Chinese Journal of Chemistry

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.

When both catecholamine and double bond are tethered to a polymer backbone simultaneously, the polymer can accelerate the curing speed of ethyl α-cyanoacrylate. Probably this is due to the catecholamine groups, which can produce free radicals and enrich them, causing free radical polymerization.

Thiol-yne click chemistry is presented as an original approach to design adamantane-decorated porous monolith for reversed phase capillary electrochromatography.

A new approach to synthesize N-alkylation of azoles by iron (III)-catalyst under solvent-free conditions was developed. The method is broad in scope and highly efficient.

A facile and biocompatible approach to generate microgrooves on water-insoluble polymeric surfaces using sugar fibers as the imprinting template was describled.

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.

A simple and practical approach for the preparation of unsymmetric bis(indolyl)-methanes (BIMs) was realized by Lewis acid InBr₃-catalyzed Friedel-Crafts reaction of indoles with 3-indolyl-substituted phthalides in water.

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.

The first direct asymmetric Mannich reaction of malononitrile to imines has been developed with cinchona alkaloid as catalyst, which provides an easy access to β-amino malononitrile with high chemical yields and excellent enantioselectivities.

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.

The first hyperpolarizability of the studied compounds can be substantially increased by structural modification, especially the introduction of tetrathiafulvalene.

A general and efficient Cu(II)-catalyzed cross-coupling method is reported for the preparation of acyclic tertiary amides. Generally moderate to excellent yields and functional group tolerance were obtained with secondary acyclic amides and aryl halides as substrates in toluene.

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.

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.

Two competitive gas-phase Smiles rearrangements initiated by nitrogen anion and oxygen anion respectively were observed in the CID fragmentation of deprotonated rimsulfuron.

An efficient, convenient and applicable method was developed for the N-arylation of azaheterocycles catalyzed by CuI and NaH under ligand free condition.

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.

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.

A series of new chiral 2(5H)-furanone derivatives containing bis-1,2,3-triazole moiety are designed and synthesized from 4 basic unit molecules under mild conditions via the sequential three steps, including asymmetric Michael addition-elimination, substitution and no-ligand click reaction.

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.

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.

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.

Photoreactive and degradable hyperbranched copolymers PCL-co-PDHCA have been synthesized, and the properties have been also discussed.

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 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.

Comparing with polysulfone (PSF) membrane, the poly(glycidylmethacrylate) (PGMA) grafted membrane has much better antifouling property, and the antifouling property was further improved by hydrolysis of the epoxy groups in the grafting chains.

A novel and ef?cient synthetic route to α-aminophosphonates containing benzothiazole moiety via a cascade three-component reaction from conveniently available starting materials has been developed.

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.

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.

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.

Seven kinds of free amino acids usually contained in milk were determined within 150 s by microchip electrophoresis coupled with florescence detection based on Cy5 derivatization.

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.

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.

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.

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.

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.

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.

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.

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.

Catalytic, intramolecular conjugate reduction-aldol addition reactions of β′-oxoalkyl α,β-unsaturated carboxylates were achieved using copper hydride ligated with bis[(2-diphenylphosphino)phenyl] ether catalyst, yielding lactones in moderate to good yields and in high diastereoselectvities.

The Zr-POSS and Hf-POSS coordination polymers have been successfully synthesized and charactered.

A practical synthesis of (R)-4-(benzyloxy)-3-methylbutanenitrile, a potential chiral building block, from the corresponding α-keto ester in high yield and large scale was presented.