Synthesis of bisquinoline–pyrrole oligoamide as G-quadruplex binding ligand

A one-pot procedure using ammonium formate under palladium catalysis for the reductive dechlorination and reduction of nitro group of 4-chloro-8-nitro–quinoline derivatives has be successfully carried out. This has lead to the synthesis of bisquinoline–pyrrole oligoamide 1, which show significant G-quadruplex selectivity in preference to duplex DNA. The cooperativity between the bisquinoline and pyrrole oligoamide moieties for good binding affinity to G-quadruplex was proven by synthesizing 2 and 3 lacking a quinoline ring and pyrrole amide, respectively, and both show much reduce affinity to G-quadruplex. Altogether, the results demostrate that the appropriate combination of two chromophores to form the hybride can attenuate binding affinity and selectivity towards G-quadruplex, an important criteria for the rational drug design.     

Synthesis of directly linked diazine isosteres of pyrrole-polyamide that photochemically cleave DNA

A distamycin model containing an isosteric diazine linked pyrrole has been designed and synthesized. The key steps of the synthesis involved the successful diazotization of the 4-amino-pyrrole derivatives to give the diazomium salts, which undergo coupling reactions with N-methylpyrrole to yield the directly linked diazine compounds. The amide isosteric-diazine pyrrole I demonstrated photo-induced DNA damage upon iradiation with UV light (365 nm). Spectrophotometric and mass spectrometric identification suggest that the azo-linkage in I did not dissociate during irradiation. Moreover, compound I produced DNase I footprints with the HexB DNA fragment at AT sites, as well as some other mixed sequences (5'-ATGTCG-3'), indicative of the additional role of the diazine-linkage for interaction at the duplex DNA.     

On linear and semidefinite programming relaxations for hypergraph matching

The hypergraph matching problem is to find a largest collection of disjoint hyperedges in a hypergraph. This is a well-studied problem in combinatorial optimization and graph theory with various applications. The best known approximation algorithms for this problem are all local search algorithms. In this paper we analyze different linear and semidefinite programming relaxations for the hypergraph matching problem, and study their connections to the local search method. Our main results are the following:

We consider the standard linear programming relaxation of the problem. We provide an algorithmic proof of a result of Füredi, Kahn and Seymour, showing that the integrality gap is exactly ${k-1+\frac{1}{k}}$ for k-uniform hypergraphs, and is exactly k ? 1 for k-partite hypergraphs. This yields an improved approximation algorithm for the weighted 3-dimensional matching problem. Our algorithm combines the use of the iterative rounding method and the fractional local ratio method, showing a new way to round linear programming solutions for packing problems.

We study the strengthening of the standard LP relaxation by local constraints. We show that, even after linear number of rounds of the Sherali-Adams lift-and-project procedure on the standard LP relaxation, there are k-uniform hypergraphs with integrality gap at least k ? 2. On the other hand, we prove that for every constant k, there is a strengthening of the standard LP relaxation by only a polynomial number of constraints, with integrality gap at most ${\frac{k+1}{2}}$ for k-uniform hypergraphs. The construction uses a result in extremal combinatorics.

We consider the standard semidefinite programming relaxation of the problem. We prove that the Lovász ${\vartheta}$ -function provides an SDP relaxation with integrality gap at most ${\frac{k+1}{2}}$ . The proof gives an indirect way (not by a rounding algorithm) to bound the ratio between any local optimal solution and any optimal SDP solution. This shows a new connection between local search and linear and semidefinite programming relaxations.

     

A Powder Based Polyaniline Carbon Paste Electrode for Urea Analysis

A new polyaniline carbon paste electrode prepared by mixing polyaniline (emeraldine), nafion, graphite powder and urease for urea analysis was exploited. The ratio of polyaniline, nafion, urease and graphite for the construction of the electrodes and the optimal conditions for urea determination were studied. The detection limit of this sensor for urea is 5 μM and the linearity from 5 μM to 7.5 mM is obtained in FIA. This sensor has a response time of 90s and shows good reproducibility and stability (RSD, 6.3%, n = 43). The blood samples from a patient during blood dialysis were taken and analyzed. The urea concentrations in blood obtained from this sensor are comparable with urea test kit method.     

Cation-induced synthesis of new polyoxopalladates

Seven polyoxopalladate compounds, [Pd(15)(SeO(3))(10)(μ(3)-O)(10)](10-), with Na(+) (1) and K(+) (2) as counterions, and Na(6)[M(II){Pd(12)(SeO(3))(8)(μ(4)-O)(8)}]·nH(2)O (M = Co (3), Zn (4), Ni (5), Cu (6), Mn (7); n = 7-9), have been prepared and characterized by SXRD, FT-IR, UV-vis, EA, TGA, and ESI-MS. These compounds comprise two distinct cluster configurations, {Pd(15)} and {M(II)Pd(12)}, which reveals the possibility of obtaining desired noble metal clusters with a certain nuclearity by using different cations as potential structural directing or template agents in synthesis. All compounds showed apparent absorptions in the visible light region, while 3 and 7 were found to show paramagnetic behavior typical of mononuclear Co(II) and Mn(II) complexes with zero-field splitting.     

Different growth regimes on prepatterned surfaces: consistent evidence from simulations and experiments

Molecule deposition on a prepatterned substrate is a recently developed technique to generate desired structures of organic molecules on surfaces via self-organization. For the case of prepatterned stripes, the time-resolved process of structure formation is studied via lattice Monte Carlo simulations. By systematic variation of the interaction strength, three distinct growth regimes can be identified: localized growth, bulge formation, and cluster formation. All three growth regimes can be recovered in the experiment when choosing appropriate organic molecules. Some key microscopic observables, reflecting the properties of the structure formation, display a non-monotonous dependence on the interaction strength.     

Quantification of glutathione in plasma samples by HPLC using 4-fluoro-7-nitrobenzofurazan as a fluorescent labeling reagent

A rapid and highly sensitive high-performance liquid chromatograpy method with fluorescence detection has been developed for determination of glutathione (GSH) in human plasma. A simple pre-column derivatization procedure with 7-flouro-4-nitrobenzo-2-oxa-1,3-diazole (NBD-F) reagent was employed. The separation of the derivatized glutathione was performed using a mobile phase consisting of phosphate buffer (0.02 mol/L, pH 6.0)-acetonitrile (77:23, v/v) at a flow rate of 1.0 mL/min with the column temperature 2°C. The eluted derivatives were fluorometrically detected at an excitation wavelength 470 nm and an emission wavelength 530 nm. Under the optimum chromatographic conditions, the calibration curve was linear over the range of 0.1 μmol/L to 10.0 μmol/L with the correlation coefficient of 0.9988. The precision of the method was satisfactory with the intra- and inter-day coefficient of variation being 6.3%, 6.9%, respectively. This method has been used to determine glutathione concentrations in plasma samples from healthy individuals.     

Reactive Polymer Coatings: A General Route to Thiol‐ene and Thiol‐yne Click Reactions

Reactive polymer coatings were synthesized via chemical vapor deposition (CVD) polymerization process. These coatings decouple surface design from bulk properties of underlying materials and provide a facile and general route to support thiol‐ene and thiol‐yne reactions on a variety of substrate materials. Through the reported technique, surface functions can be activated through a simple design of thiol‐terminated molecules such as polyethylene glycols (PEGs) or peptides (GRGDYC), and the according biological functions were demonstrated in controlled and low‐fouling protein adsorptions as well as accurately manipulated cell attachments.     

Synthesis,structure, and photophysical property of series of Ln(III) coordination polymers with different carboxylato ligands (Ln = Sm,Eu)

Four Ln(III) coordination polymers, {[Ln₂(1,3-bdc)₃(H₂O)₄]·DMF·H₂O} _n (Ln = Sm 1, Eu 2) and [Ln₂(mal)₃(H₂O)₆] _n (Ln = Sm 3, Eu 4) (1,3-H₂bdc = isophthalate acid, H₂mal = malonate acid), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, UV–Vis–NIR absorption spectra, and fluorescence spectra. The structural analyses reveal that polymer 1 is a 3D coordination polymer. Its asymmetry unit contains two crystallographically independent Sm(III) ions, both are eight-coordinated. The 1,3-bdc^2? anions show three different coordination modes. The structure of polymer 2 is isomorphous with that of 1. Polymer 3 is also a 3D coordination polymer, its asymmetry unit contains one Sm(III) ion, which is nine-coordinate. The mal^2? anions have two different coordination modes. The structure of polymer 4 is isomorphous with that of 3. The luminescent study shows that polymers 1, 2, and 4 exhibit characteristic emission bands in the visible region, corresponding to the transitions of the Ln(III) ions. By comparison and analysis of luminescence, it is found that the incidence of the same ligand on the corresponding spectra of different Ln(III) ions is different, and the influence of different ligands on luminescence of the same Ln(III) ion is also very different.

     

Impact of environmental conditions on the sorption behavior of UO<Subscript>2</Subscript><Superscript>2+</Superscript> onto attapulgite studied by batch experiments

The sorption of UO₂ ²⁺ from aqueous solution on attapulgite was investigated as a function of contact time, solid content, pH, ionic strength, foreign ions, humic acid (HA), and fulvic acid (FA) under ambient conditions by using batch technique. The attapulgite sample was characterized by XRD and FTIR in detail. The results indicated that the sorption of UO₂ ²⁺ was strongly dependent on pH and ionic strength. The sorption of UO₂ ²⁺ on attapulgite increased quickly with rising pH at pH < 6.5, and decreased with increasing pH at pH > 6.5. The presence of HA or FA enhanced the sorption of UO₂ ²⁺ on attapulgite obviously at low pH because of the strong complexation of surface adsorbed HA/FA with UO₂ ²⁺ on attapulgite surface. Sorption of UO₂ ²⁺ on attapulgite was mainly dominated by ion-exchange or outer-sphere surface complexation at low pH values, but by inner-sphere surface complexation at high pH values. The results indicate that attapulgite is a very suitable adsorbent for the preconcentration and solidification of UO₂ ²⁺ from large volumes of aqueous solutions because of its negative surface charge and large surface areas.