Syntheses,Structures, and Properties of Two Dicyanamide‐Bridged Polymers with a Schiff‐base Ligand

The dicyanamide‐bridged polymers with Schiff‐base ligand, [CoNaL(dca)]_n ( 1 ) and [Mn₂L(dca)₂]_n ( 2 ) [H₂L = bis(3‐methoxysalicylidene)benzene‐1,2‐diamine, dca = dicyanamide] were synthesized and characterized by elemental analyses, IR spectrroscopy and single‐crystal X‐ray diffraction. The solid‐state structures reveal that polymer 1 has double dca bridged loop‐like 1D chains, in which the heterodinuclear Co²⁺‐Na⁺ units (LCoNa) are bridged by dca with coordination mode μ_1,3,5. In polymer 2 , homodinuclear Mn²⁺‐Mn²⁺(LMnMn) units are linked by dca in μ_1,5‐bridging mode to form 2D planes. Magnetic susceptibility studies on 2 reveals antiferromagnetic coupling interactions between the adjacent Mn²⁺ ions in the LMnMn unit.     

磺酰脲类除草剂分子印迹聚合物制备及应用研究进展

磺酰脲类除草剂本身易降解,在环境和生物样品中痕量存在,其残留分析工作颇具挑战。分子印迹聚合物因其良好的选择性和稳定性已被广泛应用于农药残留分析的分离与富集前处理过程,提高了检测的准确度和精密度。本文从单体、溶剂与致孔剂、聚合方法三个方面概述了近15年来磺酰脲类分子印迹聚合物的制备,并对其在残留检测中的应用方式进行了综述,为磺酰脲类除草剂残留检测技术的进一步开发提供了参考。     

Recent Development of Durable and Self‐Healing Surfaces with Special Wettability

Artificial special wetting surfaces have drawn much interest due to their important applications in many fields. Nevertheless, tremendous challenges still remain for the fabrication of wetting surfaces with durable and self‐healing properties. Here, recent progress of durable, self‐healing wetting surfaces is highlighted by discussing the fabrications of several typical wetting surfaces including superhydrophobic surfaces, superamphiphobic surfaces, underwater superoleophobic surfaces, and high hydrophilic antifouling surfaces based on expertise and related research experience. To conclude, some perspectives on the future research and development of these special wetting surfaces are presented.

     

Polymeric Gene Carriers Bearing Pendant β‐Cyclodextrin: The Relevance of Glycoside Permethylation on the “In Vitro” Cell Response

The incorporation of cyclodextrins (CDs) to nonviral cationic polymer vectors is very attractive due to recent studies that report a clear improvement of their cytocompatibility and transfection efficiency. However, a systematic study on the influence of the CD derivatization is still lacking. In this work, the relevance of β‐CD permethylation has been addressed by preparing and evaluating two series of copolymers of the cationic N‐ethyl pyrrolidine methacrylamide (EPA) and styrenic units bearing pendant hydroxylated and permethylated β‐CDs (HCDSt and MeCDSt, respectively). For both cell lines, CDs permethylation shows a strong influence on plasmid DNA complexation, “in vitro” cytocompatibility and transfection efficiency of the resulting copolymers over two murine cell lines. While the incorporation of the hydroxylated CD moiety increased the cytotoxicity of the copolymers in comparison with their homopolycationic counterpart, the permethylated copolymers have shown full cytocompatibility as well as superior transfection efficiency than the controls. This behavior has been related to the different chemical nature of both units and tentatively to a different distribution of units along the polymeric chains. Cellular internalization analysis with fluorescent copo­lymers supports this behavior.

     

Thermodynamic Properties of Polymorphs of Fluorosulfate Based Cathode Materials with Exchangeable Potassium Ions

FeSO₄F‐based frameworks have recently emerged as attractive candidates for alkali insertion electrodes. Mainly owing to their rich crystal chemistry, they offer a variety of new host structures with different electrochemical performances and physical properties. In this paper we report the thermodynamic stability of two such K‐based “FeSO₄F” host structures based on direct solution calorimetric measurements. KFeSO₄F has been reported to crystallize in two different polymorphic modifications—monoclinic and orthorhombic. The obtained enthalpies of formation from binary components (KF plus FeSO₄) are negative for both polymorphs, indicating that they are thermodynamically stable at room temperature, which is very promising for the future exploration of sulfate based cathode materials. Our measurements show that the low‐temperature monoclinic polymorph is enthalpically more stable than the orthorhombic phase by ≈10 kJ mol^?1, which is consistent with the preferential formation of monoclinic KFeSO₄F at low temperature. Furthermore, observed phase transformations and difficulties in the synthesis process can be explained based on the obtained calorimetric results. The KMnSO₄F orthorhombic phase is more stable than both polymorphs of KFeSO₄F.     

New Insights into the Reactivity of Cisplatin with Free and Restrained Nucleophiles: Microsolvation Effects and Base Selectivity in Cisplatin–DNA Interactions

The reactivity of cisplatin towards different nucleophiles has been studied by using density functional theory (DFT). Water was considered first to analyze the factors that govern the transformation of cisplatin into more electrophilic aquated species by using an activation‐strain model. It was found that the selectivity and reactivity of cisplatin is a delicate trade‐off between strain and interaction energies and that the second chloride is a worse leaving group than the first. When similar studies were carried out with imidazole, guanine (G), and adenine (A), it was found that in general the second nucleophilic substitution reactions have lower activation barriers than the first ones. Finally, simulations of the structural restrictions imposed by the DNA scaffold in intra‐ and interstrand processes showed that the geometries of the reaction products are nonoptimal with respect to the unrestrained A and G nucleophiles, although the energetic cost is not considerable under physiological conditions, which thus permits nucleophilic substitution reactions that lead to highly distorted DNA.     

Synthetic,Optical and Theoretical Study of Alternating Ethylenedioxythiophene–Pyridine Oligomers: Evolution from Planar Conjugated to Helicoidal Structure towards a Chiral Configuration

A series of alternating 3,4‐ethylenedioxythiophene–alkynylpyridine oligomers (DA)_n with increased solubility are synthesized and their photophysical properties and nonlinear optical properties are investigated. Their quadratic polarizabilities are determined from hyper‐Rayleigh scattering experiments to obtain information on their conformations in solution. These chromophores, based on the alternation of electron‐rich (D) and electron‐deficient (A) moieties, exhibit optical properties that arise from the combination of dipolar and helicoidal features in the (DA)_n homologue series where n=1–4. The transition from dipolar conjugated planar structures (n=1, 2) to helicoidal structures (n=3, 4) is clearly evidenced by results from symmetry‐sensitive second‐order nonlinear optical experiments. This suggests an approach towards highly efficient chiral chromophores for second‐order nonlinear optics. Interestingly, this structural evolution also has significant impact on the photophysical properties: both absorption and fluorescence emission show bathochromic and hyperchromic shifts with increasing number of repeating units in the dipolar planar derivatives (n=1–2) but show saturation effects in the helicoidal structures (n=2–4). In addition, the helicoidal structures show sizeable two‐photon absorption at 700–750 nm (40–100 GM) for compounds lacking either electron‐donating or electron‐withdrawing substituents.     

Construction of Modified Carbon Paste Electrode for Highly Sensitive Simultaneous Electrochemical Determination of Trace Amounts of Copper (II) and Cadmium (II)

A chemically modified electrode was constructed for rapid, simple, accurate, selective and highly sensitive simultaneous determination of Cu(II) and Cd(II) using square wave anodic stripping voltammetry. The electrode was prepared by incorporation of SiO₂ nanoparticles, coated with a newly synthesized Schiff base, in carbon paste electrode. The limit of detection was found to be 0.28 ng mL^?1 and 0.54 ng mL^?1 for Cu(II) and Cd(II), respectively. The proposed chemically modified electrode was used for the determination of copper and cadmium in several foodstuffs and water samples.     

Carbon Paste Electrode Modified with Biochar for Sensitive Electrochemical Determination of Paraquat

The present work reports for the first time the determination of paraquat (PQ²⁺) by Differential Pulse Adsorptive Stripping Voltammetry (DPAdSV) using a carbon paste electrode modified (CPME) with biochar obtained from castor oil cake at different temperatures (200–600 °C). The best voltammetric response was verified using biochar yielded at 400 °C (CPME‐BC400). Linear dynamic range (LDR) for PQ²⁺ concentrations between 3.0×10^?8 and 1.0×10^?6 mol L^?1 and a limit of detection (LOD) of 7.5×10^?9 mol L^?1 were verified. The method was successfully applied for PQ²⁺ quantification in spiked samples of natural water and coconut water.