Two Vanadium(V) Complexes Derived from Bromo and Chloro-Substituted Hydrazone Ligands: Syntheses, Crystal Structures and Antimicrobial Property.

Two vanadium(V) complexes derived from the bromo and chloro-substituted hydrazones N'-(4-bromo-2-hydroxybenzylidene)- 2-chlorobenzohydrazide (H2L1) and N'-(3-bromo-5-chloro-2-hydroxybenzylidene)-3-methylbenzohydrazide (H2L2) with the formula [VOL1(OCH3)(CH3OH)] (1) and [VOL2(OCH3)(CH3OH)] (2) were newly synthesized and characterized by IR, UV-Vis and 1H NMR spectroscopy. The structures of H2L1 and the complexes were further confirmed by single crystal X-ray diffraction. Both vanadium complexes are mononuclear, with the metal atoms coordinated by the hydrazone ligands, methanol ligands, and methanolate ligands, and the oxo groups, forming octahedral geometry. The hydrazones and the vanadium complexes were assayed for the antimicrobial activities on Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Pseudomonas fluorescence, and the fungi Candida albicans and Aspergillus niger. The existence of the bromo and chloro groups in the hydrazone ligands may improve the antimicrobial property.

[Study on Characteristics of Terahertz Spectra of Organic Functional Groups].

Fourier transform infrared (FTIR) was exploited to measure terahertz (THz) spectra in the wave number range of 30-300 cm(-1) for saturated straight chain organic molecules at room temperature. The results reveal that different organic functional groups exhibit different THz spectral characteristics. The absorption peaks of vibration modes of organic crystal lattice locate in high frequency range of THz, while those of vibration modes of intermolecular hydrogen (H) bonds appear in low frequency range of THz. Moreover, a typical absorption peak of intermolecular H bonds caused by saturated straight-chain monohydric alcohol hydroxyl functional groups locates at 57 cm(-1), while a characteristic absorption peak of intermolecular hydrogen bonds caused by triacontanoic acid carboxyl functional groups appears at 74 cm(-1). The intermolecular H bonds not only result in that the THz absorbing abilities of triacontanol and triacontanoic acid are significantly stronger than that of triacontane, but also cause regular red-shift and blue-shift of the THz absorption peaks of triacontanoic acid, as compared with those of triacontanol. In addition, density functional theory (DFT) B3LYP/6-311G(d,p) basis set was employed to simulate the THz spectra of saturated straight-chain alkane, alkanol and acid, respectively. The simulation results indicate that for the organic molecules with stronger intermolecular H bonds, lower consistent degree of the THz spectrum simulated from monomer molecule with the THz spectrum experimentally measured will occur. Moreover, the simulation results of dimer structures agree well with the measured spectra as compared to those simulated from monomer molecule structures. The results presented in this work are of great significance not only to the study of the THz spectral characteristics of other organic functional groups, but also to the clarification of the vibration modes of organic molecules. Particularly, our results are also helpful for clarifying the THz response theory of organics, and for exploiting the applications of organic materials in THz devices.

Screening analysis of candidate gene mutations in a kindred with polycystic liver disease.

AIM: To find potential mutable sites by detecting mutations of the candidate gene in a kindred with polycystic liver disease (PCLD). METHODS: First, we chose a kindred with PCLD and obtained five venous blood samples of this kindred after the family members signed the informed consent form. In the kindred two cases were diagnosed with PCLD, and the left three cases were normal individuals. All the blood samples were preserved at -85 °C. Second, we extracted the genomic DNA from the venous blood samples of the kindred using a QIAamp DNA Mini Kit and then performed long-range polymerase chain reaction (PCR) with different primers. The exons of PKD1 were all sequenced with the forward and reverse primers to ensure the accuracy of the results. Next, we purified the PCR products and directly sequenced them using Big Dye Terminator Chemistry version 3.1. The sequencing reaction was conducted with BiomekFX (Beckman). Finally, we analyzed the results. RESULTS: A total of 42 normal exons were identified in detecting mutations of the PKD1 gene. A synonymous mutation occurred in exon 5. The mutation was a homozygous T in the proband and was C in the reference sequence. This mutation was located in the third codon and did not change the amino acid encoded by the codon. Missense mutations occurred in exons 11 and 35. These mutations were located in the second codon; they changed the amino acid sequence and existed in the dbSNP library. A nonsense mutation occurred in exon 15. The mutation was a heterozygous CT in the proband and was C in the reference sequence. This mutation was located in the first codon and resulted in a termination codon. This mutation had an obvious influence on the encoded protein and changed the length of the protein from 4303 to 2246 amino acids. This was a new mutation that was not present in the dbSNP library. CONCLUSION: The nonsense mutation of exon 15 existed in the proband and in the third individual. Additionally, the proband was heterozygous for this mutation, so the mutable site was a pathogenic mutation.

[Characterization and simulation of far-infrared spectroscopy for saturated monohydric alcohols].

Fourier transform infrared-attenuated total reflection (FTIR-ATR) was employed to measure the far-infrared (FIR) spectra in wavenumbers of 30-300 cm(-1) for six kinds of saturated monohydric alcohols, namely: methanol, ethanol, propanol, isopropanol, butanol and isobutanol. Further analysis of the FIR spectra for these monohydric alcohols with similar chemical structures reveals that absorption peaks are observed obviously for these alcohols in the 30-150 cm(-1) band, whereas not obvious peaks are measured in the 150-300 cm(-1) band. Moreover, it was found that the monohydric alcohols with higher hydroxy concentration possess lower average FIR transmission. In addition, the average FIR transmissions of linear chain monohydric alcohols are higher than those of the branched chain ones. Furthermore, the density functional theory (DFT) B3LYP/6-311G(d,p) basis set was employed to simulate the structures optimization and to calculate the responding frequencies of the methanol monomer and polymer. Simulation result indicates that no absorption peaks are found in the 30-150 cm(-1) band for the methanol monomer molecule, whereas there are obvious absorption peaks for the methanol polymers in the same band. In addition, the simulated absorption peak positions for the methanol polymers are in agreement with those experimentally measured. Both results indicate that the absorption of the methanol in Terahertz (THz) is attributed to the collective vibrations of different kinds of polymer, and that the polymer for methanol is mainly trimmer. This paper not only provides a new way to investigate the responding frequencies of organic molecule in THz band, but also is helpful for the FTIR-ATR study of other organic molecules.

Mechanisms of TRAIL and gemcitabine induction of pancreatic cancer cell apoptosis.

The aim of this study was to investigate induction of apoptosis by the tumor necrosis factor (TNF)-related apoptosis-inducing ligand (TRAIL) and gemcitabine in the pancreatic cancer cell line SW1990. The sensitivity of SW1990 cells to TRAIL and/or gemcitabine-induced apoptosis and the rate of apoptosis were assessed by MTT assay and flow cytometry, respectively. We used Hoechst 33342 staining to observe apoptotic morphology and expression levels of proteins were analyzed by Western blottin. Growth inhibition and apoptosis rates on treatment with the combination of TRAIL and gemcitabine were significantly higher than with each drug alone (p<0.05). Pancreatic cancer cells exhibited a typical apoptosis morphology after treatment with TRAIL or gemcitabine. The levels of cellular apoptosis-associated proteins such as Smac/DIABLO, Cyto C, and the activated fragment of caspase-3 (P17) increased, but the expression of XIAP was significantly decreased after 24 h (p<0.05). SW1990 cells responded to TRAIL and/or gemcitabine-induction of apoptosis in a time and concentration-dependent manner. The mechanism of the apoptosis-sensitization effect appeared associated with significant up-regulation of Smac/DIABLO and cytochrome C, down-regulation of XIAP, and activation of caspase-3.