Synthesis,Characterization and Crystal Structures of new Coordination Polymers of Cerium(III) and Samarium(III) Containing 2,6‐Pyridinedicarboxylic Acid

The reaction of 2,6‐pyridinedicarboxylic acid ( 1 , LH₂) with CeCl₃·7H₂O and Sm(NO₃)₃·6H₂O in the presence of triethylamine led to the coordination polymer complexes [M(L)(LH)(H₂O)₂]·4H₂O [M = Ce ( 2 ) and Sm ( 3 )]. Both complexes were characterized by elemental analyses, IR spectroscopy and the crystal structures of 2 and 3 . Crystal data for 2 at ?80 °C: monoclinic, space group P2₁/c, a = 1404.6(1), b = 1122.1(1), c = 1296.1(1) pm, β = 102.09(1)°, Z = 4, R₁ = 0.0217 and for 3 at ?80 °C: monoclinic, space group P2₁/c, a = 1395.1(1), b = 1120.1(1), c = 1282.8(1) pm, β = 102.71(1)°, Z = 4, R₁ = 0.019.     

Zinc(II) and Cadmium(II) Complexes of the 3‐(2‐Pyridyl)‐5,6‐diphenyl‐1,2,4‐triazine (PDPT) Ligand,Structural Studies of [Zn(PDPT)2Cl(ClO4)] and [Cd(PDPT)2(NO3)(ClO4)]

Two new mixed‐anion zinc(II) and cadmium(II) complexes of 3‐(2‐pyridyl)‐5,6‐diphenyl‐1,2,4‐triazine (PDPT) ligand, [Zn(PDPT)₂Cl(ClO₄)] and [Cd(PDPT)₂(NO₃)(ClO₄)], have been synthesized and characterized by elemental analysis, IR‐ and ¹H NMR spectroscopy. The single crystal X‐ray analyses show that the coordination number in these complexes is six with four N‐donor atoms from two “PDPT” ligand and two of the anionic ligands, ZnN₄ClO_perchlorate, CdN₄O_nitrateO_perchlorate. Self‐assembly of these compounds in the solid state via π–π‐stacking interactions is discussed.     

Resolution of (+/-)-ibuprofen using (-)-brucine as a chiral selector by thin layer chromatography

The enantiomeric resolution of (+/-)-ibuprofen into its enantiomers was achieved by TLC on silica gel plate using optically pure (-)-brucine as a chiral selector and acetonitrile-methanol (5:1, v/v) as the solvent system. Spots were located in an iodine chamber. The detection limit was 4.9 microg. The effect of concentration of the chiral selector, temperature and pH on resolution has been studied.     

Enatiomeric analysis of simendan by CE with beta-CD as chiral selector compared with CMPA-HPLC

The chiral separation of simendan enantiomers using capillary electrophoresis was studied with beta-cyclodextrin (beta-CD) as chiral selector. The influences of the concentration and pH of borate buffer solution, beta-CD concentration and methanol content in the background electrolyte were investigated. These factors were compared with those in an HPLC with beta-CD as chiral mobile phase additive (CMPA-HPLC). The quantification properties of the developed CE method were examined. A baseline separation of simendan enantiomers was achieved in the background electrolyte of 20 mmol/L borate buffer (pH 11.0) containing 12 mmol/L beta-CD-methanol (50:50 in volume ratio). The CE method is comparable with CMPA-HPLC in chiral resolution, although the optimal pH in CE (11.0) is much higher than that (6.0) in CMPA-HPLC. This chiral CE method is applicable to the quantitative ananlysis and enantiomeric excess value determination of L-simendan.     

共振光散射成像检测5,10,15,20-四(对三甲基氨基苯)卟吩诱导的DNA超螺旋聚集体

A resonance light scattering （RLS） imaging method was proposed based on imaging and measuring the RLS features of single suprahelical species of DNA, and its appfication to DNA assay was also investigated. In acidic medium, porphine-5,10,15,20-tetrakis（p-phenyltlimethylaminium） （PTPTMA）, could stack along the molecular surface of DNA with the mode of long-range assembly to induce the formation of suprahelical species of DNA, resulting in strong RLS signals in the range of 450-510 nm. Under the excitation of 488 nm fight beam of argon ion laser source, single suprahelical species could be observed with the aid of a common microscope due to the strong scattered fight emitted by the suprahelical species. By capturing the RLS images of the single suprahelical species with a cooled charge coupled device （CCD） camera, and analyzing the RLS data, herein an RLS imaging method of DNA was proposed based on the linear relationship between the counts of suprahelical species in the detection focus plane and the concentration of DNA in nanograms. When 1.8 μmol/L PTPTMA was employed, both calf thymus DNA （ct DNA） and fish sperm DNA （fs DNA） in the range of 25-1100 ng/mL could be detected with the limits of detection lower than 25 ng/mL （3a）. Four synthetic samples were detected satisfactorily with relative standard deviations less than 5.1%.     

Gas-phase spectroscopy of the unstable sulfur diisocyanate molecule S(NCO)2.

Sulfur diisocyanate is generated from a heterogeneous reaction of gaseous sulfur dichloride with silver cyanate and studied for the first time in the gas phase. Combined with quantum chemical calculations, the electronic structure is characterized by photoelectron spectroscopy (PES). Simultaneously, an investigation of the possible ionization and dissociation processes for the molecular cation is presented based on experimental soft ionization mass spectrometry. From the calculated bond-dissociation energies, the dissociation pathway is determined. S(NCO)2+ undergoes 1,3-sigmatropic rearrangement with a smaller barrier height (9.9 kcal mol(-1)) than the neutral counterpart. Thus, the 1,3-sigmatropic rearrangement is preferred for the molecular cation, and OCNCO+ and NS+ is produced by subsequent dissociation of the rearrangement product. The analysis agrees very well with the experimental mass spectrum.     

Thermotropic Liquid Crystals Based on Extended 2,5‐Disubstituted‐1,3,4‐Oxadiazoles: Structure–Property Relationships,Variable‐Temperature Powder X‐ray Diffraction,and Small‐Angle X‐ray Scattering Studies

A class of extended 2,5‐disubstituted‐1,3,4‐oxadiazoles R¹‐C₆H₄‐{OC₂N₂}‐C₆H₄‐R² (R¹=R²=C₁₀H₂₁O 1 a , p‐C₁₀H₂₁O‐C₆H₄‐C?C 3 a , p‐CH₃O‐C₆H₄‐C?C 3 b ; R¹=C₁₀H₂₁O, R²=CH₃O 1 b , (CH₃)₂N 1 c ; F 1 d ; R¹=C₁₀H₂₁O‐C₆H₄‐C?C, R²=C₁₀H₂₁O 2 a , CH₃O 2 b , (CH₃)₂N 2 c , F 2 d ) were prepared, and their liquid‐crystalline properties were examined. In CH₂Cl₂ solution, these compounds displayed a room‐temperature emission with λ_max at 340–471 nm and quantum yields of 0.73–0.97. Compounds 1 d , 2 a – 2 d , and 3 a exhibited various thermotropic mesophases (monotropic, enantiotropic nematic/smectic), which were examined by polarized‐light optical microscopy and differential scanning calorimetry. Structure determination by a direct‐space approach using simulated annealing or parallel tempering of the powder X‐ray diffraction data revealed distinctive crystal‐packing arrangements for mesogenic molecules 2 b and 3 a , leading to different nematic mesophase behavior, with 2 b being monotropic and 3 a enantiotropic in the narrow temperature range of 200–210 °C. The structural transitions associated with these crystalline solids and their mesophases were studied by variable‐temperature X‐ray diffractometry. Nondestructive phase transitions (crystal‐to‐crystal, crystal‐to‐mesophase, mesophase‐to‐liquid) were observed in the diffractograms of 1 b, 1 d , 2 b, 2 d , and 3 a measured at 25–200 °C. Powder X‐ray diffraction and small‐angle X‐ray scattering data revealed that the structure of the annealed solid residue 2 b reverted to its original crystal/molecular packing when the isotropic liquid was cooled to room temperature. Structure–property relationships within these mesomorphic solids are discussed in the context of their molecular structures and intermolecular interactions.     

Capillary flow behavior of worm‐like micelles studied by small‐angle X‐ray scattering and small angle light scattering

A novel capillary flow device has been developed and applied to study the orientation of worm‐like micelles, among other systems. Small‐angle X‐ray scattering (SAXS) data from micelles formed by a Pluronic block copolymer in aqueous salt solution provides evidence for the formation of worm‐like micelles, which align under flow. A transition from a rod‐like form factor to a less persistent conformation is observed under flow. Flow alignment of worm‐like micelles formed by the low molar mass amphiphile system cetyl pyridinium chloride+sodium salicylate is studied for comparative purposes. Here, inhomogenous flow at the micron scale is revealed by streaks in the small‐angle light scattering pattern perpendicular to the flow direction. Copyright © 2006 John Wiley & Sons, Ltd.     

Reinforcement of Self‐Healing Polyacrylic Acid Hydrogel with Acrylamide Modified Microcrystalline Cellulose†

Self‐healing hydrogel such as polyacrylic acid (PAA) hydrogel has attracted increasing attention based on its promising potential applications. However, it usually suffers from low strength especially as mechanical device. Herein, a commercial microcrystalline cellulose (MCC) was modified with acrylamide to graft polyacrylamide (PAM) chains on the particle surface. The acrylamide‐modified MCC (AM‐MCC) was then dispersed in monomer solution of acrylic acid to prepare composite hydrogel. The mechanical properties of the obtained composite hydrogels and the self‐healed hydrogels were carefully measured by compressive and tensile tests, and by dynamic mechanical analysis. Our results demonstrate that introduction of a small amount of AM‐MCC such as 3 wt% can not only reinforce the original hydrogel and the healed hydrogel markedly, but also improve self‐healing efficiency obviously. The analyses indicate that in addition to the reversible multi‐interactions such as hydrogen bonding and ionic interactions, the entanglements between the PAA chains of the hydrogel matrix and the PAM chains grafted on the MCC particles have also played an important role on the improvement in mechanical performances and the healing ability of the hydrogel. Moreover, the responsiveness to exterior ion has been tested to indicate potential application of the composite hydrogel as self‐healable sensor.