Mononuclear,homo- and hetero-binuclear complexes of 1-(5-(1-(2-aminophenylimino)ethyl)-2,4-dihydroxyphenyl)ethanone: synthesis,magnetic, spectral,antimicrobial, antioxidant,and antitumor studies

A new Schiff base, H₂L, was prepared by condensation of 4,6-diacetylresorcinol with o-phenylenediamine in molar ratio 1?:?1. The ligand reacted with copper(II), nickel(II), cobalt(II), iron(III), zinc(II), oxovanadium(IV), and dioxouranium(VI) ions in the absence and presence of LiOH to yield mononuclear and homobinuclear complexes. The mononuclear dioxouranium(VI) complex [(HL)-(UO₂)(OAc)(H₂O)]·5H₂O was used to synthesize heterobinuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, ¹H-, and ¹³C-NMR, electronic, ESR and mass spectra, conductivity, and magnetic susceptibility measurements as well as thermal analysis. In the absence of LiOH, mononuclear complexes (1, 4, and 9) were obtained; in the presence of LiOH, binuclear complexes (3, 5, 7, and 10) as well as mononuclear complexes (2, 6, and 8) were obtained. In the mononuclear complexes, the coordinating sites are the phenolic oxygen, azomethine nitrogen, and amino nitrogen. In addition to these coordinating sites, the free carbonyl and phenolic OH are involved in coordination in binuclear complexes. The metal complexes exhibited octahedral, tetrahedral, and square planar geometries while the uranium is seven-coordinate. The antimicrobial and antioxidant activities of the ligand and its complexes were investigated. The ligand and the metal complexes showed antitumor activity against Ehrlich Acites Carcinoma.     

Nickel versus copper: enhanced antibacterial activity in a series of new nickel(II) Schiff base complexes

Five new Ni(II) Schiff base complexes [NiL^x(Solv)₂] denoted by NiL^x, x = 1–5, were synthesized and characterized. The Schiff base ligands were synthesized from the condensation of 5-bromo-2-hydroxy-3-nitrobenzaldehyde with different aliphatic and aromatic diamines. The X-ray crystal structure of NiL³ was determined. The ligands and complexes were tested as antibacterial agents against two gram(+) and two gram(?) human pathogenic bacteria. The complexes showed moderate antibacterial activity against both gram type bacteria. The new Ni(II) complexes showed enhanced antibacterial activity compared to the previously reported Cu(II) complexes of the same ligands.     

A wine red copper(II) complex of a tetradentate nitrogen donor showing two-electron oxidation. Generation of a copper(II)-phosphine bond

Using the 1 : 2 condensate of benzil and 2-hydrazinopyridine as the ligand LH₂ (H: dissociable NH proton), the red complex Cu(LH₂)(ClO₄)₂ (1) was synthesized. The ligand also afforded the orange [Zn(LH₂)(OH₂)₂](ClO₄)₂ (2). The X-ray crystal structures of the ligand, 1 and 2 have been determined. The metals in 1 and 2 have octahedral N₄O₂ environments. 1 is paramagnetic with μ_eff of one unpaired electron (1.63 μ_B and displays an axial EPR spectrum in the solid state with <g> = 2.07, characteristic of a (d_x2_?y2)¹ ground state (g_|| > g_⊥; A_|| = 16 mT). In cyclic voltammetry, 1 displays a two-electron oxidation around 0.9 V versus NHE. The two-electron oxidized (coulometrically) solution of 1 (golden yellow) gives an EPR spectrum with <g> = 2.17 and g_|| < g_⊥. The reaction of PPh₃ with 1 yields the orange complex [Cu(LH₂)(PPh₃)](ClO₄)₂ (4). With the assumed chemical formula, the effective magnetization of 4 corresponds to one electron. Its EPR spectrum in the solid state is isotropic with g = 2.07. This g value yields a theoretical μ_eff of 1.80 μ_B at 298 K from Curie’s law, which matches very well with the experimental value of 1.89 μ_B at room temperature. Since single crystals of 4 could not be obtained, DFT calculations at the UBP86/6–311G(2d,p) level have been carried out and indicate that the cation in 4 is square pyramidal with the phosphine at the apex. The ease of the oxidation of the metal in 1 leads to the stabilization of the rare Cu(II)-P bond in 4.     

A selective chemosensor for detection of Ag(I) and Cu(I) based on an acenaphthoquinone derivative and its complexes

A new Schiff base, acenaphthoquinone bis(diphenylmethlenehydrazone) (L), was synthesized and employed as a chemosensor for detecting Ag(I) and Cu(I). Experimental results showed that the chemosensor exhibited high selectivity and sensitivity. The sensitivity of the chemosensor for Ag(I) or Cu(I) was not affected by other metal ions, such as Ni(II), Nd(III), Zn(II), Fe(III), Cu(II), Na(I), La(III), K(I), and Co(II). Complexes 1 and 2 were synthesized by coordination of L with Ag(I) and Cu(I), respectively. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction. They had the same space group P2₁/c. Based on theoretical calculation, mechanism of the chemosensor detecting Ag(I) and Cu(I) was suggested.     

Linear Schiff-base fluorescence probe with aggregation-induced emission characteristics for Al detection and its application in live cell imaging

A simple Schiff-base derivative with salicylaldehyde moieties as fluorescent probe 1 was reported by aggregation-induced emission (AIE) characterization for the detection of metal ions. Spectral analysis revealed that probe 1 was highly selective and sensitive to Al³⁺. The probe 1 was also subject to minimal interference from other common competitive metal ions. The detection limit of Al³⁺ was 0.4 μM, which is considerably lower than the World Health Organization standard (7.41 μM), and the acceptable level of Al³⁺ (1.85 μM) in drinking water. The Job's plot and the results of ¹H-NMR and FT-IR analyses indicated that the binding stoichiometry ratio of probe 1 to Al³⁺ was 1:2. Probe 1 demonstrated a fluorescence-enhanced response upon binding with Al³⁺ based on AIE characterization. This response was due to the restricted molecular rotation and increased rigidity of the molecular assembly. Probe 1 exhibited good biocompatibility, and Al³⁺ was detected in live cells. Therefore, probe 1 is a promising fluorescence probe for Al³⁺ detection in the environment.     

Mass spectrometry‐based proteomics of oxidative stress: Identification of 4‐hydroxy‐2‐nonenal (HNE) adducts of amino acids using lysozyme and bovine serum albumin as model proteins

Modification of proteins by 4‐hydroxy‐2‐nonenal (HNE), a reactive by‐product of ω6 polyunsaturated fatty acid oxidation, on specific amino acid residues is considered a biomarker for oxidative stress, as occurs in many metabolic, hereditary, and age‐related diseases. HNE modification of amino acids can occur either via Michael addition or by formation of Schiff‐base adducts. These modifications typically occur on cysteine (Cys), histidine (His), and/or lysine (Lys) residues, resulting in an increase of 156 Da (Michael addition) or 138 Da (Schiff‐base adducts), respectively, in the mass of the residue. Here, we employed biochemical and mass spectrometry (MS) approaches to determine the MS “signatures” of HNE‐modified amino acids, using lysozyme and BSA as model proteins. Using direct infusion of unmodified and HNE‐modified lysozyme into an electrospray quadrupole time‐of‐flight mass spectrometer, we were able to detect up to seven HNE modifications per molecule of lysozyme. Using nanoLC‐MS/MS, we found that, in addition to N‐terminal amino acids, Cys, His, and Lys residues, HNE modification of arginine (Arg), threonine (Thr), tryptophan (Trp), and histidine (His) residues can also occur. These sensitive and specific methods can be applied to the study of oxidative stress to evaluate HNE modification of proteins in complex mixtures from cells and tissues under diseased versus normal conditions.     

基于结构相似度评价方法的窗口效应

为了提高基于结构相似度图像评价方法的评价效果,对传统的窗口选取准则进行了改进,采用实验对比的方法,通过对窗口改进前后评价效果的对比验证,得到了不同数据库和不同失真类型的最佳窗口。结果表明,传统的单一窗口并不能得到最佳的评价效果,而且现在普遍使用的标准差为1.5的高斯加权窗口的效果也不一定好于普通的方形窗口,不同的失真类型的图像其最优窗口也是不同的。结果表明,对于亮度窗口W1来说,窗口越大效果越好;而对于对比度、结构度窗口W2而言,W2=7时效果最好。该研究成果对优化基于结构相似度评价方法的效果具有重要作用。     

Co‐tier downlink interference management in dense femtocell networks

With the adoption of long‐term evolution standard for 4G mobile communications, the deployment of femtocell base stations (FBSs) to cope with the surging traffic in mobile wireless communication is becoming increasingly popular. However, with the random installation of FBSs, the problem of interference among FBSs is still a challenge. In this paper, assuming the presence of a femtocell management system that can control and coordinate the densely deployed FBSs, a novel power backoff scheme is proposed that determines the appropriate transmit power of each FBS so that the interference is reduced. Simulation results for randomly deployed FBSs in an environment with shadowing using MATLAB are provided, showing that our proposed methods can effectively mitigate the co‐tier downlink interference while improving the system capacity in a densely deployed femtocell network with shared spectrum use. Quantitatively, the average interference is reduced by roughly 90% to 100% of dBm, and the average capacity is increased by more than 80%. These results attest to the effectiveness of the proposed scheme.     

The offloading model for green base stations in hybrid energy networks with multiple objectives

Based on green energy prediction and storage, a novel green base station (GBS) offloading model is proposed and can be employed with multiple objectives in this paper to save energy. By predicting the value of green energy collected by GBS and updating the residual energy of each GBS, we can obtain the maximum number of users that each GBS can offload theoretically. Then, the optimum number of users should be calculated in order to achieve different network performance. Eventually, under the restrictions of the maximum number of users and the optimum number of users, we can finish offloading for traditional base station in the network. Simulation results demonstrate that through the proposed GBS offloading model, we can fulfill compromise between maximizing green energy utilization and load balancing in the offloading process, and the effect of energy saving is remarkable. Copyright © 2016 John Wiley & Sons, Ltd.     

A novel HBT trigger SCR in 0.35 μm SiGe BiCMOS technology

The silicon-controlled rectifier (SCR) device is known as an efficient electrostatic discharge (ESD) protection device due to the highest ESD robustness in the smallest layout area. However, SCR has some drawbacks, such as high trigger voltage and low holding voltage. In order to reduce the trigger voltage of the SCR device for ESD protection, a new heterojunction bipolar transistor (HBT) trigger silicon controlled rectifier (HTSCR) device in 0.35 μm SiGe BiCMOS technology are proposed. The underlying physical mechanisms critical to the trigger voltage are demonstrated based on transmission line pulsing (TLP) measurement and physics-based simulation results. The simulation results prove that the trigger voltage of the HTSCR is decided by the collector-to-emitter breakdown voltage of the HBT structure in floating base configuration. The ESD experiment test results demonstrate the HTSCR can offer superior performance with a small trigger voltage, an adjustable holding voltage and a high ESD robustness. In comparison to the conventional MLSCR, the trigger voltage of the fabricated HTSCR can reduce to less than 50% of that of the MLSCR, and the I_t2 of the HBT trigger SCR is 80% more than that of the MLSCR.