Molecular-level control of the photoluminescence from PPV nanostructured films

The fabrication of varied molecular architectures in layer-by-layer (LbL) films is exploited to control the photoluminescence (PL) of poly(p-phenylene vinylene) (PPV) in an unprecedented way. This was achieved by controlling the F?rster energy transfer between PPV layers (donors) and layers of a commercial azodye, Brilliant Yellow (BY) (acceptors). Energy transfer was controlled by inserting spacer layers of inert polymers between PPV and BY layers and by photoaligning the BY molecules via trans-cis-trans isomerization. The PPV/BY LbL films displayed polarized PL whose intensity could be varied almost continuously by changing the time of photoalignment, which was carried out by impinging a linearly polarized laser light simultaneously to the PL experiments. For PPV/BY films with no spacer layers, PL was completely quenched, but its intensity increased with the number of spacing layers. Further increase in PL was obtained by photoaligning the BY molecules perpendicularly to the PPV molecules. This minimizes energy transfer, since F?rster processes are directional, dipole-dependent resonant transfers. Energy transfer is also controlled by imparting a preferential orientation of the PPV chains on PPV/BY LbL films deposited onto flexible Teflon substrates that may be stretched.     

CIS 1,2-functionalization of cyclohexane using selenium intermediates

The trans 1,2-phenylseleno acetate, acetamide, alcohol and nitrile of cyclohexane may be oxidized at selenium by halogens and the phenylseleno moiety displaced by halide to give high yields of 1,2 halide-containing products with cis geometry.     

Direct Synthesis of 3-Aryl Substituted Isocoumarins and Phthalides through Palladium Acetate Catalyzed C(sp2)−H Activation in Ionic Liquids

A novel Pd-catalysed oxidative coupling between benzoic acids and vinylarenes or acrylates to furnish isocoumarins and phthalides is reported. The reaction proceeds smoothly in molten tetrabutylammonium acetate via a selective C−H bond activation, with very low percentage of ligand-free palladium acetate as the catalyst, under atmospheric pressure of oxygen. Sub-stoichiometric amount of copper acetate is also required as a reoxidant for the palladium.     

Poly‐l‐Lactic Acid Nanofiber–Polyamidoamine Hydrogel Composites: Preparation,Properties, and Preliminary Evaluation as Scaffolds for Human Pluripotent Stem Cell Culturing

Electrospun poly‐l ‐lactic acid (PLLA) nanofiber mats carrying surface amine groups, previously introduced by nitrogen atmospheric pressure nonequilibrium plasma, are embedded into aqueous solutions of oligomeric acrylamide‐end capped AGMA1, a biocompatible polyamidoamine with arg‐gly‐asp (RGD)‐reminiscent repeating units. The resultant mixture is finally cured giving PLLA‐AGMA1 hydrogel composites that absorb large amounts of water and, in the swollen state, are translucent, soft, and pliable, yet as strong as the parent PLLA mat. They do not split apart from each other when swollen in water and remain highly flexible and resistant, since the hydrogel portion is covalently grafted onto the PLLA nanofibers via the addition reaction of the surface amine groups to a part of the terminal acrylic double bonds of AGMA1 oligomers. Preliminary tested as scaffolds, the composites prove capable of maintaining short‐term undifferentiated cultures of human pluripotent stem cells in feeder‐free conditions.

     

Ethyl N‐[2‐(hydroxy­acetyl)­phenyl]­carbamate,ethyl N‐[2‐(hydroxy­acetyl)‐4‐iodo­phenyl]­carbamate and ethyl N‐[2‐(hydroxy­acetyl)‐4‐methyl­phenyl]­carbamate

In ethyl N‐[2‐(hydroxy­acetyl)phenyl]carbamate, C₁₁H₁₃NO₄, all of the non‐H atoms lie on a mirror plane in the space group Pnma; the mol­ecules are linked into simple chains by a single C—H⋯O hydrogen bond. The mol­ecules of ethyl N‐[2‐(hydroxy­acetyl)‐4‐iodo­phenyl]carbamate, C₁₁H₁₂INO₄, are linked into sheets by a combination of O—H⋯I and C—H⋯O hydrogen bonds and a dipolar I⋯O contact. Ethyl N‐­[2‐(hydroxy­acetyl)‐4‐methyl­phenyl]carbamate, C₁₂H₁₅NO₄, crystallizes with Z′ = 2 in the space group P; pairs of mol­ecules are weakly linked by an O—H⋯O hydrogen bond and these aggregates are linked into chains by two independent aromatic π–π stacking inter­actions.     

Synthesis of new imidazole derivatives as potential inhibitors of thromboxane synthetase

The preparation of new imidazole derivatives containing a carboxylic moiety such as succinic, adipic or benzoic into the side chain, is reported starting from the suitable imidazole intermediates.     

Screening of matrix metalloproteinases available from the protein data bank: insights into biological functions, domain organization, and zinc binding groups

A total of 142 matrix metalloproteinase (MMP) X-ray crystallographic structures were retrieved from the Protein Data Bank (PDB) and analyzed by an automated and efficient routine, developed in-house, with a series of bioinformatic tools. Highly informative heat maps and hierarchical clusterograms provided a reliable and comprehensive representation of the relationships existing among MMPs, enlarging and complementing the current knowledge in the field. Multiple sequence and structural alignments permitted better location and display of key MMP motifs and quantification of the residue consensus at each amino acid position in the most critical binding subsites of MMPs. The MMP active site consensus sequences, the C-alpha root-mean-square deviation (RMSd) analysis of diverse enzymatic subsites, and the examination of the chemical nature, binding topologies, and zinc binding groups (ZBGs) of ligands extracted from crystallographic complexes provided useful insights on the structural arrangements of the most potent MMP inhibitors.     

HPLC with diode-array detection for the simultaneous determination of di(2-ethylhexyl)phthalate and mono(2-ethylhexyl)phthalate in seminal plasma

A high-performance liquid chromatographic method for the simultaneous determination of di(2-ethylhexyl)phthalate (DEHP) and its major metabolite mono(2-ethylhexyl)phthalate (MEHP) in seminal plasma was developed and validated. The method involves liquid-liquid extraction followed by isocratic reversed-phase chromatography with diode-array detection. The recovery, selectivity, linearity, precision and accuracy of the method were evaluated from the analysis of spiked seminal plasma samples. The effect of mobile-phase composition and pH on the retention of the target analytes was investigated. The limits of detection were 0.010 and 0.015 microg/mL, for DEHP and MEHP, respectively. This method was used to analyze real samples in support of clinical studies on these potential endocrine disruptors.     

Negative ion tandem mass spectrometry of leukotriene E4, and LTE4, metabolites: Identification of LTE4, in human urine

The sulfidopeptide leukotrienes, leukotriene E₄, (LTE₄,) and its N-acetyl derivative and several ω? and β-oxidized metabolites of LTE₄, have been analyzed by tandem mass spectrometry. [M?H]^? ions were produced by continuous flow fast atom bombardment, and collision-induced dissociation of these ions was studied by using a triple quadrupole instrument. The product ion spectra obtained were characteristic of the structure of LTE₄, and mechanisms of ion formation were investigated by using deuterated compounds. β-Elimination of the peptide portion of LTE₄, by loss of CO₂, and ethylene amine leaves the C-l carboxyl group ionized in the most abundant fragment ion for LTE₄, and all metabolites. Tandem mass spectrometry of fast atom bombardment-generated anions from ω? and β-oxidized metabolites of LTE₄, produced similar ions with only a minor influence of the third carboxyl group at the omega terminus evident. Tandem mass spectrometry was used to identify unequivocally the presence of unmodified LTE₄, in a high performance liquid chromatography-purified fraction of urine from a normal healthy volunteer after infusion with LTE₄.