Studies on the Enzymatic Acylation of Quinic Acid,Shikimic Acid,Shikimic Acid,and Their Derivatives in Organic Solvents

Quinic acid ( 1a ), shikimic acid ( 2 ), and their derivatives were acylated in organic solvents by several lipases and by the protease subtilisin Carlsberg. The most satisfactory results were obtained with methyl (or benzyl) quinate ( 7a (or 8a )) and lipase from Chromobacterium viscosum adsorbed on Celite, which showed an overshelming preference towards the acylation of OH–C(4). Under optimized conditions, the syntehtically useful 4-O -acetylquinate 8d was isolated in ca. 90% yield. On the other hand, acylation of methyl shikimate ( 10a ) showed no regioselectivity with any of the enzymes tested. A possible rationale for the different behavior of Chromobacterium viscosum lipase towards 7a and 10a is given, comparing the conformations of these two molecules, as deducted from ¹H-NMR and molecular-mechanics calculation.     

Metal-Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S-Oxides

Benzothiophenes, activated by oxidation to the corresponding S-oxides, undergo C−H/C−H-type coupling with phenols to give C4 arylation products. While an electron-withdrawing group at C3 of the benzothiophene is important, the process operates without a directing group and a metal catalyst, thus rendering it compatible with sensitive functionalities—e.g. halides and formyl groups. Quantum chemical calculations suggest a formal stepwise mechanism involving heterolytic cleavage of an aryloxysulfur species to give a π-complex of the corresponding benzothiophene and a phenoxonium cation. Subsequent addition of the phenoxonium cation to the C4 position of the benzothiophene is favored over the addition to C3; Fukui functions predict that the major regioisomer is formed at the more electron-rich position between C3 and C4. Varied selective manipulation of the benzothiophene products showcase the synthetic utility of the metal-free arylation process.     

Biological and Catalytic Applications of Pd(II)-Indenyl Complexes Bearing Phosphine and N-Heterocyclic Carbene Ligands

A general synthetic entryway into novel cationic Pd(II) indenyl complexes bearing one alkyl/aryl phosphine and one N-heterocyclic carbene is reported. All metal complexes have been exhaustively characterized by spectroscopic and structural analyses, highlighting that the indenyl fragment has an hapticity intermediate between η³ and η⁵. Most of the target complexes are stable in solid state and in solution for a long time. Two different applications of these organopalladium compounds are proposed. Firstly, they have been tested as antiproliferative agents towards three different ovarian cancer cell lines, showing a cytotoxicity significantly higher than that of cisplatin, with a clear dependence on the nature of the coordinated phosphine. Moreover, the similar cytotoxicity towards cisplatin-sensitive and cisplatin-resistant cell lines suggests that these new palladium derivatives act with a different mechanism of action with respect to classical platinum-based drugs. Finally, the water-soluble palladium complexes bearing 1,3,5-triaza-7-phosphaadamantane (PTA) have demonstrated interesting catalytic performances in Suzuki–Miyaura coupling in aqueous media, being, inter alia, readily and efficiently recyclable.     

Side-chain chlorination of methylquinolines

Methylquinolines 1–4 were chlorinated by heating with phosphorus pentachloride in chlorobenzenes to side-chain halogen derivatives 5–14 . Methyl groups of compounds 1–4 can be chlorinated to chloromethyl, dichloromethyl or trichloromethyl groups depending on their positions and the reaction conditions.     

Flexible conducting polymer transistors with supercapacitor function

Planar organic electrochemical transistors (OECTs) using PEDOT:PSS as the channel material and nanostructured carbon (nsC) as the gate electrode material and poly(sodium 4‐styrenesulfonate (PSSNa) gel as the electrolyte were fabricated on flexible polyethylene terephthalate (Mylar^®) substrates. The nsC was deposited at room‐temperature by supersonic cluster beam deposition (SCBD). Interestingly, the OECT acts as a hybrid supercapacitor (to give a device that we indicate as transcap). The energy storage ability of transcaps has been studied with two cell configurations: one featuring PEDOT:PSS as the positive electrode and nsC as the negative electrode and another configuration with reversed electrode polarity. Potentiostatic charge/discharge studies show that both supercapacitors show good performance in terms of voltage retention, in particular, when PEDOT:PSS is used as the positive electrode. Galvanostatic charge–discharge characteristics show typical symmetric triangular shape, indicating a nearly ideal capacitive behavior with a high columbic efficiency (close to 100%). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 96–103     

Exploring the Phase-Selective,Green, Hydrothermal Synthesis of Upconverting Doped Sodium Yttrium Fluoride: Effects of Temperature,Time, and Precursors

The aim of this work was i) to develop a hydrothermal, low-temperature synthesis protocol affording the upconverting hexagonal phase NaYF₄ with suitable dopants while adhering to the “green chemistry” standards and ii) to explore the effect that different parameters have on the products. In optimizing the synthesis protocol, short reaction times and low temperatures (below 150 °C) were considered. Yb³⁺ and Er³⁺ ions were chosen as dopants for the NaYF₄ material. Within the context of the second goal, parameters including nature of the precursors, treatment temperature, and treatment time were investigated to afford a pure hexagonal crystalline phase, both in the doped and undoped materials. To fully explore the synthesis results, the prepared materials were characterized from a structural (XRD), compositional (XPS, ICP-MS), and morphological (SEM) point of view. The upconverting properties of the compounds were confirmed by photoluminescence measurements.     

电感耦合等离子体原子发射光谱测定铬矿中的铅、锌、镍、钛、磷

提出了电感耦合等离子体原子原子发射光谱测定铬矿中的铅、锌、镍、钛、磷含量的方法,选择各元素的分析谱线,采用正交试验的方法确定仪器的工作参数,方法的检出限0.22 ~1.50ug·L-1 ,方法的回收率在89%~112%,测定值的相对标准偏差（n=5）小于1.45%,方法用于铬矿杂元素的分析结果与现有的国标检验方法测定值一致。填补无铬矿中铅、锌、钛元素检测方法的空白。     

Organic contamination in clams,Venerupis aurea laeta and Cerastoderma edule glaucum,from Sicily (Italy)

Two species of edible clams Venerupis aurea laeta and Cerastoderma edule glaucum from Ganzirri Lake (Sicily, Italy) were investigated to determine OCP and PCB residues by GC-MS. Thirty-five samples were examined for two years in order to perform: a) their actual contamination; b) the daily dietary exposure of seafood consumers to the pollutants in question. In all the clams analysed in this study, PCB and OCP (4,4′-DDE) residues are always below the limits fixed by law. It seems that there is some seasonality of concentrations observed. In fact the more high concentrations of residues are detected in the hot months, for both species and years. Given the consumption of clams and the values obtained in this study for the two species analysed, it is possible estimate that the average daily dietary intake of NDL-PCB and of 4,4′-DDE for adults is really low.     

High‐Pressure Synthesis of a Nitrogen‐Rich Inclusion Compound ReN8⋅x N2 with Conjugated Polymeric Nitrogen Chains

A nitrogen‐rich compound, ReN₈?x N₂, was synthesized by a direct reaction between rhenium and nitrogen at high pressure and high temperature in a laser‐heated diamond anvil cell. Single‐crystal X‐ray diffraction revealed that the crystal structure, which is based on the ReN₈ framework, has rectangular‐shaped channels that accommodate nitrogen molecules. Thus, despite a very high synthesis pressure, exceeding 100 GPa, ReN₈?x N₂ is an inclusion compound. The amount of trapped nitrogen (x) depends on the synthesis conditions. The polydiazenediyl chains [?N=N?]_∞ that constitute the framework have not been previously observed in any compound. Ab initio calculations on ReN₈?x N₂ provide strong support for the experimental results and conclusions.     

Synthesis of aggregation pheromone components of cerambycid species through α-hydroxylation of alkylketones

The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and l- and d-proline respectively, in several reaction media.