of drug‐like phenyl and heterocyclic sulfides under mild conditions with H₂O₂, a cheap and environmentally friendly oxidant. Synthetic utility was demonstrated through the preparation of (S)‐Lansoprazole, a commercial proton‐pump inhibitor. The active ion‐pair catalyst was identified to be bisguanidinium diphosphatobisperoxotungstate using Raman spectroscopy and computational studies.     

Fe (III)‐grafted Bi2MoO6 nanoplates for enhanced photocatalytic activities on tetracycline degradation and HMF oxidation

Fe (III)‐grafted Bi₂MoO₆ nanoplates (Fe (III)/BMO) with varying small quantity of Fe (III) clusters modification were fabricated through a simple hydrothermal and impregnation process. The characterization results indicate that the modification of Fe (III) clusters on the surface of Bi₂MoO₆ nanoplates with intimate interfacial contact is beneficial to the expansion of visible light absorption range and the separation of photoinduced carriers during the interface charge transfer process. The photocatalytic properties of the samples were studied by degradation of tetracycline (TC) and selective aerobic oxidation of biomass‐derived chemical 5‐hydroxymethylfuraldehyde (HMF) under visible light. The 1.5 wt% Fe (III) clusters‐grafted Bi₂MoO₆ nanoplates exhibited optimum photocatalytic activity, which is the TC degradation kinetic rate constant is 5.3 times higher than that of bare BMO, and the highest HMF conversion of 32.62% can be obtained with a selectivity of 95.30%. Furthermore, a possible visible light photocatalysis mechanism over Fe (III)/BMO sample has been proposed. This study may supply some insight for the development of visible‐light‐driven Bi₂MoO₆‐based photocatalysts applicable to both environmental remediation and biomass‐derived chemical transformation.     

A mass‐fraction‐based interface‐capturing method for multi‐component flow

An interface‐capturing method based on mass fraction is developed to solve the Riemann problem in multi‐component compressible flow. Equations of mass fraction with modified form, which is derived from conservative equations of mass, are employed here to capture the interface. By introducing mass fraction into Euler equations system, as well as other conservative coefficients, a quasi‐conservative numerical model is created. Numerical examples show that the mass fraction model performs well not only in multi‐component fluids modeled by simple stiffened gas equation of state (EOS) but also in that modeled by complex Mie–Grüneisen EOS. Moreover, the mass fraction model is applied to Riemann problem with piecewise EOS; the expression of which depends on density. It is found that the mass fraction model can well adapt to the analytic change in piecewise EOS and produce accuracy solutions with fewer unknown quantities, and the model can be easily extended to m‐component fluid mixture by using only m + 4 equations with no additional conditions. Copyright © 2013 John Wiley & Sons, Ltd.     

A comparative study of truly incompressible and weakly compressible SPH methods for free surface incompressible flows

In this paper, the performance of the incompressible SPH (ISPH) method and an improved weakly compressible SPH (IWCSPH) method for free surface incompressible flows are compared and analyzed. In both methods, the Navier–Stokes equations are solved, and no artificial viscosity is used. The ISPH algorithm in this paper is based on the classical SPH projection method with common treatments on solid boundaries and free surfaces. The IWCSPH model includes some advanced corrective algorithms in density approximation and solid boundary treatment (SBT). In density approximation, the moving least squares (MLS) approach is applied to re‐initialize density every several steps to obtain smoother and more stable pressure fields. An improved coupled dynamic SBT algorithm is implemented to obtain stable pressure values near solid wall areas and, thus, to minimize possible numerical oscillations brought in by the solid boundaries. Three representative numerical examples, including a benchmark test for hydrostatic pressure, a dam breaking problem and a liquid sloshing problem, are comparatively analyzed with ISPH and IWCSPH. It is demonstrated that the present IWCSPH is more attractive than ISPH in modeling free surface incompressible flows as it is more accurate and more stable with comparable or even less computational efforts. Copyright © 2013 John Wiley & Sons, Ltd.     

Controlled fabrication of hierarchically microstructured surfaces via surface wrinkling combined with template replication

In this paper,we present a simple method by combining surface wrinkling and template replication to create a series of hierarchical structures on polydimethylsiloxane(PDMS) elastomer.The primary stable lined patterns are formed by duplicating commercialized compact disk and digital versatile disk with PDMS.The secondary microscale patterns are from surface wrinkling,which is elicited by oxygen plasma(OP) treatment of the prestrained PDMS stamp followed with the prestrain release.By systematically varying the OP exposure duration,the prestrain,and the angle(θ) between the primary pattern orientation and the prestrain direction,we obtain highly ordered well-organized composite patterns from different patterning techniques and with different length scales and mechanical stabilities.     

High Performance of PVA Nanocomposite Reinforced by Janus-like Asymmetrically Oxidized Graphene: Synergetic Effect of H-bonding Interaction and Interfacial Crystallization

Chinese Journal of Polymer Science - Macromolecule nanocrystal network and strong interfacial interaction are always beneficial to enhance the mechanical property of polymer-based nanocomposites....     

Synthesis,properties and mechanism of photodegradation of core–shell structured upconversion luminescent NaYF4:Yb3+,Er3+@BiOCl

Microspherical bismuth oxychloride (BiOCl) can only utilize ultraviolet (UV) light to promote photocatalytic reactions. To overcome this limitation, a uniform and thin BiOCl nanosheet was synthesized with a particle size of about 200 nm. As results of UV–visible diffuse reflectance spectroscopy showed, the band gap of this nanostructure was reduced to 2.78 eV, indicating that the BiOCl nanosheet could absorb and utilize visible light. Furthermore, the upconversion material NaYF₄ doped with rare earth ions Yb³⁺ and Er³⁺ emitted visible light at 410 nm following excitation with near‐infrared (NIR) light (980 nm), which could be utilized by BiOCl to produce a photocatalytic reaction. To produce a high‐efficiency photocatalyst (NaYF₄:Yb³⁺,Er³⁺@BiOCl), BiOCl‐loaded NaYF₄:Yb³⁺,Er³⁺ was successfully synthesized via a simple two‐step hydrothermal method. The as‐synthesized material was confirmed using X‐ray diffraction, scanning electron microscopy, X‐ray photoelectron spectroscopy as well as other characterizations. The removal ratio of methylene blue by NaYF₄:Yb³⁺,Er³⁺@BiOCl was much higher than that of BiOCl alone. Recycling experiments verified the stability of NaYF₄:Yb³⁺,Er³⁺@BiOCl, which demonstrated excellent adsorption, strong visible‐light absorption and high electron–hole separation efficiency. Such properties are expected to be useful in practical applications, and a further understanding of the NIR‐light‐responsive photocatalytic mechanism of this new catalytic material would be conducive to improving its structural design and function.     

An efficient and facile synthesis of novel substituted pyrimidine derivatives: 4-amino-5-carbonitrile-2-nitroaminopyrimidine

One-pot, multicomponent reaction for the synthesis of novel substituted pyrimidine derivatives: 4-amino-5-carbonitrile-2-nitroaminopyrimidine from aromatic aldehydes, 1-nitroguanidine, and malononitrile under ethanol is described. Because of containing many active functional groups, such as amino, cyan and nitro, these products are important intermediate of organic synthesis. The advantages of this procedure include the short reaction time, mild reaction conditions, and excellent yields.