Enantioselective synthesis of 1-deoxy-d-gulonojirimycin from a phenylglycinol-derived lactam

Cyclocondensation of (R)-phenylglycinol with appropriately γ-substituted δ-oxo acid derivatives provides bicyclic lactams from which the enantioselective synthesis of 1-deoxy-d-gulonojirimycin has been reported.     

Comparison of micro- and mesoporous inorganic materials in the uptake and release of the drug model fluorescein and its analogues

The uptake of the three species of the drug model fluorescein (fluorescein sodium salt (FNa), fluorescein free acid (F), and fluorescein diacetate (FDA)) by zeolite NaX and the mesoporous zeotype MCM-41 was investigated as well as their release rates into solutions at pH 7 and pH 4.5. UV/Vis analysis was carried out at a wavelength of 490 nm. Uptakes of the sodium salt of 9 % for zeolite X and 14 % for MCM suggest little penetration of the pores. The use of ethanol as the loading solvent for F resulted in little uptake for both zeolitic materials due to the successful competition of the ethanol for binding sites. Use of acetone (weaker proton acceptor) as loading solvent significantly improved the uptake of F to 17 % and 12 % for zeolite X and MCM, respectively, whilst the uptake of FDA in acetone increased still further to 22 % and 17 % for zeolite X and MCM, respectively. Generally there was a large initial release of the fluorescein analogues from the surface of the zeolites with very little further increase over time. The prescence of an esterase enzyme in the release medium of FDA tripled the release from MCM to 15 % but left the release from zeolite X unaffected at 6 %. The results obtained show that uptake of fluorescein and its analogues is dependent on the loading solvent used, the amount released is influenced by not only the solvent but the pH and the presence of enzymes in the release medium.     

Efficient combination of task-specific ionic liquid and microwave dielectric heating applied to one-pot three component synthesis of a small library of 4-thiazolidinones

The first report of the use of task-specific ionic liquid as synthetic equivalent of ionic liquid-phase matrice for the preparation of a small library of 4-thiazolidinones is reported in this paper. The starting (ethyleneglycol)ionic liquid-phase is functionalized in good yields with 4-(formylphenoxy)butyric acid by using usual esterification reaction conditions (DCC/DMAP as catalyst). The synthesis of the ionic liquid-phase bound 4-thiazolidinones was performed by a one-pot three-component condensation under microwave dielectric heating. The final cleavage under microwave/catalysis strategy provides the expected 4-thiazolidinones in high purity after flash-chromatography purification. According to the ionic liquid-phase organic synthesis (IoLiPOS) methodology, it was found that optimized reaction conditions were performed by standard analytical methods (NMR, TLC). The ¹H, ¹³C NMR spectrum of some representative 4-thiazolidinones and ionic liquid-phase bound benzaldehyde are also reported.     

Using second-order calibration to identify and quantify aromatic sulfonates in water by high-performance liquid chromatography in the presence of coeluting interferences

We used the Generalized Rank Annihilation Method (GRAM), a second-order calibration method, to quantify aromatic sulfonates in water with high-performance liquid chromatography (HPLC) when interferences coeluted with the analytes of interest. With GRAM, we can quantify in only two chromatographic analyses, one for a calibration sample and one for the unknown sample. The calculated concentrations were not statistically different to those obtained when the chromatographic separation of the unknown sample was modified in order to completely separate the analyte from the interferences before univariate calibration. With GRAM, the concentrations are determined much more quickly because a complete resolution is not required.     

Determination of rotational barriers of carbon?carbon bonds in 2-arylpiperidines

Carbon-carbon sp³-sp² rotational barriers of 3,3-dimethyl-2-(3,4,5-trimethoxyphenyl)-4-piperidones and their ethylene ketals have been evaluated using nmr techniques. The conformation of 1 hydrochloride has been studied by NOE determinations. Values found for the hydrochlorides of the title compounds are discussed in terms of equilibria with free bases and nitrogen inversion.     

The behavior of the form factor in two dimensions for linear polymers in different regimes

Off-lattice Monte Carlo simulations employing the PIVOT algorithm are used to generate ideal and excluded volume linear polymers in two dimensions. The form factor at small and large wave vectors is calculated from the resulting configurations and compared to the exact equation for ideal chains and to both scaling and renormalization group predictions for excluded volume chains. It is found that using the des Cloizeaux form for the distance distribution function in an analytic calculation of the form factor leads to close agreement with the Monte Carlo data and that simple expressions for both the small and large wave vector expansions reproduce the essential features of the form factor.     

Innovations in high-pressure liquid injection technique for gas chromatography: pressurized liquid injection system

In gas chromatography (GC), highly volatile liquefied hydrocarbons are commonly injected using devices such as high-pressure syringes, piston valves, liquid rotary sampling valves, or vaporizing regulators. Although these techniques are adequate in some cases, there are known deficiencies. A new generation of sampling valve has been recently innovated and commercialized. Some of the highlights of the pressurized liquid injection system (PLIS) include compact size, the capability to directly couple to an injection port without the need for preinjection vaporization and transfer lines, and sample sizes ranging from 0.2 to 2.0 micro L. Although the valve has a specification of helium leak-free rating of 82.7 bar (1200 psig), the valve passes a hydrostatic pressure test of up to 414 bar (6000 psig). In the unheated version of PLIS, vaporization of solutes occur mainly because of the sheering effect of carrier gas in combination with thermal energy drawn from an injection port or a heated adaptor. This was found to be adequate for solutes with high to medium volatility of up to nC14 hydrocarbon. A higher molecular weight range of up to nC44 hydrocarbon can be achieved with the implementation of a heated version of PLIS, in which the channel of the shaft can be resistively heated at a rate of up to 400 degrees C/s. With its first introduction in May 2002, PLIS has gained acceptance amongst practitioners in GC because it addresses a key unarticulated need in sample introduction/enrichment and by specifically targeting many deficiencies encountered in contemporary high-pressure injection devices. In this paper, the design and performance of the various valve systems of PLIS, as well as industrial chromatographic applications, is presented.     

一维链状配位聚合物{[Cu(μ-H_2L)(L)Cl](ClO_4)_3}_∞的合成、结构及磁性研究(L=N,N'-双(吡啶基-3-亚甲基)-1,5-二氮环辛烷)

设计合成了一个新型吡啶基二氮环配体L(N,N'-双(吡啶基-3-亚甲基)-1,5-二氮环辛烷)及其铜配位聚合物{[Cu(滋-H2L)(L)Cl](ClO4)3}∞(1),研究了此配合物的晶体结构、光谱及磁性质。该配合物属正交晶系,Pnma空间群,晶胞参数为a=3.5170(17)nm,b=1.0440(5)nm,c=1.1966(6)nm,V=4.394(4)nm3,Z=4。配体L以顺式螯合和反式桥联两种不同的配位形式将铜离子连接起来形成一维链状阳离子结构。     

Electrical conductivities of halide salts in aqueous formamide solutions

The electrical conductivities of sodium chloride and sodium iodide solutions in formamide-water mixtures of different composition have been measured at 25°C. From these data, the limiting equivalent conductances for these salts have been determined. The correspondingWalden products are compared together with the one reported for sodium bromide in the same solvent mixtures, and they are analysed as functions of the anion size. Further, the limiting ionic equivalent conductances are estimated for the different ions. The variation of the ionicWalden products with solvent composition is discussed in terms of ionic solvation and solvent structure.

---

Elektrische Leitfähigkeit von Halogensalzen in wäßrigen Formamid-Lösungen

Zusammenfassung Es wurden die elektrischen Leitfähigkeiten von Natriumchlorid- und Natriumjodidlösungen in Formamid-Wasser-Mischungen verschiedener Zusammensetzung bei 25°C gemessen. Aus diesen Daten wurden die Grenzäquivalenzleitfähigkeiten für diese Salze bestimmt. Die entsprechendenWalden-Produkte wurden mit den für Natriumbromid in den gleichen Lösungsmittelgemischen berichteten verglichen und hinsichtlich der Anionengrößen analysiert. Außerdem wurden die ionischen Grenzäquivalenzleitfähigkeiten für die einzelnen Ionen abgeschätzt. Die Variation der ionischenWalden-Produkte mit der Lösungsmittelzusammensetzung wurde bezüglich Ionensolvatation und Lösungsmittelstruktur diskutiert.