Stereoselective synthesis of novel types of cyclopropyl carbocyclic nucleosides containing quaternary stereogenic centers

Versatile and stereocontrolled synthetic entries to novel types of cyclopropyl carbocyclic nucleosides are described. The target products have been synthesized from suitable cyclopropane precursors obtained, in turn, from olefinic compounds derived from D-glyceraldehyde as a chiral precursor. Selective manipulation of the functional groups has allowed the preparation of enantiopure nucleosides, some of them displaying opposite chirality. All these molecules contain a quaternary stereogenic carbon at C-1 or C-3 of the cyclopropane ring and bear an amino, a hydroxymethyl, or a methyl group as an additional substituent. In one instance, thymine is directly linked to the cyclopropane. A methylene unit serves as the spacer in the other synthesized nucleosides.     

The sonochemical coating of cotton withstands 65 washing cycles at hospital washing standards and retains its antibacterial properties

Hospital-acquired nosocomial infections are a major health, and consequently financial issue, in the world healthcare system. The problem of bacterial infections in general, and in hospitals in particular, has led to extensive scientific and industrial efforts to fabricate antibacterial textiles. A sonochemical coating machine was developed and built and its ability to coat antibacterial nanoparticles (NPs) onto 40–50 meter length of materials on a roll to roll basis at a speed of 22 cm/min. Cotton coated sonochemically with copper oxide nanoparticles (CuO NPs) was found to maintain its antibacterial properties even after 65 cycles of washings according to hospital protocols of hygienic washing (75 °C). This demonstrates the good quality and high stability of this sonochemically produced NPs coating on textiles. Durable antibacterial textiles such as these may be suitable for wide spread use in future hospital environments where hygiene control is of paramount importance.     

A novel algorithm for chromatogram matching in qualitative analysis

The matching of the pattern of peaks produced during gas chromatography is of importance to many applications. At present, this task is generally performed manually, but this generates the usual problems associated with human inspection, such as a lack of objectivity and reproducibility, proneness to errors, and practical restriction of the volume of data which can reasonably be processed. This paper explores the use of a novel algorithm for automation of this task. The performance of the method on well controlled simulated data sets and real chromatograms is used to show not only how problems of manual inspection can be circumvented, but also how the existence of such a powerful method should open up the possibility of many new analyses for quality control, discrimination of varieties of sample, and the identification of specific components within a sample.     

Very long-distance magnetic coupling in a dicopper(II) metallacyclophane with extended π-conjugated diphenylethyne bridges

Self-assembly of the rigid rodlike ligand N,N'-4,4'-diphenylethynebis(oxamate) (dpeba) and Cu(2+) ions affords a novel dinuclear copper(II) metallacyclophane (nBu(4)N)(4)[Cu(2)(dpeba)(2)]·4MeOH·2Et(2)O (1) featuring a very long intermetallic distance (r = 15.0 ?). Magnetic susceptibility measurements for 1 reveal a moderately weak but nonnegligible intramolecular antiferromagnetic coupling between the two metal centers across the double para-substituted diphenylethynediamidate bridge (J = -3.9 cm(-1); H = -JS(1)S(2), where S(1) = S(2) = S(Cu) = (1)/(2)). Density functional electronic structure calculations on 1 support the occurrence of a spin polarization mechanism.     

About the calculation of exchange coupling constants in polynuclear transition metal complexes

The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data.     

Carbon dioxide induced separation of ionic liquids and water

Both hydrophobic and hydrophilic room-temperature ionic liquids can be separated from aqueous solutions with relatively low-pressure gaseous carbon dioxide.     

Highly stereoselective aldol reactions of titanium enolates from lactate-derived chiral ketones

[reaction: see text] Highly stereoselective titanium-mediated aldol reactions based on lactate-derived ketones are reported. The stereochemical outcome of the process depends on the protecting group (PMB or Bn) and the Lewis acid (i-PrOTiCl(3) or TiCl(4)) used in the enolization step, the corresponding anti-syn or syn-syn aldols being prepared in high yields and with diastereomeric ratios up to 99:1.     

Access to Enantiopure Advanced Intermediates en Route to Madangamines

The synthesis of enantiopure ABCE and ABCD tetracyclic advanced intermediates en route to madangamine alkaloids and studies for the construction of the triunsaturated 15-membered D ring of madangamine B and the saturated 13-membered D ring of madangamine E are reported.     

Synthesis of lactate derivatives via reductive radical addition to α-oxyacrylates

Lactate derivatives are important synthetic precursors to a variety of pharmaceutical products. Previously reported methods to prepare lactates require multiple steps or have limited scopes. Herein, we report a Ni-catalyzed reductive addition of a variety of alkyl iodides to α-oxyacrylates to afford substituted lactates. Exploring the scope of radical acceptors reveals that electron-deficient alkenes, ranging from cyclohexenone to para-caboxystyrene, undergo efficient coupling with alkyl iodides. This method represents an alternative strategy access lactate derivatives.     

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。