Adsorption Isotherm of Water Vapor and Its Large Hysteresis on Highly Ordered Mesoporous Silica

The first and second adsorption–desorption isotherms of water vapor on a new mesoporous material derived from kanemite have been measured. The isotherms show unusual type V isotherms and large hysteresis. The type V isotherms, which have never been observed for the other adsorbates, suggest that the mesoporous material has a hydrophobic surface, although the hydrophobicity decreased after treatment with water vapor because of rehydration of the surface. The significantly large hysteresis could be explained by the difference in contact angle between adsorption and desorption.     

Application of water as a solvent in microwave-assisted extraction for analysis of PCBs and CBzs in fly ash

Polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs) are two classes of dioxin precursors formed in municipal solid waste incinerators (MSWIs); they produce negative health effects similar to those of dioxins. Reducing the analytical time required for determining the concentrations of these compounds in MSWIs is important for quickly evaluating their importance and assessing associated health risks. In the present study, water is used as a safe and environmentally friendly solvent in microwave-assisted extraction (MAE) for PCB and CBz analyses. MAE is compared with traditional Soxhlet extraction (SE) to determine the extraction efficiencies. The evaluation of extraction efficiencies shows that MAE has a high extraction efficiency compared with that of SE when water content is lower than 60%. Furthermore, the extraction time and organic solvent consumption are reduced with MAE compared with SE.     

Syntheses and characterizations of three-dimensional channel-like polymeric lanthanide complexes constructed by 1,2,4,5-benzenetetracarboxylic acid

The hydrothermal reaction of YbCl(3) small middle dot6H(2)O with 1,2,4,5-benzenetetracarboxylic dianhydride resulted in [[Yb((b)btec)(1/4)((d)btec)(3/6)(H(2)O)(2)](4).6H(2)O](n)() (1) (H(4)btec = 1,2,4,5-benzenetetracarboxylic acid), and the solvothermal reaction of Er(NO(3))(3) small middle dot6H(2)O or TbCl(3).6H(2)O with 1,2,4,5-benzenetetracarboxylic dianhydride in H(2)O/acetic acid gave rise to [[Er(2)((c)btec)(2/4)((e)btec)(2/4)((f)btec)(2/4)(H(2)O)(4)].4H(2)O](n)() (2) and [[Tb(H(2)btec)(2/4)((f)btec)(3/6)(H(2)O)].2H(2)O](n)() (3), respectively. Complex 1 crystallizes in monoclinic space group C2/m with a = 20.8119(5) A, b = 17.6174(1) A, c = 5.7252(2) A, beta = 92.324(1) degrees, and Z = 1. 1 possesses a three-dimensional framework consisting of eight-coordinate ytterbium centers and two kinds of channels along the c axis. Complex 2 crystallizes in triclinic space group P with a = 9.6739(5) A, b = 11.0039(5) A, c = 11.5523 A, alpha = 104.8330(10) degrees, beta = 91.0000(10) degrees, gamma = 114.2570(10) degrees, and Z = 2. 2 has a three-dimensional framework comprising both eight- and nine-coordinate erbium centers and channels along the a axis. Complex 3 crystallizes in monoclinic space group P2(1)/n with a = 10.7246(12) A, b = 7.1693(9) A, c = 17.158(2) A, beta = 97.109(2) degrees, and Z = 4. 3 shows a three-dimensional framework containing nine-coordinate terbium centers and channels along the b axis. Uncoordinated water molecules occupy the channels in the three complexes. TGA and XRPD were determined for the three complexes, and the results illustrate that the framework of 1 is retained upon removal of uncoordinated and coordinated water molecules.     

Massenspektren der von Aminosäuren bzw. Peptiden abgeleiteten Triazin-Derivate

A mass spectrometric study of about 30 triazine derivatives from amino acids and peptides is reported. These derivatives incorporated the C-terminal of amino acids and peptides in the ring. In contrast to the mass spectra of amino acids and peptide esters reported previously, they always showed characteristic fragments, denoting the presence of the terminal triazine ring. By using this peak as a marker, it is easy to estimate the C-terminal of peptides. In dipeptides, the N-terminal and C-terminal are determined simultaneously.     

Ru3(CO)12-catalyzed silylation of benzylic C-H bonds in arylpyridines and arylpyrazoles with hydrosilanes via C-H bond cleavage

Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes involving triethyl-, dimethylphenyl-, tert-butyldimethyl-, and triphenylsilanes can be used as a silylating reagent. Coordination of an sp2 nitrogen atom to the ruthenium complex is important for achieving this silylation reaction.     

Selective Formation of Spinel Iron Oxide in Thin Films by Complexing Agent-Assisted Sol-Gel Processing

The structure of iron oxide was controlled by regulating the hydrolytic polymerization of aquo iron complexes with organic polydentate ligands such as diols. Iron oxides were prepared by calcining the precursor polymers obtained from iron nitrate nonahydrate and diols. When the diols were 1,2-pentanediol, 1,2-hexanediol and 1,2-octanediol, α-Fe₂O₃ with corundum structure appeared exclusively or as the main crystalline phase, in spite of the amount of diol used and the calcination temperature. In the case of 1,2-decanediol and 1,2-dodecanediol, when five moles of the diols were used to one mole of iron nitrate and the calcination temperatures were below 400°C, ψ-Fe₂O₃ with spinel structure appeared as the main phase and, when less than five moles of the diols were used, α-Fe₂O₃ appeared exclusively or as the main phase, irrespective of the calcination temperature. This tendency was also observed in thin films. Thus, a transparent magnetic film composed of γ-Fe₂O₃ could be prepared by applying a benzene solution of the iron polymer, obtained with 5 equivalents of 1,2-decanediol, on quartz and calcining the gel film at 350°C.     

Targeting of mitomycin C to the liver by the use of asialofetuin as a carrier.

Desialylated fetuin (asialofetuin) was adopted as a carrier for introducing drugs in parenchymal liver cells. Mitomycin C, as a model guest-compound, was covalently attached to asialofetuin through a spacer of the succinyl group. The asialofetuin-mitomycin C conjugate contained 4.4 w/w% of mitomycin C and liberated it gradually at physiological conditions (t1/2 = 37 h). The survival time of the conjugate in rat blood circulation was significantly smaller than that of the non-desialylated fetuin conjugate; the elimination half-life was 7.3 min after intravenous injection. At 30 min after injection of the conjugate in rats, 40% of the dose was present in the liver. Parenchymal cells in the liver selectively took up the conjugate, which was highly distributed to the lysosomal fraction in the cell. The greater uptake of the conjugate by hepatocytes reflected the increased excretion in the bile; totally 10.4% of the dose was recovered.     

Artificial model for cystathionine β-synthase: efficient β-replacement reaction with thiols employing a novel pyridoxal model compound having an imidazole function

As a second-generation pyridoxal model compound for cystathionine β-synthase, we designed a novel model compound having an ionophore function and an imidazole function, application of which to the β-replacement reaction with various thiols smoothly took place to give S-substituted cysteines. Peptides having a serine-O-carbonate residue at the N-terminal position were also converted to the corresponding peptides having an S-substituted cysteine residue under the catalytic conditions of the novel pyridoxal model compound.