Facial synthesis of key intermediate of obeticholic acid via Pd-catalyzed Kumada-Tamao-Corriu cross-coupling reaction.

Obeticholic acid (OCA) is used to treatment for Primary Biliary Cholangitis and other Famesoid X Receptor related diseases. Through the palladium catalyzed Kumada-Tamao-Corriu cross-coupling reaction, a novel and efficient method for synthesis of OCA with satisfied yield was successfully developed. The absolute configuration of the key intermediate was confirmed by Single-crystal X-ray Diffraction. It affords good strategy for large-scale synthesis of OCA.

Pd(NHC)(cinnamyl)Cl-catalyzed Suzuki cross-coupling reaction of aryl sulfonates with arylboronic acids.

A series of N-heterocyclic carbene (NHC)-palladium catalysts have been synthesized and applied to catalyze the Suzuki coupling reaction efficiently between aryl sulfonates and arylboronic acids with the potassium phosphate heptahydrate as a base. The desired yields are obtained even with less reactive aryl tosylates or aryl mesylates as substrates. This method was applied successfully to the synthesis of the (R)-2-(t-butoxycarbonylamino)-3-(biphenyl-4-yl)-propan-1-ol which is the key intermediate of sacubitril, a component of the newly approved antihypertensive drug "Entresto."

Hydrogen-Bonded Duplexes with Lengthened Linkers.

Connecting basic hydrogen-bonding units with lengthened flexible or rigid linkers generates oligoamide strands that carry new H-bonding sequences and association specificity, leading to H-bonded homo- and heteroduplexes with association constants in the 104 M-1 range in chloroform. Computational and experimental studies indicate that in duplexes with rigid aromatic linkers the oligoamide strands adopt bent conformations that allow the formation of interstrand H-bonds and accommodate the introduced aromatic liners, offering a new series of association units.

A Biocompatible Colorimetric Triphenylamine- Dicyanovinyl Conjugated Fluorescent Probe for Selective and Sensitive Detection of Cyanide Ion in Aqueous Media and Living Cells.

A colorimetric and turn-on fluorescent probe 1 bearing triphenylamine-thiophene and dicyanovinyl groups has been synthesized and used to detect cyanide anion via a nucleophilic addition reaction. Probe 1 exhibited prominent selectivity and sensitivity towards CN- in aqueous media, even in the presence of other anions such as S2-, HS-, SO32-, S2O32-, S2O82-, I-, Br-, Cl-, F-, NO2-, N3-, SO42-, SCN-, HCO3-, CO32- and AcO-. Moreover, a low detection limit (LOD, 51 nM) was observed. In addition, good cell membrane permeability and low cytotoxicity to HeLa cells were also observed, suggesting its promising potential in bio-imaging.

[Transient Storage Characteristics of Artificial Pool Geomorphic Structure in an Agricultural Headwater Stream].

From November 2015 to February 2016, five short-term tracer injections were performed with a conservative tracer (NaCl) in an agricultural headwater stream, Lake Chaohu basin. Thus the data sets of tracer experiments were finally employed for calculating the physical characteristics and transient storage metrics. Through the comparisons between the artificial pool reach and straight reach, characteristics of transient storage for the artificial pool geomorphic structure were interpreted and explored. Study results showed that: ① The ratio of As/A in artificial pool was larger than that in straight reach, whereas its value of exchange coefficient α was lower by an order of magnitude than that of straight reach. ② Artificial pool geomorphic structure had greater influence of transient storage on solute retention than that in straight reach, but its solute retention capacity of flowing water was weaker than that of straight reach. ③ It had a large ratio of As/A for the pool geomorphic structure, whereas its impact on the migration and transformation of solutes was less than that of straight reach. ④ Based on the Fmed200 metric, the transient storage accounted for 18.86% to 26.05% of travel time in artificial pool. For the straight reach, the Fmed200 metric had a range of 5.28% to 33.87%. In most cases, the values of Fmed200 metric in straight reach were higher than those in artificial pool. ⑤ Significant differences existed between artificial pool geomorphic structure and straight reach in the values of φw, φA and Ts, however, the differences were not significant in other indicators.

[Fractions and Release Risk of Phosphorus in Surface Sediments of Three Headwater Streams with Different Styles of Water Supply].

From May to September 2015, seasonal sediment samples were collected from three headwater streams and ditches which were discharged from sewage plant tail water, food processing wastewater and agricultural drainage-groundwater seepage, respectively, in Hefei, Chaohu Lake basin. The stream-bed sediments were analyzed for phosphorus fractions. The risk assessment on phosphorus release from sediments was conducted using the phosphorus sorption index (PSI), degree of phosphorus saturation (DPS) and the phosphorus release risk index (ERI). Moreover, nonparametric tests method was used to explore the difference among the three studied streams and ditches. Study results showed that:1 Guanzhenhe Distributary and Taochong Stream were seriously damaged by phosphorus pollution both in waters and stream-bed sediment, and the phosphorus pollution levels could be arranged in the order of Guanzhenhe Distributary >Taochong Stream >Modian Stream. The mean content of total phosphorus (TP) in sediments in Guanzhenhe Distributary was 1376.95 mg·kg-1, which was 2.94 and 1.91 times as high as those of Modian Stream and Taochong Stream, respectively. 2 Significant differences and different sort orders in contents of phosphorus fractions were found for each of the three streams. 3 Obvious seasonal variations existed in PSI for the three streams, and all the sampling points in the same stream had similar changing law, namely, the maximum content emerged in autumn, followed by winter, and the minimum occurred in spring or summer. 4 The same conclusions were drawn in phosphorus release risk according to the PSI, DPS and ERI, and the risk ranked as follows:Guanzhenhe Distributary >Taochong Stream >Modian Stream. 5 According to the difference analysis, significant differences existed in almost all of the indexes among the three streams.

Chiral surfactant-type catalyst: enantioselective reduction of long-chain aliphatic ketoesters in water.

A series of amphiphilic ligands were designed and synthesized. The rhodium complexes with the ligands were applied to the asymmetric transfer hydrogenation of broad range of long-chained aliphatic ketoesters in neat water. Quantitative conversion and excellent enantioselectivity (up to 99% ee) was observed for α-, ß-, γ-, δ- and ε-ketoesters as well as for α- and ß-acyloxyketone using chiral surfactant-type catalyst 2. The CH/π interaction and the strong hydrophobic interaction of long aliphatic chains between the catalyst and the substrate in the metallomicelle core played a key role in the catalytic transition state. Synergistic effects between the metal-catalyzed site and the hydrophobic microenvironment of the core in the micelle contributed to high stereoselectivity.

Preparation and helical folding of aromatic polyamides.

Long aromatic polyamide chains are prepared from the corresponding monomers. The resultant polymer adopts a hollow helical conformation that is stabilized by intramolecular H-bonding interaction between side chains.