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To establish the method for determining total saponins and paeoniflorin in Suanzaoren Hehuan Formula (SHF) and an HPLC fingerprint of its saponins parts.The total saponins in SHF was determined by ultraviolet spectrophotometry at 545 nm. The content of paeoniflorin and the chromatographic fingerprints were determined by HPLC.There was a good linear relationship in the range of 2.3-11.8 microg/mL for oleanolic acid (r1 = 0.9997) of UV, and 12.8-38.4 pg/mL for paeoniflorin (r2 = 0.9996) of HPLC. The average recovery of oleanolic acid and paeoniflorin was 99.60% and 99.98%, respectively. Thirteen peaks were selected as common peaks in fingerprint and four of them were recognized.The method is accurate, sensitive, rapid and suitable for quality control of this formula.

Common and variation peak rates were calculated as dual-index for drug samples based on the infrared spectrogram of Angelicae Pubescentis Radix samples from different places. The results indicated that the common peak rates of 4 samples from Sichuan province, 2 samples from Gansu province, and 2 samples from Hubei province were higher than 73% , 79. 5% and 76. 3%, respectively. Also, the variation peak rates of 2 samples from Gansu province were lower than 12. 9%. Therefore, there is similar germplasm resources and similar chemical composition in the samples originated from the same place. However, for the samples originated from different places, their germplasm resources and chemical composition maybe have been changed. Fourier transform infrared spectrometry could be used to evaluate the rule of the fingerprint and overview of Angelicae Pubescentis Radix originated from different places by its changes of germplasm resources and chemical composition.

A short and efficient approach to aza-quaternary pyrrolo[1,2-a]azepine 8 and aza-quaternary indolizine 23, as the crucial intermediates for syntheses of stemonamine (1a) and cephalotaxine (1b), has been developed on the basis of the key intramolecular Schmidt reaction of symmetric azido-diones 5 and 18, respectively.

Molecularly imprinted polymers (MIPs), using ( S )-naproxen as template and the combination of butyl methacrylate (BMA) and MAA (1:1 molar ratio) as functional monomers were synthesized by an in situ polymerization reaction. The rendered monolithic column was evaluated in HPLC mode. The result showed that the monolithic MIPs with the combination of two monomers produced better chiral resolution of rac-naproxen (Rs = 1.55) and column efficiencies of imprinted molecules ( N = 2860 plates/m) than that with pure MAA.

The common peak ratio and variant peak ratio were calculated by FTIR spectroscopy of six medicinal plants of polygonatum. The index sequence of common peak ratio and variant peak ratio of six medicinal plants was established and the FTIR spectroscopy was analyzed by cluster analysis, which indicated the sibship of the six medicinal plants, polygonati rhizoma, polygonati odorati rhizoma and their adulterant such as Polygonatum filipes Merr., Polygonatum macropodium Turcz. and Polygonatum humile Fisch Ex Maxim. could be identified by comparing second derivative spectrum of the samples. FTIR with good characteristics such as simple and rapid procedures, nondestructive testing, small amount of sample required, good reproducibility and specificity of fingerprint, provides a new method for identification of polygonati rhizoma, polygonati odorati rhizoma and their adulterant.

A highly chemoselective one-pot reaction has been developed involving a tandem semipinacol rearrangement/oxa-Michael addition sequence in which the in situ generated ketol diene intermediate can be transformed specifically to either the spiro- or fused-dihydrofuran products (see scheme). This one-pot tandem reaction represents a general synthetic methodology for the syntheses of the two different kinds of furan derivatives.

Thin-flap laser in situ keratomileusis (LASIK) is the new trend of refractive error correction surgery, the formation of corneal flap is crucial for a success of LASIK surgery. This study aimed to assess and compare the variations of LASIK flap created by the IntraLase femtosecond laser, Moria One Use-Plus SBK and Moria M2 Single-Use 90 µm-head microkeratome using Anterior segment optical coherence tomography (Visante OCT).One hundred and sixty-one eyes of 81 consecutive patients were enrolled in this prospective study and randomly divided into three groups depending on the flap creation method: flap creation with the the IntraLase femtosecond laser (IntraLase group, 59 eyes), flap creation with the Moria One Use-Plus SBK (SBK group, 44 eyes), and flap creation with the Moria M2 Single-Use 90 µm-head microkeratome (M2SU90 group, 58 eyes). The nominal flap thickness was 110 µm for all patients and for the three devices. One month after surgery, Visante OCT was used to measure the flap thickness at 20 locations on each cornea and the results were assessed for uniformity, regularity, and accuracy.At 1 month after surgery, the mean central flap thickness was (111 ± 3) µm in the IntraLase group, (114 ± 8) µm in the SBK group, and (118 ± 13) µm in the M2SU90 group respectively. The flaps in the IntraLase group and the SBK group were more regular, showing an almost planar configuration, than the meniscus-shaped flaps in the M2SU90 group. The maximum deviation from the intended flap thickness (110 µm) was 6 µm in the IntraLase group, 10 µm in the SBK group, and 20 µm in the M2SU90 group respectively. A difference greater than 20 µm was observed in 0.42% of measurements in the IntraLase group; 2.95% of the measurements in the SBK group and 21.12% of measurements in the M2SU90 group.The flaps created by the IntraLase femtosecond laser and Moria One Use-Plus SBK are more uniform; more regular, and more accurate than those created by the Moria M2 Single-Use 90 µm-head microkeratome. The first two methods can make precise flaps for Sub-Bowman Keratomileusis.

The title reaction affords a complex tricyclic system with four continuous stereogenic centers.

Diaryl allylic tertiary alcohols afford up to 93% enantioselectivity by use of a cinchona-derived catalyst and NBS as brominating reagent.

High stereoselectivity in an aqueous medium, the introduction of tri-oxygenated functional groups, and the efficient construction of at least two chiral centers are features of this transformation.

Trabecular meshwork (TM) cell volume may be an important determinant of aqueous humor outflow in the eye. This study aimed to evaluate the role of HepII domain peptides V on corneal permeability, corneal endothelial cells, intraocular pressure (IOP) and morphology of trabecular meshwork in rats.The IOP of rat eyes was measured before and 3, 5, 7 and 8 hours after topical delivery of HepII domain peptides V through intracameral injections. The peptide's concentration in aqueous humor was assessed by high performance liquid chromatography (HPLC). The shape and density of endothelial cells were observed by laser confocal microscopy 8 hours, 3 and 14 days after intracameral injections of HepII domain peptides V. The morphological changes in TM of rat eyes were assessed by transmission electron microscopy (TEM).Intracameral injection of HepII domain peptides V significantly (P0.001) decreased IOP by (5.71 ± 2.10) mmHg in rats at 5 hours after injection. There were no obvious changes of the shape and the density of corneal endothelial cells. In addition, morphological changes in the TM of rats were observed including the expansion of intercellular spaces in the juxtacanalicular meshwork, removal of extracellular material, cellular relaxation, and cytoskeleton reorganization.HepII domain peptides V could not penetrate cornea and was safe to corneal endothelial cells. HepII domain peptides V could significantly decrease IOP in rat probably by disorganizing actin cytoskeleton and cell-junction in the TM.

The reaction allows the construction of two adjacent stereocenters: a chiral oxo-quaternary carbon, and a functionalizable halogen.

This report provided the first example of using pivot concept to prepare monolithic molecularly imprinted polymers (MIPs) with ketoprofen (KET) imprints, in which metal ions were employed as mediator between the functional monomer and the template to achieve higher fidelity of imprint. To solve metal ions in pre-polymerization system, a new ternary porogen of dimethyl sulfoxide–toluene–isooctane was developed for preparation of MIP monoliths with high porosity and good permeability. The effect of polymerization parameters such as the nature of metal ions, the ratio of template to metal ion and the degree of crosslinking, on the permeability, morphology and affinity of the metal ion mediated MIP monolith were studied. The experiments demonstrated that Ni 2+ , Co 2+ and Zn 2+ can be applied as pivot to prepare KET-imprinted monolith. Relative to monolithic MIP without metal ions, all the ion-mediated macropore MIP monoliths showed enhanced permeability, capacity factor and selectivity factor. High permeability (1.06 × 10 −7 mm 2 ) was obtained on the Co 2+ -mediated MIP monolith and great selectivity factor (3.84) was achieved on the Ni 2+ -mediated one. The stoichiometric displacement model was constructed to investigate the recognition mechanism of metal-ion mediated MIP. The results indicate that metal ion as pivot not only improves the affinity but also allows the fine-tuning on the macroporous structure of MIP monolith.

A novel asymmetric halogenation/semipinacol rearrangement reaction catalyzed by cinchona alkaloid derivatives was developed. Two types of β-haloketones (X = Br, Cl) were obtained with up to 95% yield and 99% enantiomeric excess. The desired (+) and (−) enantiomers of the β-haloketones were readily obtained.

High stereoselectivity in an aqueous medium, the introduction of tri-oxygenated functional groups, and the efficient construction of at least two chiral centers are features of this transformation.

To evaluate the accuracy, uniformity and relevant factors of LASIK flaps created with a mechanical microkeratome Moria II (90, 110 and 130 heads).It was a case-control study. Eighty-seven patients underwent LASIK in both eyes using Moria II 90 head (52 eyes, 26 cases), 110 head (58 eyes, 29 cases), or 130 head (64 eyes, 32 cases). One week after surgery, anterior segment optical coherence tomography was performed four times on each eye to measure flap thickness at 20 points in four meridians. The results were assessed for accuracy, uniformity and relevant factors.The central thickness of corneal flaps was (119.23±15.65), (140.42±12.26), and (165.92±17.00) µm by Moria II 90, 110 and 130 heads, respectively. The shape of the corneal flaps in the three groups resembled a concave lens, the central zone was significantly thinner than the paracentral and peripheral zones. The central flap thicknesses were statistically significantly more accurate and regular than the flap in the peripheral zone (F=212.419, P0.05). The mean difference of right eye (19.58±0.44) µm was higher than that of the left eye (16.55±0.44) µm. The mean difference of knife in-side (21.30±0.55) µm was higher than the knife out-side (14.36±0.64) µm (F=25.341, 44.461; P0.05).The central flap thicknesses were more accurate as compared with the expected value. The mean flap thickness in the three groups was not uniform. Variation of the thickness in corneal flaps was greater in thicker flaps. The flap thickness in right eye was greater than that in left eye, according to the surgical sequence between two eyes. The flap thickness of blade in-side was thicker than that of out-side.

The formation of the target compounds proceeds via formation of triazoline intermediates and subsequent 1,2-migration.

To determine the effects of Heparin II (Hep II) domain on cultured human trabecular meshwork (HTM) cells.HTM cells were cultured and treated with Hep II domain for 18 and 24 h. The morphological changes in HTM cells were assessed by light and electron microscopy. Changes in cell morphology and the organization of actin cytoskeleton, Vinculin, beta-Catenin were assessed by using immunofluorescence.Treatment of Hep II domains resulted in morphological changes from 10 to 24 h. In light microscopy, cells rounded up, retracted and detached from each other. In high performance liquid chromatography, Hep II domains-treated cells showed that actin fibre bundles were highly concentrated at the periphery of the cells with few actin filaments left in this area; decreased vinculin staining was observed toward the cell periphery; decreased beta-Catenin staining was also observed around the cell sub-membrane. Transmission electron microscopy showed expended intercellular space. After 24 h, changes of HTM cells were recovered.Hep II domains reversibly blocks actin cytoskeleton and cell-junction of HTM cells. Disorganization of actin cytoskeleton and cell-junction in trabecular meshwork through signal transduction may be a useful strategy for the decrease of intraocular pressure.

An efficient first approach to the Stemona alkaloid (±)-Stemonamine has been developed on the basis of a key TiCl4 promoted tandem Semipinacol rearrangement/Schmidt reaction and a Dieckmann condensation reaction.

To optimize amic solution hydrolysis technique for improving the content of astragaloside IV in extract of Radix Astragali.Orthogonal design was adopted to investigate the main factors that influenced hydrolysis. Choosing the content of astragaloside IV as inspecting index which determined by HPLC, total saponins was purified with the macro-reticular resine, and contents of saponins before and after hydrolysis were determined by colorimetry at 544 nm.The ratio of amic solution to herb medicine was most notable in the four inspected factors. The optimal technique of hydrolysis was that the ratio was 1:5, concentration of amic solution was 2%, and the time of regurgitant extraction at 90 degrees C was two hours. The content of astragaloside IV was notably higher than before by hydrolysis. Difference wasnt significant between the content of saponins before and after hydrolysis by colorimetry.Content of astragaloside IV was obviously higher than that before hydrolysis,but the content of total saponins was not changed before and after hydrolysis. The results showed that the other saponins can be transformed into astragaloside IV by hydrolysis. This method was valuable, which provided basis on its industrialization.

An efficient first approach to the Stemona alkaloid (+/-)-Stemonamine has been developed on the basis of a key TiCl4 promoted tandem Semipinacol rearrangement/Schmidt reaction and a Dieckmann condensation reaction.

AIM: To determine the gene expression profile data for the whole liver during development of dimethylni-trosamine (DMN)-induced hepatic fibrosis. METHODS: Marker genes were identified for different types of hepatic cells, including hepatic stellate cells (HSCs), Kupffer cells (including other inflammatory cells), and hepatocytes, using independent temporal DNA microarray data obtained from isolated hepatic cells. RESULTS: The cell-type analysis of gene expression gave several key results and led to formation of three hypotheses: (1) changes in the expression of HSC-specific marker genes during fibrosis were similar to gene expression data in in vitro cultured HSCs, suggesting a major role of the self-activating characteristics of HSCs in formation of fibrosis; (2) expression of mast cell-specific marker genes reached a peak during liver fibrosis, suggesting a possible role of mast cells in formation of fibrosis; and (3) abnormal expression of hepatocyte-specific marker genes was found across several metabolic pathways during fibrosis, including sulfur-containing amino acid metabolism, fatty acid metabolism, and drug metabolism, suggesting a mechanistic relationship between these abnormalities and symptoms of liver fibrosis. CONCLUSION: Analysis of marker genes for specific hepatic cell types can identify the key aspects of fibrogenesis. Sequential activation of inflammatory cells and the self-supporting properties of HSCs play an important role in development of fibrosis.

A catalytic intermolecular carbon electrophile induced semipinacol rearrangement was realized and the asymmetric version was also preliminarily accomplished with 92% and 82% ee. The complex tricyclic system architecture with four continuous stereogenic centers could be achieved from simple starting materials in a single step under mild conditions.

A bromination/semipinacol rearrangement reaction catalyzed by cinchona alkaloid derivatives was developed. With 5 mol% (DHQD)2PYDZ, β-bromoketones containing an all-α-carbon quaternary center, which were synthetically useful but challenging to construct, were obtained in up to 97% yield and 93% ee.

To investigate the relationship of changes in expression of marker genes in functional categories or molecular networks comprising one functional category or multiple categories in progression of hepatic fibrosis in hepatitis C (HCV) patients.Marker genes were initially identified using DNA microarray data from a rat liver fibrosis model. The expression level of each fibrosis associated marker gene was analyzed using reverse transcription-polymerase chain reaction (RT-PCR) in clinical biopsy specimens from HCV-positive patients (n = 61). Analysis of changes in expression patterns and interactions of marker genes in functional categories was used to assess the biological mechanism of fibrosis.The profile data showed several biological changes associated with progression of hepatic fibrosis. Clustered genes in functional categories showed sequential changes in expression. Several sets of clustered genes, including those related to the extracellular matrix (ECM), inflammation, lipid metabolism, steroid metabolism, and some transcription factors important for hepatic biology showed expression changes in the immediate early phase (F1/F2) of fibrosis. Genes associated with aromatic amino acid (AA) metabolism, sulfur-containing AA metabolism and insulin/ Wnt signaling showed expression changes in the middle phase (F2/F3), and some genes related to glucose metabolism showed altered expression in the late phase of fibrosis (F3/F4). Therefore, molecular networks showing serial changes in gene expression are present in liver fibrosis progression in hepatitis C patients.Analysis of gene expression profiles from a perspective of functional categories or molecular networks provides an understanding of disease and suggests new diagnostic methods. Selected marker genes have potential utility for biological identification of advanced fibrosis.