Novel Hydrogen‐bond Three Dimensional Networks Generated from the Reaction of Metal Nitrate Hydrate (M = Co,Ni) with Ammonium Thiocynate and Bidentate Ligand Piperazine

The reaction of Co(NO₃)₂·6H₂O with two equivalents of PPz (PPz = piperazine hexahydrate) and two equivalents of NH₄SCN in CH₃OH afforded the complex [Co(NCS)₂(PPz)₂(CH₃OH)₂]. The reaction of Ni(NO₃)₂·6H₂O with two equivalents of PPz and four equivalents of NH₄SCN in CH₃OH afforded the complex [Ni(NCS)₄(PPz)₂]. Their IR spectra have been recorded and the structures have been determined. Crystal data for 1 : space group P&1bar;, a = 6.7208(6) Å, b = 8.4310(8) Å, c = 8.5923(8) Å, a = 77.881(2)°, β = 76.342(2)°, γ = 83.936(2)°, V = 461.75(1) ų, Z = 1 with final residuals R1 = 0.0650 and wR2 = 0.1725. Crystal data for 2 : space group P2(1)/n, a = 7.4209(6) Å, b = 11.0231(9) Å, c = 12.317(1) Å, β = 96.642(9)°, V = 1000.9(2) ų, Z = 2 with final residuals R1 = 0.0378 and wR2 = 0.0809. Important NCS—H‐N and O‐H—N(PPz) hydrogen‐bonding interactions in compound 1 and NCS···H‐N hydrogen‐bonding interactions and NCS—SCN interactions in compound 2 play a significant role in aligning the polymer strands in crystalline solids.     

On the behaviour of cerium(III) in hydrochloric acid

Summary The sorption of Ce³⁺ from hydrochloric acid and its chromatography on a column filled with Dowex 50 X8 was studied. The break-through volumes and elution volumes, together with the sorption profile and band broadening were determined at different temperatures and are discussed. The Chromatographic results are interpreted in terms of cerium complex formation.

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Über das Verhalten von Cerium(III) in salzsaurer Lösung

Zusammenfassung Die Sorption von Ce³⁺ aus salzsaurer Lösung in einer mit Dowex 50 X8 gefüllten Säule sowie dessen Chromatographie wurden untersucht. Die Durchbruchs- und Elutionsvolumina wurden bestimmt und diskutiert. Die Ergebnisse wurden im Sinne einer Komplexbildung interpretiert.

     

马心血红蛋白在氧化铟电极上的直接电子传递反应

马心血红蛋白在氧化铟电极上的直接电子传递反应杨秀娟，菊，陆天虹（中国科学院长春应用化学研究所电分析化学开放实验室，长春，１３００２２）关键词血红蛋白，氧化铟电极，循环伏安法蛋白质与电极之间的电子转移在某种程度上类似于生物体内蛋白质分子之间的电子转移过...     

Application of dodecyldimethyl (2-hydroxy-3-sulfopropyl) ammonium in wall modification for capillary electrophoresis separation of proteins

A zwitterionic surfactant, dodecyldimethyl (2-hydroxy-3-sulfopropyl) ammonium (C12H25N+(CH3)2CH2CHOHCH2SO3-), named dodecyl sulfobetaine (DSB), was used as a novel modifier to coat dynamically capillary walls for capillary electrophoresis separation of basic proteins. The DSB coating suppressed the electroosmotic flow (EOF) in the pH range of 3-12. At high DSB concentration, the EOF was suppressed by more than 8.8 times. The DSB coating also prevented successfully the adsorption of cationic proteins on the capillary wall. Anions, such as Cl-, Br-, I-, SO4(2-), CO3(2-), and ClO4-, could be used as running buffer modifiers to adjust the EOF for better separation of analytes. Using this dynamically coated capillary, a mixture of eight inorganic anions achieved complete separation within 4.2 min with the efficiencies from 24,000 to 1,310,000 plates/m. In the presence of ClO4- as EOF adjustor, the separation of a mixture containing four basic proteins (lysozyme, cytochrome c, alpha-chymotrypsinogen A, and myoglobin) yielded efficiencies of 204,000-896,000 plates/m and recoveries of 88%-98%. Migration time reproducibility of these proteins was less than 0.5% relative standard deviation (RSD) from run to run and less than 3.1% RSD from day to day, showing promising application of this novel modifier in protein separation.     

The Structure of Bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium in the Solid State and in Solution

The complex, bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium, Pd[(S)‐APCS]₂, 1 , was prepared by reaction of 2‐[(1S)‐(+)‐10‐camphorsulfonamino]‐6‐aminopyridine with PdCl₂ in THF. Complex 1 has been characterized by spectroscopic methods and its structure has been determined by X‐ray crystallography. Crystal data: space group C2, a= 16.082 (2), b = 17.104 (2), c = 13.051 (2)Å, β = 99.95 (1)°, V = 3535.9 (8) ų, Z = 2 with final residuals R1 = 0.0491 and wR2 = 0.0944. Two independent molecules, (S,S)‐Pd[(S)‐APCS]2, 1a , and (R,R)‐Pd[(S)‐APCS]2, 1b , were found in each asymmetric unit, which exchange to each other via a series of nitrogen inversion and C‐C bond rotation. The inversion energy (ΔGc₁^≠) and the energy barrier (δGc₂^≠) were 11.5 ± 0.1 Kcal mol^?1 at 246 K and 9.8 ± 0.1 Kcal mol^?1 at 199 K, respectively, calculated by dynamic NMR data.     

Molecular spectroscopy of symmetric fragmentary exchange in N-oxypyridinium salts

A number of N-acetyloxypyridinium salts has been studied, using molecular spectroscopy methods. These compounds exist in solutions of bipolar solvents as ions and ion pairs of various structure. The association to ion pairs effects the frequences and intensities of characteristic vibrations, the chemical shifts of proton peaks, and the reaction rate of symmetric exchange of acetyl groups. Based on the spectrochemical correlations, data on the structure of the salts, the acetyl exchange reaction mechanism, and the influence of the solvent nature, the reagent structures, the additions of the base electrolyte and crown-ether on its kinetic characteristics have been obtained.     

Resveratrol derivatives potently induce apoptosis in human promyelocytic leukemia cells

Resveratrol has been shown to possess antioxidant and anticancer activities, but little is known on the effect of resveratrol derivatives. Recently we have isolated resveratrol and its dimers and trimers from peony (Paeonia lactiflora) seeds, and reported their strong antioxidant and cytotoxic activity. In the present study, we have evaluated cellular effects of resveratrol derivatives; viniferin, gnetin H, and suffruticosol B on the proliferation and apoptosis in HL-60 cells in vitro. All resveratrol and its derivatives reduced viability of HL-60 cells in a dose-dependent manner with their IC(50) values of 20-90 microM. Ascending orders of IC(50) values were suffruticosol B, gnetin H, viniferin and resveratrol respectively. HL-60 cells treated with the four stilbenes exhibited the distinct morphological changes characteristics of cell apoptosis such as chromatin condensation, apoptotic bodies, and DNA fragmentations. A time-dependent histogram of the cellular DNA analyzed by flow cytometry revealed a rapid increase in subdiploid cells and a concomitant decrease in diploid cells exposed to 100 microM resveratrol for 0-24 h. Cells treated with 25 microM of resveratrol, viniferin, gnetin H, and suffruticosol B for 24 h resulted in increment of sub-G1 population by 51, 5, 11 and 59%, respectively. Treatment of cells with 0-20 microM resveratrol for 5 h produced a concentration-dependent decrease in cytochrome P450 (CYP) 1B1 mRNA levels. Suffruticosol B also suppressed CYP1B1 gene expression. These results demonstrated that resveratrol oligomers also strongly suppressed HL-60 cell proliferation, and induced DNA damage. In addition, CYP1B1 gene supression may suggest an involvement in the resveratrol-induced apoptosis in HL-60 cells.     

Role of sphingomyelin-MAPKs pathway in heat-induced apoptosis

The role of sphingomyelinase (SMase) activation and mitogen activated protein kinases (MAPKs) activation in cellular apoptosis was investigated during the hyperthermic treatment of HL-60 human leukemia cells. Treating the cells for 1 h at 43(o)C caused more than 50% of cellular apoptosis within several hours. The neutral-SMase activity in the cells treated for 1 h at 42(o)C was slightly increased but decreased in the cells treated at 43(o)C or 44(o)C for the same period whereas the acid SMase activity was slightly increased after heating the cells at 42(o)C and 43(o)C and markedly increased at 44(o)C for 1 h. Treatment of cells with inhibitors of SMase activation and ceramide formation significantly reduced the heat-induced apoptosis. Three major families of mitogen-activated protein kinases (MAPKs), i.e. ERK1/2, p38 and JNK, were activated by the hyperthermic treatment of cells. Inhibition of ERK1/2 with PD98059 exerted little effect on the heat-induced apoptosis and p38 inhibition with SB203580 slightly lessened apoptosis whereas, inhibition of JNK with SP600125 markedly suppressed the heat-induced apoptosis. These results indicate that heat-shock induced the activation of SMase, particularly acid-SMase, thereby causing apoptosis and that JNK played a pivotal role in heat-induced apoptosis in HL-60 leukemia cells.