Diverse redox-active molecules bearing O-, S-, or Se-terminated tethers for attachment to silicon in studies of molecular information storage

A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols.     

Water-Soluble imide-amide copolymers. II. Preparation and characterization of poly (acrylamide-co-p-maleimidobenzoic acid)

The comonomer required, p-maleimidobenzoic acid (MBA) was first prepared in good yield by refinements of published methods. p-Carboxysuccinanilic acid (CSA), and p-succinimidobenzoic acid (SBA), were also prepared to provide models useful for IR and NMR for spectroscopic assignments of the new copolymers. Polymerization of MBA with acrylamide in glacial acetic acid at 60°C gave copolymers with estimated viscosity average molecular weights of 60,000 to 90,000. Yields and viscosity average molecular weights decreased as the MBA to acrylamide monomer feed ratio was increased. The rate of incorporation of MBA into the copolymer rose from 7 to 23% when the mole ratio in the feed was raised from 5 to 20%. Decreasing the initiator concentration increased molecular weights by less than predicted and reduced the yield of copolymer for any given feed ratio of MBA to acrylamide. In all cases about 30–40% of the MBA units in the purified copolymers were hydrolyzed. A change to dimethyl sulfoxide solvent gave good, and poor yields of copolymer at 5 and 10 mol % MBA, respectively, and no copolymer at 20 mol % MBA. Viscosity average molecular weights of the copolymer products prepared in DMSO were somewhat lower than obtained for the copolymers prepared in acetic acid. Polymerization in a DMSO-water mixture gave a negligible yield of polymeric product. Instead, only hydrolysates of MBA precipitated when the coloured polymerization solutions were added to methanol.     

PROBING THE STRUCTURE OF HPD BY FLUORESCENCE SPECTROSCOPY

Fluorescence emission spectra indicate that oligomers containing both hematoporphyrin and its dehydration products (vinyl porphyrins) comprise the tumor-localizing fraction of HPD. In the relatively polar solvent methanol, the vinyl porphyrins exhibit reduced fluorescence yields while the hematoporphyrin residues are relatively resistant to fluorescence quenching by Fe+3. In the less polar solvent tetrahydrofuran, fluorescence from oligomeric vinyl porphyrins was enhanced, and Fe+3-induced quenching of oligomeric hematoporphyrin promoted. These, together with other studies in biological systems, suggest a substantial degree of interaction among the porphyrin units contained in these oligomers, as a function of the polarity of the environment.     

深圳市1408例儿童发中钙,铁,镁含量调查与分析

用火焰原子吸收法检测了深圳市１４０８例１３岁以下儿童发中钙，铁，镁的元素含量，并探讨了元素含量与年龄，性别的关系，结果显示，性别差异有显著意义，钙，镁含量随年龄增长有相似变化。     

Synthesis of a tetraazacyclotetradecadiene and a pentaazacyclotetradecatriene

Useful procedures for preparing a novel tetraazacyclotetradecadiene and a pentaazacyclotetradecatriene are reported. J. Heterocyclic Chem., 14, 1097 (1977)     

Regioselective uncatalysed hydrophosphination of alkenes: a facile route to P-alkylated phosphine derivatives

The synthesis of alkylarylphosphines is easily carried out by hydrophosphination of unactivated alkenes under mild thermal activation; gram scale amounts of products can be prepared by this simple methodology.     

Photodegradation of a 1,3,4-thiadiazole-urea herbicide. Isolation,characterization, X-ray crystal structure and synthesis of photoproducts

The photodegradation of 1,3-dimethyl-1-(2-(3-fluorobenzylthio)-1,3,4-thiadiazol-5-yl)urea as a thin film and in solution is described. The two photoproducts from thin-film photolysis were characterized by spectral and synthetic methods. The X-ray crystal structure of one of the photoproducts is also reported. The rearrangements were shown to involve an S-to-N benzyl migration, followed by a sulfur-oxygen substitution.     

Calculation of molecular geometries by SCF perturbation theory

An SCF perturbation method for investigating the effects of an arbitrary change in nuclear configuration on the electronic structure of a molecule is reported. Illustrative calculations for CO₂ and CH₃OH are presented. It is found that, when taken to second order, the error in the calculated change in energy which results from a change in nuclear configuration is typically in the range of 0.1 to 7%.     

Suggested calculations using transition density matrices

It is suggested that certain transition density matrices, N-representable in a limit, be used in a variational calculation. It is noted that such trial matrices should yield reasonable values for the ground state energies of small atoms or molecules provided a set of overlap integrals is maximised.

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Zusammenfassung Es wird vorgeschlagen, bestimmte Übergangsdichtematrizen, die im Limit N-darstellbar sind, in einer Variationsrechnung zu benutzen. Es wird festgestellt, daß solche Näherungsmatrizen gute Werte für die Energie des Grundzustandes kleiner Atome oder Moleküle geben sollten, falls im Satz von Überlappungsintegralen maximiert wird.

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Résumé On propose d'utiliser dans un calcul variationnel certaines matrices densité de transition, N représentables à la limite. Ces matrices d'essai devraient fournir des valeurs raissonnables pour l'énergie de l'état fondamental dans les petits atomes et les petites molécules à condition de maximiser un ensemble d'intégrales de recouvrement.

     

Determination of panaxadiol and panaxatriol in ginseng and its preparations by capillary supercritical fluid chromatography (SFC).

Capillary supercritical fluid chromatographic (SFC) method has been developed for the determination of panaxadiol and panaxatriol in ginseng and its preparations. 0.1 g ginseng or an appropriate amount of its preparations was hydrolysed by 15% H2SO4 in an ethanol:water (1:1 v/v) solution for 4 h followed by 15% NaOH for 0.5 h. The mixture was extracted by cyclohexane. The cyclohexane extracts were purified by a partition column and concentrated by an adsorption column and then analysed by SFC. Methyltestosterone was used as the internal standard.