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Cover Picture: Sugar-fiber Imprinting to Generate Microgrooves on Polymeric Film Surfaces for Contact Guidance of Cells (Chin. J. Chem. 10/2012)
- Page: 2257
- First Published: 23 October 2012

The cover picture shows a facile and biocompatible approach to generate microgrooves on water-insoluble polymeric surfaces using sugar fibers as the imprinting template. The cover shows a "cotton candy", a favorite food for many children. This time, a research group in Fudan University employed it to serve science, using the sugar fibers in this "cotton" as a sacrificed template to physically modify a biomaterial. The present report is aimed to confirm the feasibility of this idea in the cases of two dimensional films, using poly(lactic-co-glycolic acid) (PLGA) as the model biomaterial matrix. Microgrooves were conveniently generated on PLGA films after removing sugar fibers simply by water. The contact guidance of cells by the microgrooves was confirmed on the resulting surface. More details are discussed in the article by Qu and Ding on page 2292–2296.
Contents
Communications
Accelerated Curing Speed of Ethyl α-Cyanoacrylate by Polymer with Catecholamine Groups
- Pages: 2275-2280
- First Published: 27 September 2012
Thiol-yne Click Adamantane Monolithic Stationary Phase for Capillary Electrochromatography
- Pages: 2281-2284
- First Published: 23 October 2012
Communication
Iron(III)-Catalyzed Direct N-Alkylation of Azoles via Oxidative Transformation of sp3 CH Bonds under Solvent-Free Conditions
- Pages: 2285-2291
- First Published: 23 October 2012
Full Papers
Sugar-fiber Imprinting to Generate Microgrooves on Polymeric Film Surfaces for Contact Guidance of Cells
- Pages: 2292-2296
- First Published: 23 October 2012
Studies toward the Synthesis of (R)-(+)-Harmicine
- Pages: 2297-2302
- First Published: 23 October 2012
Synthesis and Application of a Full Water-Soluble and Red-Emitting Chemosensor Based on Phenoxazinium for Copper(II) Ions
- Pages: 2303-2308
- First Published: 27 September 2012

A phenoxazinium-based chemosensor (1) bearing di(2-picolyl)amine unit was successfully synthesized. The result shows it is a red-emitting and full water-soluble chemosensor for the selective detection of Cu2+ in pure water. The fluorescence on-off mechanism was studied by ab initio calculations. It was also indicated that 1 had good membrane permeability and could be useful for the fluorescence microscopic imaging.
Highly Efficient Synthesis of Unsymmetrical 3,3′-Bis(1H-indol-3-yl)methanes in Water
- Pages: 2309-2314
- First Published: 14 August 2012
Molecular Design of D-π-A Type II Organic Sensitizers for Dye Sensitized Solar Cells
- Pages: 2315-2321
- First Published: 23 October 2012
Palladium-Catalyzed N-Alkylation of Amides and Amines with Alcohols Employing the Aerobic Relay Race Methodology
- Pages: 2322-2332
- First Published: 14 August 2012

By employing the aerobic relay race methodology with Pd-catalyzed aerobic alcohol oxidation being a more effective protocol for alcohol activation, ligand-free homogeneous palladiums are successfully used as active catalysts in the dehydrative N-alkylation reactions of amines and amides with alcohols, giving high yields and selectivities of the alkylated amines and amides. Mechanistic studies implied that the reaction most probably proceeds via the novel relay race mechanism we recently discovered and proposed.
Cinchona Alkaloid-catalyzed Asymmetric Direct Mannich Reaction of Malononitrile to Imine for Synthesis of β-Amino Malononitrile
- Pages: 2333-2337
- First Published: 23 October 2012
Preparation of Covalently-colored Polymer Latex via Batch Emulsion Polymerization
- Pages: 2338-2342
- First Published: 23 October 2012

Covalently-colored polymer latex was obtained by batch emulsion copolymerization with a red polymerizable dye. Results showed that the chromophores were mostly covalently bonded to polymer chain with consistent color brilliance and unchanged UV-Vis spectrum, and the light fastness of the resulting latex film was greatly improved.
Imidazole-catalyzed Three-component Cascade Reaction for the Facile Synthesis of Highly Substituted 3,4-Dihydropyridin-2-one Derivatives
- Pages: 2343-2348
- First Published: 14 August 2012
Density Functional Theory Investigation on the Second-Order Nonlinear Optical Properties of Chlorobenzyl-o-Carborane Derivatives
- Pages: 2349-2355
- First Published: 23 October 2012
A General and Efficient CuBr2-Catalyzed N-Arylation of Secondary Acyclic Amides
- Pages: 2356-2362
- First Published: 23 October 2012
An Efficient α-Alkylation of Aromatic Ketones with Primary Alcohols Catalyzed by [Cp∗︁IrCl2]2 without Solvent
- Pages: 2363-2366
- First Published: 14 August 2012
Theoretical Investigation on the Electron and Energy Transfer between Peripheral Carrier Transport Groups and Central Chromophores in Electroluminescent Materials
- Pages: 2367-2375
- First Published: 23 October 2012

The molecular materials with structure of luminescent core and peripheral carrier groups (e.g. carbazoles), have exhibited high-performance in organic light-emitting diodes (OLEDs). There are two possible processes for the following charge bound pair generation (exciton formation): one is based on the cation of TCBzC with a positive charge on carbazole (Process 1), the other is from the anion of TCBzC with a negative charge on the central chromophore core (Process 2). These two situations lead to two kinds of exciton formations respectively (carbazole and central chromophore). Process 1 is the main factor to dominate EL, and energy-transfer process from carbazole exciton to central chromophore cores contributes to highly efficient EL.
Comparison of Hair Fatty Alcohols by N-Alkylpyridinium Isotope Quaternization and Matrix-assisted Laser Desorption/ionization Mass Spectrometry for Drug Abuse Monitoring
- Pages: 2376-2382
- First Published: 23 October 2012

N-Alkylpyridinium isotope quaternization (NAPIQ) method was used for comparison of fatty alcohols between normal and drug abuse group. The attached N-cationic pyridinium significantly improved the detection sensitivity for these fatty alcohols in matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometric (MALDI-FTMS) analysis. The levels of fatty alcohols in the hair of heroin abuse group decreased significantly compared with the normal groups, which may be the results of the inducing of peroxidation enzyme. NAPIQ was proven to be an effective method in the research of fatty alcoholic metabolism for drug abuse monitoring without the use of isotopically coded internal standards.
Gas-phase Smiles Rearrangement of Sulfonylurea Herbicides in Electrospray Ionization Mass Spectrometry
- Pages: 2383-2388
- First Published: 23 October 2012
Direct N-Arylation of Azaheterocycles with Aryl Halides under Ligand-free Condition
- Pages: 2389-2393
- First Published: 27 September 2012
Highly Efficient CN Bond Forming Reactions in Water Catalyzed by Copper(I) Iodide with Calix[4]arene Supported Amino Acid Ionic Liquid
- Pages: 2394-2400
- First Published: 23 October 2012
![Highly Efficient C<span class='icomoon'></span>N Bond Forming Reactions in Water Catalyzed by Copper(I) Iodide with Calix[4]arene Supported Amino Acid Ionic Liquid](/cms/asset/72829d0b-0cf3-4fc2-9fb9-28deab6fc0ef/mcontent.jpg)
A novel and effective protocol has been developed for the Ullmann-type CN coupling reaction catalyzed by calix[4]arene supported amino acid ionic liquid and copper(I) iodide in water under microwave irradiation condition. The protocol uses calix[4]arene supported amino acid ionic liquid as double function of the ligand and phase-transfer catalyst, and shows good tolerance in good to excellent yields.
Effect of End-capping Functional Groups on the Optoelectronic Properties of Oligothiophene Derivatives
- Pages: 2401-2410
- First Published: 23 October 2012

The five novel oligothiophene derivatives (MSO2RP3T, MSP3T, EtOP3T, AcP3T and BP3T) with different functional groups were synthesized. The effect of end-capping groups on optoelectronic properties of the oligothiophene derivatives was explored. This paper provides useful information for design of tailored molecule through searching the relationships between functional groups and optoelectronic properties.
Synthesis of 2(5H)-Furanone Derivatives with Bis-1,2,3-triazole Structure
- Pages: 2411-2422
- First Published: 23 October 2012
Design, Synthesis and Antiproliferative Activities of Diaryl Thiourea Derivatives as Anticancer Agents
- Pages: 2423-2430
- First Published: 23 October 2012

Two series of diaryl thiourea derivatives have been designed, prepared, and tested for cytotoxicity against human tumor cells PC-3, HCT116 and MDA-MB-231. The results showed that all compounds generally had antiproliferative activity against PC-3 cells, and some compounds demonstrated competitive antiproliferative activities to sorafenib.
Structural, Electronic and Optical Properties of Multifunctional Iridium(III) and Platinum(II) Metallophosphors for Organic Light-Emitting Diodes
- Pages: 2431-2439
- First Published: 23 October 2012

Obvious metal-to-ligand charge transfer (MLCT) occurs during low energy transitions, which is the decisive factor for the occurrence of spin-forbidden electron transition. The introduction of triphenylamino (TPA) units improves hole-creation ability and the extent of conjugation, leading to red-shifts in absorption and emission spectra.
Synthesis of CdTe Quantum Dots with Tunable Photoluminescence Using Tellurium Dioxide as Tellurium Source
- Pages: 2440-2444
- First Published: 23 October 2012

A simple and convenient method has been developed for synthesis of water-soluble CdTe quantum dots (QDs) under ambient atmospheric conditions. In contrast to the traditional aqueous synthesis, green to red emitting CdTe QDs were prepared by using TeO2 to replace Te or Al2Te3 as tellurium source in this method. With reflux time increasing from 5 to 180 min, the photoluminescence (PL) spectrum of CdTe QDs shifts from 533 to 612 nm.
Synthesis and Properties of Degradable Copolymers Composed of Poly(ε-caprolactone) and 3,4-Dihydroxycinnamic Acid
- Pages: 2445-2452
- First Published: 23 October 2012
Slightly Cross-Linked Polyrotaxanes Made by Linking α-Cyclodextrins Entrapped in Polyrotaxanes Using Hexamethylene Diisocyanate
- Pages: 2453-2460
- First Published: 27 September 2012

Polyrotaxane-based triblock copolymers were first synthesized via the ATRP of NIPAAm initiated with the self-assembly of a distal 2-bromoisobutyryl end-capped Pluronic 17R4 with a varying amount of α-CDs in the presence of CuCl/PMDETA at 25°C in aqueous solution. Those α-CDs entrapped on the polymer chain were then linked with hexamethylene diisocyanate to give rise to novel slightly cross-linked polyrotaxanes in DMF at 45°C.
A Convenient Hydrogenation Method for the Synthesis of Metallo-mesoporphyrin IX Dimethyl Esters via Self-catalyzed CoCl2-NaBH4 Reagent System
- Pages: 2461-2465
- First Published: 23 October 2012
Synthesis and Properties of New Fluorinated Polyimides Derived from an Unsymmetrical and Noncoplanar Diamine
- Pages: 2466-2472
- First Published: 14 August 2012

A new unsymmetrical and noncoplanar aromatic diamine monomer has been successfully synthesized in high yield by a facile reaction route. New series of highly soluble fluorinated polyimides with moderate to high molecular weights have been prepared by a one-step polycondensation procedure. The resulting polyimides could be readily solution-cast into transparent and flexible films with light color, good optical transparency, moderate to high glass-transition temperatures, and low dielectric constants. The eminent combination of several properties guaranteed the obtained polyimides as potential high-temperature resistant materials for optical and photoelectric applications.
Hydrophilic Modification of Microporous Polysulfone Membrane via Surface-Initiated Atom Transfer Radical Polymerization and Hydrolysis of Poly(glycidylmethacrylate)
- Pages: 2473-2482
- First Published: 14 August 2012
Novel Synthetic Route to α-Aminophosphonates Containing Benzothiazole Moiety
- Pages: 2483-2487
- First Published: 23 October 2012
White-Light Electroluminescence with Tetraphenylethylene as Emitting Layer of Aggregation-Induced Emissions Enhancement
- Pages: 2488-2494
- First Published: 27 September 2012
Synthesis of 2-Mercaptobenzaldehyde, 2-Mercaptocyclohex-1-enecarboxaldehydes and 3-Mercaptoacrylaldehydes
- Pages: 2495-2500
- First Published: 14 August 2012

One-pot synthesis of 2-mercaptobenzaldehyde, 2-mercaptocyclohex-1-enecarboxaldehydes and 3-mercaptoacrylaldehydes was developed by the reaction of the Grignard reagent with sulfur. The novel procedure showed high yields of the desired products, easy work-up, short reaction time, no catalyst, no hazardous phosphine ligands, no strong and foul smell sulfur-containing reagents, no environmental problem and mild reaction conditions in comparison with other methods, which are the strong points of the present procedure.
Theoretical Investigation into Electronic Structures and Charge Transfer Properties of π-Conjugated System with Different Combinations of Thiophene and Vinyl/Butadiene
- Pages: 2501-2508
- First Published: 14 August 2012

The presence of vinyl and butadiene in thiophene chain leads to many excellent properties. The different combinations of thiophene and vinyl/butadiene are absent in the theoretical calculation. The designed 3c (T5B4) is recommended as the promising ambipolar material for possessing the equal minimum λh (0.24 eV) and λe (0.24 eV). The linear relationships are found between experimental lowest singlet excited energies (Eexp) and theoretical ΔEH-L and Eg.
Synthesis, Crystal Structure and Anticancer Activities of Tetrahydropyrido[4,3-d]dihydropyrimidine-2-thiones
- Pages: 2509-2516
- First Published: 23 October 2012
![Synthesis, Crystal Structure and Anticancer Activities of Tetrahydropyrido[4,3-d]dihydropyrimidine-2-thiones](/cms/asset/b86aaad9-262b-4398-84c9-0b3479996626/mcontent.jpg)
A new series of tetrahydropyrido[4,3-d]dihydropyrimidine-2-thiones (3a–3x) were synthesized and the conformation of compound 3j was confirmed by X-ray diffraction. Preliminary bioassays indicated that most of the target compounds presented good antiproliferative activities against leukemic K562 cells, ovarian cancer HO-8910 cells and liver cancer SMMC-7721 cells in vitro. Preliminary mechanism of action studies revealed that compound 3i caused DNA fragmentation and activated caspase-3/7 in leukemic K562 cells.
Rapid Determination of Free Amino Acids in Milk by Microchip Electrophoresis Coupled with Laser-induced Fluorescence Detection
- Pages: 2517-2521
- First Published: 23 October 2012
Synthesis, Bioactivities and Structure Activity Relationship of N-4-Methyl-1,2,3-thiadiazole-5-carbonyl-N′-phenyl Ureas
- Pages: 2522-2532
- First Published: 23 October 2012

29 novel N-4-methyl-1,2,3-thiadiazole-5-carbonyl-N′-phenyl ureas were designed and synthesized. Target compounds exhibit insecticidal activities. Bioassays indicated that compounds V-24 and V-22 exhibit outstanding insecticidal activity against Culex pipiens pallens and Plutella xylostella, respectively. Compound V-11 also has a broad-spectrum of fungicide activity against all the fungi tested. Five compounds show good SAR-inducing activity as well. These results establish basis for both disease and insect control in agricultural practice and novel pesticide development. Structure-activity relationship studies reveal that, with the contour maps based on steric and electrostatic CoMFA coefficients, we can conclude the relationship between the structures and bioactivity and continue the further design of highly active compounds.
Homology Modeling and Molecular Docking Studies of (S)-Scoulerine 9-O-Methyltransferase from Coptis chinensis
- Pages: 2533-2538
- First Published: 27 September 2012

In order to study the interactions of SMT with its substrate and further to understand the catalytic mechanism and substrate specificity, a three dimensional model of SMT from Coptis chinensis was constructed by homology modeling using the crystal structure of caffeic acid/5-hydroxyferulic acid 3/5-O-methyltransferase (COMT) as a template. The three dimensional structure of SMT, which was mainly composed of α-helices and some β-sheets, was similar to that of COMT. In contrast with COMT, the non-conserved residues in the substrate binding pocket of SMT might be responsible for their differences in the substrate specificity. Val119 and Asp254 in SMT were the key residues for orienting substrate for methylation as both residues had H-bonds with (S)-scoulerine. The methylation of (S)-scoulerine involved deprotonation of the 9-hydroxyl group by His253 and Asp254 in SMT followed by a nucleophilic attack on the SAM-methyl resulting in the product, (S)-tetrahydrocolumbamine.
Adsorption and Decomposition Mechanism of 1,1-Diamino-2,2-dinitroethylene on Al(111) Surface by Periodic DFT Calculations
- Pages: 2539-2548
- First Published: 14 August 2012

The adsorption of 1,1-diamino-2,2-dinitroethylene molecule on the Al(111) surface was investigated by the density functional theory (DFT). The largest adsorption energy is −940.5 kJ/mol. The charge transfer is as large as 3.31e from the Al surface to the FOX-7 fragment. The largest activation energy for a dissociation step is 428.8 kJ/mol, while activation energies of other con?gurations are much smaller, in the range of 2.4 to 147.7 kJ/mol.
Immobilization of Antibodies on Magnetic Carbonaceous Microspheres for Selective Enrichment of Lysine-acetylated Proteins and Peptides
- Pages: 2549-2555
- First Published: 23 October 2012

In this study, for the first time, antibody-immobilized magnetic carbonaceous microspheres were developed for selective enrichment of acetylated proteins and peptides. The antibody immobilization strategy had high efficiency and specificity. Meanwhile, owing to the strong magnetism of the materials, the microspheres showed much convenience in operation. In a word, it provides a novel technique and may have more applications in the large-scale proteomic study.
Iodine-Mediated Thioetherification of Alcohols with Disulfides or NaSH under Microwave Irradiation
- Pages: 2556-2562
- First Published: 23 October 2012
Syntheses, Characterizations and Adsorption Properties of MIL-101/Graphene Oxide Composites
- Pages: 2563-2566
- First Published: 23 October 2012

Composites of MIL-101 and grapheme oxide (GO) were prepared with varying ratios of two components. The parent material MIL-101 and composites MIL-GO were characterized by X-ray diffraction, scanning electron microscopy and nitrogen adsorption. The incorporation of GO layers has an obvious impact on the formation of MIL-101 units, the size of crystals and the porosities of composites.
Tetrahydropyranylation of Alcohols and Phenols Using Polystyrene Supported Lewis Acids as Catalysts
- Pages: 2567-2572
- First Published: 23 October 2012

Polystyrene supported TiCl4 (Ps-TiCl4) and polystyrene supported FeCl3 (Ps-FeCl3) were prepared by coordinating Lewis acids with polystyrene. The catalysts were characterized by TGA, BET, SEM, IR and pyridine-adsorbed IR. The loading of Ps-TiCl4 and Ps-FeCl3 were 0.35 and 0.3 mmol·g−1 respectively. Both catalysts were found to be efficient for the tetrahydropyranylation and detetrahydropyranylation of various alcohols and phenols in different solvents. Two catalysts can be recovered and reused for five times with good activity.
Density Functional Theoretical Analysis of the Molecular Structural Effects on Raman Spectra of β-Carotene and Lycopene
- Pages: 2573-2580
- First Published: 23 October 2012

The ν1 bands of β-carotene and lycopene shift respectively to higher and lower frequencies in solution compared with those in the solid state due to the release of the crystal packing forces. The B3LYP/6-31G(d) method can predict reasonable Raman spectrum of β-carotene, but the calculated ν1 Raman activity of lycopene overflows. The solvent has slight (significant) effects on the Raman frequencies (intensities) of both carotenoids.
Palladium-Catalyzed Suzuki-Miyaura Type Coupling Reaction of Aryl Halides with Triphenylborane-Pyridine
- Pages: 2581-2586
- First Published: 23 October 2012

The Suzuki-Miyaura type coupling reaction of aryl halides with triphenylborane-pyridine was described. The reaction can be catalyzed by Pd(OAc)2 (5 mol%) in the presence of Cs2CO3 at 50°C or 80°C, and functionalized biaryls were obtained in good to excellent yields. This protocol is general and can tolerate a wide range of functional groups.
Note
Catalytic, Conjugate Reduction-Aldol Addition Reaction of β′-Oxoalkyl α,β-Unsaturated Carboxylates
- Pages: 2587-2590
- First Published: 14 August 2012
Group IV M-POSS (M=Zr, Hf) Coordination Polymers
- Pages: 2591-2594
- First Published: 23 October 2012
Facile and Efficient Synthesis of (R)-4-(Benzyloxy)-3-methylbutanenitrile: Toward Developing a Versatile Chiral Building Block
- Pages: 2595-2597
- First Published: 14 August 2012
Erratum
Erratum: Synthesis, Insecticidal Assay and Molecular Docking Study of Novel Neonicotinoids N-Oxide Analogues
- Page: 2598
- First Published: 23 October 2012