Synthesis α‐aminonitrile through anodic cyanation of N‐benzylpiperidine

Six‐membered cyclic α‐aminonitrile has been prepared from anodic cyanation of N‐benzylpiperidine. Good yields of α‐aminonitriles could be obtained through potentiostatic electrolysis under different conditions. The results also explain why high yield α‐aminonitriles could not be obtained under constant current electrolysis.     

A new regioselective synthesis and bioactivity of 1H‐pyrazolo[3,4‐d]pyrimidin‐4(5H)‐one derivatives

A series of new 1H‐pyrazolo[3,4‐d]pyrimidin‐4(5H)‐one Derivatives 5 has been designed and regio‐selectively synthesized via a tandem aza‐Wittig reaction. The structures of all compounds prepared have been confirmed by ¹H NMR, IR, EI‐MS spectroscopy and elemental analyses. The results of preliminary bioassay indicate that most compounds 5 possess an inhibition effect against Botrytis cinereapers and Pyricularia oryzae at the concentration of 50 mg/L.     

Effect of Pluronic F127 on the pore structure of macrocellular biodegradable polylactide foams

Thermally induced phase separation technique was utilized to fabricate biodegradable poly(l ‐lactic acid) (PLLA) macrocellular foams which were capable of being applied in tissue engineering. The block copolymer Pluronic F127 composed of (polyethyleneoxide)‐(polypropyleneoxide)‐(polyethyleneoxide) [(PEO)‐(PPO)‐(PEO)] was used as a porogen. Water/dioxane mixtures with different volume ratios were used as solvents. The addition of Pluronic F127 could induce an appearance of large pores (50–200 μm) besides small pores (10–20 μm) or a change from a solid–liquid phase separation to a liquid–liquid phase separation. The role of Pluronic F127 depends on the water/dioxane ratios in the PLLA/dioxane/water system. The X‐ray diffraction patterns and porosity measurement results showed that Pluronic F127 was crystallized and existed on the pore wall. The effect of Pluronic F127 on changing pore structure is attributed to the occurrence of the interaction of the lipophilic PPO blocks in Pluronic F127 with PLLA clews, consequently, this results in PLLA aggregation and early phase separation on cooling. Copyright © 2004 John Wiley & Sons, Ltd.     

Syntheses and Crystal Structures of Two Metal Succinates Modified by Bipyridines

Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C₄H₄O₄)·1/4H₂O ( 1 ) and Cu(2, 2′‐bpy)(C₄H₄O₄)_0.5(NO₃)(H₂O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) ų, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) ų, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the Cu^II atom adopts a distorted octahedral in which the Cu^II atoms are bridged by two H₂O molecules into an infinite zigzag chain, [Cu₂(H₂O)₂(C₄H₄O₄)]_n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure.     

Two-dimensional Anhydrous Cadmium(II) Phthalate

The in situ hydrolysis of phthalyl-γ-glutaminyl-histidine with Cd(ClO₄)₂·6H₂O in the presence of water and methanol affords a novel two-dimensional cadmium coordination polymer, a new phase, anhydrous cadmium(II) phthalate, ( 1 ). The structure was determined by single crystal X-ray diffraction. Crystal data: P2₁/c, a = 13.8168(14), b = 7.0351(7), c = 8.2054(8) Å, β = 105.540(2)°, V = 768.43(13) ų, Z = 4, R₁ = 0.0380, wR₂ = 0.1111.     

Displaced π–π stacking and hydrogen bonds in 3‐bromo‐N‐(2‐hydroxy‐1,1‐di­methyl­ethyl)­benz­amide

The mol­ecules of the title compound, C₁₁H₁₄BrNO₂, are assembled into a two‐dimensional network by a combination of hydrogen bonds and stacking interactions. The phenyl rings are stacked along the c direction by displaced π–π interactions, forming a lipophilic layer. The aliphatic amide residues are interconnected along [100] by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, forming hydro­philic layers.     

Polymeric (μ2‐nitrato‐κ2O:O′)(μ2‐nitrato‐κ2O:O)(μ4‐pyridinium‐4‐thiol­ato‐κ4S:S:S:S)­disilver(I)

The title compound, [Ag₂(NO₃)₂(C₅H₅NS)]_n, was obtained from the reaction of silver nitrate with bis(4‐pyridyl) disufide (4‐PDS) in a mixture of ethanol and water, which suggests that the di­sulfide bond of 4‐PDS can be cleaved under mild conditions. The structure of the title compound is a two‐dimensional infinite array in which the asymmetric unit contains two Ag atoms, a pyridinium‐4‐thiol­ate mol­ecule and two nitrate groups. Each pyridinium‐4‐thiol­ate mol­ecule acts as a μ₄ bridge, linking four Ag atoms, with Ag—S bond distances of 2.4870 (19), 2.5791 (19), 2.5992 (19) and 2.848 (2) Å. The Ag⋯Ag distances lie in the range 2.889 (2)–3.049 (1) Å.     

An unusual mixed-valence Cu(I)-Cu(II) 3-D framework

The reaction of Cu(CH(3)CN)(4)ClO(4) with 2-pyridylacrylic acid (2-HPYA) affords an unusual mixed-valence Cu(I)-Cu(II) 3-D framework ([Cu(II)(2-PYA)(2)](3).[Cu(I)(2-PYA)](2).(H2O)(2))n (1) with a novel topology which features Cu(II) dimeric units (or paddle-wheel unit). The almost perpendicular coordinating direction between the N atom of pyridyl and the O atom of carboxylate groups may be responsible for the formation of such a novel network.     

High-throughput purification of combinatorial libraries I: a high-throughput purification system using an accelerated retention window approach

We have developed a high-throughput purification system to purify combinatorial libraries at a 50-100-mg scale with a throughput of 250 samples/instrument/day. We applied an accelerated retention window method to shorten the purification time and targeted one fraction per injection to simplify data tracking, lower QC workload, and simplify the postpurification processing. First, we determined the accurate retention time and peak height for all compounds using an eight-channel parallel LC/UV/MS system, and calculated the specific preparative HPLC conditions for individual compounds. The preparative HPLC conditions include the compound-specific gradient segment for individual compounds with a fixed gradient slope and the compound-specific UV or ELSD threshold for triggering a fraction collection device. A unique solvent composition or solvent strength was programmed for each compound in the preparative HPLC in order to elute all compounds at the same target time. Considering the possible deviation of the predicted retention time, a 1-min window around the target time was set to collect peaks above a threshold based on UV or ELSD detection. Dual column preparative instruments were used to maximize throughput. We have purified more than 500 000 druglike compounds using this system in the past 3 years. We report various components of this high-throughput purification system and some of our purification results.     

Determination of Dopamine in the Presence of Ascorbic Acid Using a Poly(Amidosulfonic Acid) Modified Glassy Carbon Electrode

A glassy carbon electrode (GCE) was modified with electropolymerized films of amidosulfonic acid in pH 7.0 phosphate buffer solution (PBS) by cyclic voltammetry (CV). The modified electrode showed an excellent electrocatalytical effect on the oxidation of dopamine (DA). In pH 7.0 PBS, the anodic peak current increased linearly with the concentration of DA in the range of 5.0×10^–7 1.0×10^–4moldm^–3, with a correlation coefficient of 0.9932, and a detection limit (S/N=3) of 1.0× 10^–7moldm^–3. The relative standard deviation of 10 successive scans was 2.5% for 1.0×10^–6moldm^–3 DA. The interference of ascorbic acid (AA) with the determination of DA could be eliminated because of the very distinct attracting interaction between DA cations and the negatively poly(amidosulfonic acid) film in pH 7.0 PBS. The proposed method exhibited good recovery and reproducibility.