Spectroscopic and biological studies on newly synthesized nickel(II) complexes of semicarbazones and thiosemicarbazones

Nickel(II) complexes, having the general composition Ni(L)2X2, have been synthesized [where L: isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC) and 4-aminoacetophenone thiosemicarbazone (LLD) and X=Cl-, 1/2SO(4)2-]. All the Ni(II) complexes reported here have been characterized by elemental analyses, magnetic moments, IR, electronic and mass spectral studies. All the complexes were found to have magnetic moments corresponding to two unpaired electrons. The possible geometries of the complexes were assigned on the basis of electronic and infrared spectral studies. Newly synthesized ligand and its nickel(II) complexes have been screened against different bacterial and fungal growth.     

Comparison of the retention behaviour of phenol derivatives on porous graphitized and octadecylsilica columns

Summary The retention of 22 ring-substituted phenol derivatives on porous graphitized carbon (PGC) (eluents: acetonitrile — water and methanol — water mixtures) and on octadecylsilica (ODS) (eluents: methanol — 0.025 M KH₂PO₄ mixtures) was determined, and the relationship between retention and physicochemical parameters were evaluated by principal component analysis followed by two-dimensional nonlinear mapping and by cluster analysis as well as by canonical correlation analysis. Calculations proved that marked differences can be detected between the retention characteristics of PGC and ODS columns, and the electronic parameters of phenol derivatives have the highest impact on their retention. The comparison of various multivariate mathematical-statistical methods indicated that principal component analysis followed by two dimensional non-linear mapping is the most appropriate method for the evaluation of large data matrices in RP-HPLC.     

“鱼”乐圈大揭秘

This article introduces the relationship between chemistry and fish farming, fish selling, and fish food. The nitrogen cycle process in fish ponds is introduced to explain the fish farming. "Yufuling" is used as the entry point to fish selling to connect food safety with chemistry. Fishy smell is explained from a chemical perspective for fish food. This paper aims at making a scientific explanation of life phenomena, deepening the consciousness of chemical life, helping people establish a correct view of chemical science, and inspiring youth to learn to use the knowledge that they have learned to explain life phenomena. This paper also tries to show the youth that life cannot be separated from chemistry, and chemistry cannot be separated from life.     

Insights on the origin of the structural phase transition in BaV10O15 from electronic structure calculations and the effect of Ti-doping on its structure and electrical transport properties

Band structure calculations at the level of LMTO-ASA provide insight into the electronic structure of BaV₁₀O₁₅ and the origin of the structural phase transition. A crystal orbital Hamiltonian population/integrated crystal orbital Hamiltonian population analysis provides evidence that the crystallographic phase transition is driven by V-V bond formation. As well, the energy bands near the Fermi level are very narrow, <1 eV, consistent with the fact that the observed insulating behavior can be due to electron localization via either Mott-Hubbard correlation and/or Anderson disorder. The partial solid solution, BaV_10−xTi_xO₁₅, was examined to study the effect of Ti-doping at the V sites on the structure and electronic transport properties. In spite of the non-existence of “BaTi₁₀O₁₅”, the limiting x=8, as indicated by a monotonic increase in the cell volume and systematic changes in properties. This limit may be due to the difficulty of stabilizing Ti²⁺ in this structure. For x=0.5 both the first order structural phase transition and the magnetic transition at 40 K are quenched. The samples obey the Curie-Weiss law to x=3 with nearly spin only effective moments along with θ values which range from −1090 K (x=0.5) to −1629 K (x=3). For x>3 a very large, ∼2×10⁻³ emu/mol, temperature independent (TIP) contribution dominates. Conductivity measurements on sintered, polycrystalline samples show semiconducting behavior for all compositions. Activation energies for Mott hopping derived from high temperature data range from ∼0.1 eV for x=0-1 and fall to a plateau of 0.06 eV for x=3-7. Low temperature data for x=3, 5 and 7 show evidence for Mott variable range hoping (VRH) with a T^1/4 law and in one case between 5 and 17 K, a Efros-Shklovskii correlated hopping, T^1/2 law, was seen, in sharp contrast to BaV₁₀O₁₅ where only the E-S law was observed up to 75 K. Seebeck coefficients are small (<35 μV/K), positive, roughly TIP and increase with increasing x up to x=5. This may point to a Heikes hopping of holes but a simple single carrier model is impossible. The compositions for x>3 are remarkable in that local moment behavior is lost, yet a metallic state is not reached. The failure of this system to be driven metallic even at such high doping levels is not fully understood but it seems clear that disorder induced carrier localization plays a major role.     

Preparation of block copolymer vesicles in solution

Block copolymer vesicles can be prepared in solution from a variety of different amphiphilic systems. Polystyrene‐block‐poly(acrylic acid), polystyrene‐block‐poly(ethylene oxide), and many other block copolymer systems can produce vesicles of a wide range of sizes; those in the range of 100–1000 nm have been explored extensively. Different factors, such as the absolute and relative block lengths, the presence of additives (ions, homopolymers, and surfactants), the water content in the solvent mixture, the nature and composition of the solvent, the temperature, and the polydispersity of the hydrophilic block, provide control over the types of vesicles produced. Their high stability, resistance to many external stimuli, and ability to package both hydrophilic and hydrophobic compounds make them excellent candidates for use in the medical, pharmaceutical, and environmental fields. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 923–938, 2004     

一种低磁矩、大功率复合稀土石榴石铁氧体的工艺和性能研究

为满足低场区几百兆赫的超大功率器件的性能要求,以钇铁石榴石铁氧体为基础,制备了一种低磁矩复合稀土石榴石铁氧体YGd CaVInIG,研究了少量Mn3+替代Fe3+和预烧温度、烧结温度对铁氧体性能和结构的影响。实验表明,以少量Mn3+替代Fe3+可以提高铁氧体电阻率,降低磁损耗和介电损耗。Mn3+掺入量以x为0.04～0.06比较合适,铁氧体最佳予烧温度为1050℃,最佳烧结温度1350～1380℃,保温5h,氧气中烧结,其性能为:4πMs=500±10%kA·m-1,ΔH=5.25～5.55kA·m-1,TC>180℃,tgδe≤0.5×10-5,这种材料适合微波低频段器件性能要求。X射线衍射分析指出,掺Mn3+的YGdCaVInIG铁氧体相变完全,呈单相复合石榴石铁氧体,空间群为I230,点阵常数1.25057～1.25101nm,单胞分子数n为7.75～7.80。     

New unsymmetrical difluoroaromatic compounds and estimation of their reactivities in nucleophilic substitution

A series of previously unknown unsymmetrical difluoroaromatic compounds, viz., p-fluorobenzoylphenyl(p-fluorophenyl)-substituted imidazoles, pyrazines, and quinoxalines, were synthesized according to multistep procedures with the use of chloral as the key compound. The reactivities of the resulting difluoroaromatic compounds were estimated based on ¹⁹F and ¹³C NMR spectral data and the results of quantum-chemical calculations. The calculated charge densities on the C_ipso atoms correlate linearly with the experimental chemical shifts in the ¹⁹F and ¹³C NMR spectra. Difluoroaromatic compounds, which are characterized by _F > –110 and _C > 163 and by the charge density on the C_ipso atom higher than 0.08 e, are sufficiently activated to be used for the preparation of high-molecular-weight polyethers.     

Activated bis- and tetrafluoroaromatic compounds containing bis-phenylquinoxaline fragments

New activated bis- and tetrafluoroaromatic compounds containing the bis-phenylquinoxaline fragments, viz., methylene-bis-6(7),6"(7")-{2-(p-fluoro)phenyl-3[4-(p-fluorobenzoyl)phenyl]quinoxalines}, were prepared according to multistep procedures with the use of chloral as the starting compound. The presence of the activating carbonyl groups in the para positions with respect to two fluorine atoms opens up the possibility of the use of these monomers for the synthesis of high-molecular-weight aromatic quinoxaline-containing polyether ketones.     

Effect of selenium oxidation state on cadmium translocation in chamomile plants

Syntheses and spectral characteristics of cadmium(II) compounds (CdSeO₄, CdSeO₃, and Cd(NCSe)₂(nia)₂) containing selenium in oxidation states (VI), (IV), and (-II) are described. In Cd(NCSe)₂(nia)₂, nicotinamide (nia) and selenocyanate anions are bonded to Cd atom as N-donor monodentate ligands. Nicotinamide is coordinated through the ring nitrogen atom. The effects of these selenium compounds as well as Cd(NCS)₂(nia)₂ on the growth and Cd accumulation in roots and shoots of hydroponically cultivated chamomile plants (cultivar Lutea) were studied. In the applied concentration range (12–60 μmol dm⁻³) Cd(NCS)₂(nia)₂ affected neither the length nor the dry mass of roots and shoots. Other compounds applied at 24 μmol dm⁻³ and 60 μmol dm⁻³ significantly reduced dry mass of roots and shoots. Selenium oxidation state in the cadmium compounds affected Cd accumulation in plant organs as well as Cd translocation within the plants, which was reflected in the values of bioaccumulation (BAF) and translocation factors (S/R). Cd amount accumulated by shoots was lower than that in the roots. The highest BAF values determined for Cd accumulation in shoots were obtained with CdSeO₄. Substitution of S with Se in the Cd(NCX)₂(nia)₂ (X = Se or S) caused an increase of Cd translocation into the shoots. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Hierarchical Structure‐Within‐Structure Morphologies in A2‐star‐(B‐alt‐C) Molecules

We employ dissipative particle dynamics (DPD) to examine the self‐assembly behavior of A₂‐star‐(B‐alt‐C) molecules. We successfully observe various types of hierarchical structure‐within‐structures, such as A‐formed spheres in the matrix formed by B and C alternating layers, hexagonally packed A‐formed cylinders in the matrix with B and C segregated layers, B and C alternating layers‐within‐lamellae, coaxial B and C alternating domains within hexagonally packed BC‐formed cylinders in the A‐matrix, and co‐centric BC‐alternating domains within BC‐formed spheres in the A‐matrix, by increasing the A composition. Generally speaking, the small length‐scale B and C segregated domains are in parallel to the large length‐scale structures. This hierarchical periodicity along the same axis as well as the various characteristic structures, that the A₂‐star‐(B‐alt‐C) copolymers display, are quite different from those in A‐block‐(B‐graft‐C) coil‐comb copolymers. Moreover, it is interesting to find that when the copolymer chain length increases, though the hierarchical structure type is maintained, the number of small length‐scale lamellae that can form within the large length‐scale structure increases. These hierarchical structures under various compositions are reported theoretically for the first time in the copolymer systems consisting of the alternating blocks, and are in good agreement with the most recent experimental work by Matsushita and co‐workers (Macromolecules 2007 , 40, 4023).