Carrier doping effect into quasi-one-dimensional bromo-bridged Ni(III) complexes with strong electron-correlation by Cu(II) ions, [Ni1-xCux(chxn)2Br]Br2-x

This communication will describe the electron doping effect into Ni(III) complexes by Cu(II) ions, [Ni(1-x)Cu(x)(chxn)(2)Br]Br(2-x) (x = 0.038 and 0.101) by using an electrochemical oxidation method. A drastic increase of electrical conductivity as well as a new absorption band around 0.5 eV in single crystal reflectance spectra was observed by doping Cu(II) ions, indicating the electron doping was successfully made. An ESR result shows unpaired electrons locate in the d(x2-y2) orbitals of Cu(II) and have almost no interaction with those of other ions.     

A novel tetranuclear copper(II) complex with alternating mu 1,1-azido and phenoxo bridges: synthesis,structure, and magnetic properties of [Cu4(mu-salen)2(mu 1,1-N3)2(N3)2

A novel tetranuclear copper(II) complex containing alternating mu(1,1)-azido and monophenoxo bridges has been synthesized and characterized by spectroscopic methods, X-ray single-crystal analysis, and variable-temperature magnetic measurements. The magnetic behavior, investigated in the temperature range 2-300 K, indicates that the interactions between copper ions are antiferromagnetic in nature for both azido and phenoxo bridges. The temperature dependence of the magnetic susceptibility was fitted with J(1) = -12.8 cm(-1), J(2) = -10 cm(-1), g = 2.171, 2.1% paramagnetic component, and negligible temperature-independent paramagnetism (5 x 10(-8)). At variance with the earlier reports of these types of complexes containing a mu(1,1)-azido group, the end-on double-azido-bridged copper(II) center in this complex shows an antiferromagnetic interaction.     

Reaction of 2-(5-aminopyrazol-1-yl)quinoxaline 4-oxides with dimethyl acetylenedicarboxylate

The reaction of 6-chloro-2-hydrazinoquinoxaline 4-oxide 6 with ethyl 2-(ethoxymethylene)-2-cyanoacetate or (1-ethoxyethylidene)malononitrile gave 2-(5-amino-4-ethoxycarbonylpyrazol-1-yl)-6-chloroquinoxaline 4-oxide 7a or 2-(5-amino-4-cyano-3-methylpyrazol-1-yl)-6-chloroquinoxaline 4-oxide 7b , respectively. The reaction of compound 7a or 7b with dimethyl acetylenedicarboxylate resulted in the 1,3-dipolar cycloaddition reaction and then ring transformation to afford 4-(5-amino-4-ethoxycarbonylpyrazol-1-yl)-8-chloro-1,2,3-trismethoxycarbonylpyrrolo[1,2-α]quinoxaline 8a or 4-(5-amino-4-cyano-3-methylpyrazol-1-yl)-8-chloro-1,2,3-trismethoxycarbonylpyrrolo[1,2-α]quinoxaline 8b , respectively.     

Reaction of 4-acetoxy-1,4-benzoxazin-3-one with DNA. A possible chemical mechanism for the antifungal and mutagenic activities

A reaction of 4-acetoxy-7-methoxy-2H-1,4-benzoxazin-3(4H)-one with DNA and nucleotides was described. The N⁴ position of the benzoxazinone reacted with the C₈ position of the guanine residue of DNA and guanylic acid.     

Retention behaviour in micro-HPLC on various types of glasses modified with phenyl groups

Summary The retention and selectivity behaviour of some antiepileptic drugs were studied by micro high-performance liquid chromatography on nine types of phenyl-modified glasses, prepared with xylene solution containing phenyldimethylchlorosilane (P), diphenylmethylchlorosilane (D) or triphenylchlorosilane (T), using three types of glass with various mean pore diameters and/or specific surface areas. From elemental analysis data for carbon, the maximum number of accessible phenyl surface groups per 100?² of glass (mean pore diameter: 335?, specific surface area: 69m²/g) in P, D and T gel was calculated to be 2.38, 1.58 and 0.76, respectively. Using various CH₃CN−0.01 M KH₂PO₄ mixtures as eluents, the antiepileptic drugs were separated on all the glasses studied, but with different degrees of resolution. With an increase in the specific surface area, the k′ values of some antiepileptic drugs also increased.     

Degradation of poly(lactic acid) into repolymerizable oligomer using montmorillonite K10 for chemical recycling

The degradation of poly(L-lactic acid) (PLLA) into a repolymerizable oligomer was carried out using a clay catalyst, montmorillonite K10 (MK10), with the objective of developing a chemical recycling process. PLLA having an Mw of 120,000 was degraded by MK10 in toluene at 100 degrees C for 6 h to produce the corresponding linear-type oligomers having a molecular weight of a few hundreds in a yield of greater than 90%. The oligomer was readily polymerized by a conventional chemical catalyst to give a high-molecular-weight PLLA. No isomerization of L-lactic acid occurred during the degradation process using MK10. The MK10 could be repeatedly used at least five times without any significant decrease in its activity. The degradation of PLLA was accelerated by the addition of a small amount of ethanol in toluene using anhydrous MK10 to produce oligomers with ethyl ester end groups.     

Evaluation of carbon dioxide equivalent values for greenhouse gases: CEWN as a new indicator replacing GWP

A new indicator, the CEWN (Carbon Dioxide Equivalent Warming Number), is proposed as an alternative to the GWP (Global Warming Potential). CEWN is a metric where the global warming by the emission of gases is compared unifying the removal rate of each gas from the atmosphere, using carbon dioxide as a reference. To comply with the basket system of the Kyoto Protocol, GWP is used with a 100-year time horizon, making it unsatisfactory for the evaluation of long-lived compounds. As the removal rate from the atmosphere depends on the lifetime, the CEWN presents a fair assessment of the relative global warming.     

Synthesis of Glc1Man9‐Glycoprotein Probes by a Misfolding/Enzymatic Glucosylation/Misfolding Sequence

Glycoproteins in non‐native conformations are often toxic to cells and may cause diseases, thus the quality control (QC) system eliminates these unwanted species. Lectin chaperone calreticulin and glucosidase II, both of which recognize the Glc₁Man₉ oligosaccharide on glycoproteins, are important components of the glycoprotein QC system. Reported herein is the preparation of Glc₁Man₉‐glycoproteins in both native and non‐native conformations by using the following sequence: misfolding of chemically synthesized Man₉‐glycoprotein, enzymatic glucosylation, and another misfolding step. By using synthetic glycoprotein probes, calreticulin was found to bind preferentially to a hydrophobic non‐native glycoprotein whereas glucosidase II activity was not affected by glycoprotein conformation. The results demonstrate the ability of chemical synthesis to deliver homogeneous glycoproteins in several non‐native conformations for probing the glycoprotein QC system.     

Asymmetric Synthesis of 2H‐Azirines with a Tetrasubstituted Stereocenter by Enantioselective Ring Contraction of Isoxazoles

Highly strained 2H‐azirines with a tetrasubstituted stereocenter were synthesized by the enantioselective isomerization of isoxazoles with a chiral diene–rhodium catalyst system. The effect of ligands and the coordination behavior support the proposed catalytic cycle in which the coordination site is fixed in favor of efficient enantiodiscrimination by a bulky substituent of the ligand. In silico studies also support the existence of a rhodium–imido complex as a key intermediate for enantiodiscrimination.