High spin chemistry underlying organic molecular magnetism: Topological symmetry rule as the first principle of spin alignment in organic open-shell systems of π-conjugation and their ions

This review paper deals with an overview of molecule-based magnetism as a rapidly developing interdisciplinary field, topological symmetry rule as the first principle of spin alignment in organic open-shell systems in the ground state, the proposal of organic through-bond 1D and 2D ferro- and superparamagnets and the detection of the first organic high-spin molecule, m-phenylenebis(phenylmethylene) in the quintet ground state (S = 2), followed by extended organic high-spin systems with π-conjugation such as aromatic hydrocarbons having S = 3, 4, 5. The paper also describes a theoretical approach to the understanding of electronic spin structures of organic high-spin molecules by invoking both Heisenberg and Hubbard model Hamiltonians, weakly interacting intramolecular high-spin systems from both experimental and theoretical sides, the spin density distribution of the first organic high-spin molecule in terms of electron- nuclear multiple resonance spectroscopy and the detection and characterization of ionic high-spin hydrocarbons, emphasizing the establishment of high spin chemistry underlying organic molecular magnetism.     

Enantioselective spiro ene-carbocyclization of 1,6-enynes catalyzed by tropos rhodium(I) complex with skewphos ligand

A tropos rhodium(I) complex having skewphos ligand is shown to be a highly enantioselective catalyst for asymmetric ene-type carbocyclization of 1,6-enynes with tri-substituted olefins to control quaternary stereogenic centers or spiro-rings.     

Reaction kinetics and pathway of hydrothermal decomposition of aspartic acid

The kinetics and pathway of hydrothermal decomposition of aspartic acid were studied using a continuous‐flow tubular reactor. The reaction was carried out in the temperature range of 200–260°C and at a pressure of 20 MPa. Deamination was the primary reaction, indicated by the presence of significant amount of ammonia, fumaric acid, or maleic acid in the products. Other reaction products were pyruvic acid, malic acid, and traces of succinic and lactic acid. Traces of alanine were also detected, showing the possibility of decomposing high‐molecular weight amino acids to obtain simple amino acids such as glycine or alanine. Results on the effect of reaction parameters demonstrated that decomposition of aspartic acid is highly temperature dependent under hydrothermal conditions. For a slight temperature difference of 60°C (from 200 to 260°C), the first‐order reaction rate constants of 0.003 significantly increased to 0.231 s^?1. The activation energy was 144 kJ/mol, as calculated by the Arrhenius equation. No significant effect was exhibited by other reaction parameters such as pH and pressure. The results are useful in controlling the hydrolysis of proteinaceous materials toward high yield of aspartic acid under hydrothermal conditions. © 2007 Wiley Periodicals, Inc. 39: 175–180, 2007     

Preparation and certification of the new reference materials; plastics (disk form, JSAC 0621-0625) for determination of mercury using x-ray fluorescent analysis.

The Japan Society for Analytical Chemistry has developed some new plastic certified reference materials (CRMs) for the analysis of mercury in polyester disks using XRF analysis. These CRMs (named as JSAC 0621-0625) were prepared by casting polyesters including a toluene solution of organometallic compounds as a standard. Concentrations of the five levels of mercury ranged from 0 to 250 mg/kg. Homogeneity tests of prepared disks had shown excellent results. Interlaboratory comparison study for the certification was performed by 15 laboratory participants. The z-scores in robust statistical method was applied for the evaluation of outliers. The certified values were assigned after discarding outliers. The uncertainties of certified values were determined as the confidence levels of 95%.     

Singular integral operators on 53-0153-0153-01-spaces

Summary It is shown that certain singular integral operators with variable kernels leave invariant theL ^v, -spaces studied by Campanato, Stampacchia, Peetre and others. Our results extend Peetre's work on convolution operators.     

Metal components analysis of metallothionein-III in the brain sections of metallothionein-I and metallothionein-II null mice exposed to mercury vapor with HPLC/ICP-MS

Mercury vapor is effectively absorbed via inhalation and easily passes through the blood–brain barrier; therefore, mercury poisoning with primarily central nervous system symptoms occurs. Metallothionein (MT) is a cysteine-rich metal-binding protein and plays a protective role in heavy-metal poisoning and it is associated with the metabolism of trace elements. Two MT isoforms, MT-I and MT-II, are expressed coordinately in all mammalian tissues, whereas MT-III is a brain-specific member of the MT family. MT-III binds zinc and copper physiologically and is seemed to have important neurophysiological and neuromodulatory functions. The MT functions and metal components of MTs in the brain after mercury vapor exposure are of much interest; however, until now they have not been fully examined. In this study, the influences of the lack of MT-I and MT-II on mercury accumulation in the brain and the changes of zinc and copper concentrations and metal components of MTs were examined after mercury vapor exposure by using MT-I, II null mice and 129/Sv (wild-type) mice as experimental animals. MT-I, II null mice and wild-type mice were exposed to mercury vapor or an air stream for 2 h and were killed 24 h later. The brain was dissected into the cerebral cortex, the cerebellum, and the hippocampus. The concentrations of mercury in each brain section were determined by cold vapor atomic absorption spectrometry. The concentrations of mercury, copper, and zinc in each brain section were determined by inductively coupled plasma mass spectrometry (ICP-MS). The mercury accumulated in brains after mercury vapor exposure for MT-I, II null mice and wild-type mice. The mercury levels of MT-I, II null mice in each brain section were significantly higher than those of wild-type mice after mercury vapor exposure. A significant change of zinc concentrations with the following mercury vapor exposure for MT-I, II null mice was observed only in the cerebellum analyzed by two-way analysis of variance. As for zinc, the copper concentrations only changed significantly in the cerebellum. Metal components of metal-binding proteins of soluble fractions in the brain sections were analyzed by size-exclusion high-performance liquid chromatography (HPLC) connected with ICP-MS. From the results of HPLC/ICP-MS analyses, it was concluded that the mercury components of MT-III and high molecular weight metal-binding proteins in the cerebellum of MT-I, II null mice were much higher than those of wild-type mice. It was suggested that MT-III is associated with the storage of mercury in conditions lacking MT-I, and MT-II. It was also suggested that the physiological role of MT-III and some kind of high molecular weight proteins might be impaired by exposure to mercury vapor and lack of MT-I and MT-II.     

Solvent-free Synthesis of Dihydrofuran-fused [60]Fullerene Derivatives by High-speed Vibration Milling

Solvent-free organic reactions have been attracting great interest of chemists due to the elimination of the usage of harmful organic solvents,low costs,and simplicity in the procedure1.Solvent-free mechanochemical reactions of fullerenes were explored and are significant for the reactions of fullerenes because the low solubility of fullerenes in common organic solvents requires large quantity of organic solvents and some novel fullerene reactions could only occur in the solid-state reaction2.…     

Senecicannabine,a new pyrrolizidine alkaloid from senecio cannabifolius

The structure of senecicannabine($\text{1}$), a new mcrocyclic pyrrolizidine alkaloid isolated from $\text{Senecio cannabifolius}$, has been established by chemical study and X-ray analysis.