Enantioselective synthesis of trans-dihydrobenzofurans via primary amine-thiourea organocatalyzed intramolecular Michael addition.

A primary amine-thiourea organocatalyzed intramolecular Michael addition access was developed for the synthesis of trans-dihydrobenzofurans. Under the catalysis of an (R,R)-1,2-diphenylethylamine derived primary amine-thiourea bearing a glucosyl scaffold, the corresponding trans-dihydrobenzofurans were obtained in high yields with excellent level of enantioselectivities (94 to >99% ee). Moreover, an in situ isomerization occurring at high temperature gave good to excellent trans/cis ratios as well (trans/cis: 84/16-96/4).

5-(3-Chloro-phen-ylsulfan-yl)-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carbaldehyde O-[(2-chloro-1,3-thia-zol-5-yl)meth-yl]oxime.

In the title compound, C(16)H(11)Cl(2)F(3)N(4)OS(2), the benzene ring and the thia-zole ring make dihedral angles of 83.2 (3) and 78.3 (3)°, respectively, with the pyrazole ring. The crystal packing shows S⋯N contacts of 3.309 (2) Å.

A recyclable organocatalyst for asymmetric Michael addition of acetone to nitroolefins.

Based on different chiral diamine skeletons, a series of bifunctional primary amine-thiophosphoramides were synthesized and screened as the catalysts for the asymmetric Michael addition of acetone to both aromatic and aliphatic nitroolefins. Under the catalysis of a thiophosphoramide derived from 1,2-diphenylethane-1,2-diamine, the corresponding adducts were obtained in high yields (up to >99%) with excellent enantioselectivities (97-99% ee) under mild reaction conditions. Moreover, the catalyst could be recovered via simple phase separation and reused at least five times without any loss of both catalytic activity and stereocontrol.

Synthesis and herbicidal activity of 5-(4-hydroxybenzyl)-2-thioxoimidazolidin-4-one esters.

A series of novel 5-(4-hydroxybenzyl)-2-thioxoimidazolidin-4-one esters were synthesized under mild conditions by the reaction of 5-(4-hydroxybenzyl)-2-thioxoimidazolidin-4-one and carboxylic acids with DCC and DMAP as the promoters. Their structures were confirmed by ¹H-NMR, IR, ESI-MS and elemental analysis. The preliminary bioassy results indicated that some of compounds exhibit good herbicidal activity against Zea mays, Triticum aestivum and Arabidopsis thaliana. The further greenhouse test showed that compounds 6-16 and 6-28 have 60%, 50% and 50% efficacy against Stellaria media, Echinochloa crus-galli and Setaria viridis at 1,000 g/ha, respectively.

1-Methyl-5-phen-oxy-3-trifluoro-methyl-1H-pyrazole-4-carbaldehyde oxime.

In the title compound, C(12)H(10)F(3)N(3)O(2), the dihedral angle between the phenyl and pyrazole rings is 96.6 (3)°. In the crystal, pairs of O-H⋯N hydrogen bonds link the mol-ecules, forming inversion dimers. Weak inter-molecular C-H⋯F hydrogen bonds are also observed.

5-(4-Chloro-phen-oxy)-1-methyl-3-tri-fluoro-methyl-1H-pyrazole-4-carbaldehyde O-[(2-chloro-pyridin-5-yl)meth-yl]oxime.

In the title mol-ecule, C(18)H(13)Cl(2)F(3)N(4)O(2), the intra-molecular distance between the centroids of the benzene and pyridine rings is 3.953 (3) Å, and the trifluoro-methyl group is rotationally disordered over two orientations in a 0.678 (19):0.322 (19) ratio. The crystal packing exhibits weak inter-molecular C-H⋯F inter-actions.

Synthesis and herbicidal activities of 2-cyano-3-benzylaminoacrylates containing thiazole moiety.

Two series of novel 2-cyano-3-benzylaminoacrylates containing long-chain thiazole ring moiety were synthesized as herbicidal inhibitors of photosystem II (PS II) electron transportation. Their structures were confirmed by (1)H NMR and elemental analysis. The bioassay showed that these compounds retain high herbicidal activities and especially compounds 13a and 13h have excellent herbicidal activities.

[Full sibling identification based on the number of matched STR locus].

OBJECTIVE: To establish and evaluate the method of matched locus numbers in full sibling identification. METHODS: Two hundred and eighty full sibling (FS) pairs and 2003 unrelated individual (UI) pairs were genotyped with Identifiler system. The number of locus matched with 0 identical allele (A0), matched with 1 allele (A1) or matched with 2 alleles (A2) were counted and full sibling index (FSI) were calculated based on ITO method. Fisher discriminant functions were established based on the numbers of matched STR locus or FSI. Power of different Fisher discriminant functions was statistically analyzed. RESULTS: The distribution of A1 and A2 in FS group and that of A0 and A1 in UI group were in accord with normal distribution. Contrarily, A0 in FS group and A2 in UI group fitted to skew distribution, respectively. Difference of A1 distribution was not statistically significant in the two groups (P>0.01). The established Fisher discriminant functions based on A0 and A2 for each group were Z(FS)=0.99817A0+4.24442A2-12.77970 and Z(UI)=2.01456A0+1.54658A2-7.28076, respectively, the average error probability of which was as low as 0.0490. The power of discrimination for full sibling showed no statistically significant difference between ITO method and the established Fisher discriminant functions. CONCLUSION: The number of matched STR locus in Identifiler system is a valuable method in full sibling identification. The discriminating power of the established Fisher discriminant functions based on the matched STR locus number is similar with that of classic ITO method in full sibling identification.

[Evaluation of allelic alterations in 13 CODIS STR loci in tumor tissues from human digestive system].

OBJECTIVE: To study genetic alterations in 13 CODIS STR loci in various tumor tissue samples from human digestive system. METHODS: Malignant tumor tissues and blood samples taken from 55 different unrelated individuals were collected. DNA samples were extracted using Chelex100 extraction kit, amplified using Profiler and Cofiler PCR amplification kit and analyzed using API 310 analyzer. RESULTS: Aberrant cell divisions were detected in all of the 55 tumor tissue samples, with STR alternations detected in two samples including allelic alteration, partial and complete loss or unbalance of heterozygosity. Moreover, the alternations might occur simultaneously at more than one loci. CONCLUSION: Caution must be taken in STR analysis of tumor tissue samples since the exclusion loci in forensic identification or paternity testing may be resulted from mutations in the tumor tissue.

[Evaluation on the number and value of STR loci applied in paternity identification].

OBJECTIVE: The study was carried out on the evaluation of number and value of STR loci applied in paternity identification. METHODS: A total of 13 STR loci, divided into four groups, was observed in 102 cases of paternity exclusion and 100 cases of paternity inclusion. PCR amplified products of 13 STR loci were injected into a capillary on the ABI PRISM 310 Genetic Analyzer. GeneScan software analyzed the collected data, which can then be imported into Genotyper software for genotyping of alleles. RESULTS: At least 3 STR loci incompatibilities between alleged father and child were found in all paternity exclusion cases of two observed groups which Cumulative Probability of Exclusion (CPE) was more than 99.99%, and in all paternity inclusion cases of those same observed groups, their Relative Chance of Paternity(RCP) could be over 99.99%. CONCLUSION: The exclusion of paternity should be based on at least three STR loci incompatibilities in the identification practice. As a criterion for evaluation of the number and value of STR loci applied in paternity test, CPE should reach 99.99%.

[ABO genotyping by duplex amplification and oligonucleotide arrays assay].

OBJECTIVE: ABO genotyping for forensic identification by oligonucleotide chip. METHODS: Oligonucleotide microarrays which could detect 3 different SNPs in exon 6 and exon 7 for ABO genotyping were used. Population studies on ABO was carried out in a sample of 115 unrelated Chinese Han individuals. The method was also applied to cases. RESULTS: The technique could identify 6 genotypes of ABO system. According to the results of population studies, no significant deviations from Hardy-Weinberg equilibrium could be found. The observed and expected heterozygosities were 0.591 and 0.616 respectively. The polymorphic information content was 0.544. The average exclusion probabilities in buos and trios was 0.188 and 0.344 respectively. The discrimination power is 0.777. CONCLUSION: The data and case application demonstrated that ABO typing by oligonucleotide probe arrays was a useful technique for paternity testing and individual identification.

Immobilization of anti-CD31 antibody on electrospun poly(ɛ-caprolactone) scaffolds through hydrophobins for specific adhesion of endothelial cells.

Hydrophilicity improvement and bioactive surface design of poly(ɛ-caprolactone) (PCL) grafts are of key importance for their application in tissue engineering. Herein, we develop a convenient approach for achieving stable hydrophilic surfaces by modifying electrospun PCL grafts with a class II hydrophobin (HFBI) coating. Static water contact angles (WCA) demonstrated the conversion of the PCL grafts from hydrophobic to hydrophilic after the introduction of amphiphilic HFBI. ATR-FTIR and XPS confirmed the presence of self-assembled HFBI films on the surface of the PCL nanofibers. The biocompatibility of the HFBI-modified PCL grafts was evaluated by cell proliferation in vitro, and by arteriovenous shunt (AV shunt) experiments ex vivo. Anti-CD31 antibody, which is specific for endothelial cells (ECs), was subsequently immobilized on the HFBI-coated PCL scaffolds through protein-protein interactions. This bioactive PCL graft was found to promote the attachment and retention of endothelial cells. These results suggest that this stepwise strategy for introducing cell-specific binding molecules into PCL scaffolds may have potential for development of vascular grafts that can endothelialize rapidly in vivo.

Synthesis and biological activities of novel pyrazole oxime derivatives containing a 2-chloro-5-thiazolyl moiety.

A series of novel pyrazole oxime derivatives containing a 2-chloro-5-thiazolyl moiety were synthesized. Their structures were confirmed by (1)H NMR, (13)C NMR, and elemental analysis. The preliminary bioassays showed that all of the title compounds had low acaricidal activity against Tetranychus cinnabarinus . However, most of them exhibited excellent insecticidal activity against Aphis medicagini at the dosage of 0.5 mg/mL, and some compounds still showed good insecticidal activity against A. medicagini even at the dosage of 0.2 mg/mL. Meanwhile, some title compounds displayed fungicidal and plant growth regulatory activities.

Synthesis and insecticidal activity of N-substituted (1,3-thiazole)alkyl sulfoximine derivatives.

The N-substituted alkyl sulfoximine derivatives are a new chemical family of neonicotinoid insecticides. We have designed and synthesized 10 (1,3-thiazole)alkyl sulfoximine derivatives. All compounds were identified by (1)H and (13)C nuclear magnetic resonance (NMR), IR, and elemental analyses. Preliminary bioassays indicated that some title compounds exhibited good insecticidal activities at 10 mg/L against Myzus persicae . The relationship between structure and biological activity was also discussed.