Preparation and properties of metallacyclobutanes of nickel and palladium

Bis(phosphine)-3,3-dimethylnickela- and palladacyclobutanes have been prepared by intramolecular C-H insertion reaction of the corresponding dineopentyl metal complexes. Nickelacyclobutane complexes decompose when heated thereby undergoing competitive carbon-carbon bond cleavage to give isobutene and ethylene, with reductive elimination affording 1,1-dimethylcyclopropane and skeletal isomeri-zation of the metallacyclic ring yielding 3-methyl-1-butene, whereas the palladium analog gave no significant amounts of CC bond cleavage products.Added phos-phine was seen to have an effect on CC bond scission of nickelacyclobutane complexes. Nickelacyclobutane complexes in solution are thought to be in equilibrium with olefin-coordinated nickel-carbene complex on the basis of available experimental evidence from hydrogenolysis, carbene-trap reactions with olefins and reaction with carbon monoxide     

XPS analysis of NH3 plasma-treated polystyrene films utilizing gas phase chemical modification

Gas phase chemical modification (GCM) is found to be more preferable as a pretreatment for the XPS surface analysis of polymer materials than the conventional liquid phase treatment because it can circumvent problems such as solvent contamination and swelling. We have tried the quantification of the surface composition successfully by estimating the yield of the reaction from model samples. GCM was then applied to correlate the surface composition of NH₃ plasma-treated polystyrene films with their cell-affinity. The amount of primary-amine and that of carboxylic acid were directly determined by GCM. Although the amount of primary-amine, 15–20% of total nitrogen, did not depend on the treatment intensity, the total amine content for the treated samples increased with the plasma treatment intensity. The quantity of carboxylic acid generated was found to be very small. All treated samples had better cell-affinity than the control. The sample N2 (of medium treatment) showed the best cell-affinity. The most strongly treated sample N3, with larger amine content than N2, showed worse cell-affinity because of the interference by the sputtered SiO₂ on the surface.     

Synthesis of pyrazolo[3,4-d]pyrimidine derivatives using ketene dithioacetals

The cyclization of 5-amino-3-methylthiopyrazole-4-carbonitriles or 4-carboxamides 3a-j , which were prepared by the reaction of ketene dithioacetals 1a,b [1a : bis(methylthiomethylenemalononitrile; 1b : bis(methylthio)methylenecyanoacetamide] with hydrazines (hydrazine hydrate, phenylhydrazine, p-chlorophenylhydrazine, p-nitrophenylhydrazine), with formamide or carbon disulfide proceeded to give the corresponding 4-amino- or 4-hydroxy-3-methylthiopyrazolo[3,4-d]pyrimidines 6a-h in good yields. 3-Aminopyrazolo[3,4-d]pyrimidine derivatives 6i-1 were also obtained by the application of the cyclization reaction of 3,5-diaminopyrazoles with formamide.     

Regio- and stereoselective synthesis of (E)-alkene trans-Xaa-Pro dipeptide mimetics utilizing organocopper-mediated anti-S(N)2' reactions

Proline dipeptides (Xaa-Pro) exist as an equilibrium mixture of cis- and trans-rotamers, which depends on the energy barriers for imide isomerization. This conformation mixture contributes to both structure and function of proline-containing peptides and proteins. Structural motifs resembling these cis- or trans-conformers have served as useful tools for elucidating contributions of proline residues in the physicochemical and biological profiles of structures which contain them. Among such motifs are alkene dipeptide isosteres which mimic cis- or trans-imide using (Z)- or (E)-alkene, respectively. In this report, the first regio- and stereoselective syntheses of (E)-alkene dipeptide isosteres (20, 31, and 35) corresponding to trans-proline dipeptides are described. Key to the synthesis of these mimetics is the anti-S(N)2' reaction of vinyl aziridines such as 15 or vinyl oxazolidinones such as 28 and 32 with organocopper reagents "RCu" (R = CH(2)SiMe(2)(Oi-Pr)). Reaction of cis-vinylaziridine 15 derived from L-serine with organocopper reagent gave a precursor of the trans-L-Ser-D-Pro type alkene isosteres 20, accompanied by an S(N)2 side product. One limitation with the use of such aziridine-mediated methodology is formation of the corresponding trans-aziridine 22, which leads to L-L type isosteres, that is unstable and obtainable only in low yield. On the other hand, both isomers of oxazolidinone derivatives can be easily obtained from N-Boc-protected amino alcohols. The reaction of trans- 28 or cis-oxazolidinone derivative 32 with organocopper reagents proceeds quantitatively with high regio- and diastereoselectivities in anti-S(N)2' fashion. Subsequent oxidative treatment of the newly introduced isopropoxydimethylsilylmethyl group yields trans-L-Ser-L-Pro 31 or trans-L-Ser-D-Pro type isosteres 35, respectively. Of note, synthesized isostere 31 can also be converted to trans-phosphoSer-Pro 42 and trans-Cys-Pro mimetics 44. The present synthetic methodology affords trans-Xaa-Pro alkene-type dipeptide isosteres in high yield with relatively simple manipulation.     

Analysis of serum protein precipitated with antiserum by matrix-assisted laser desorption ionization/time-of-flight and electrospray ionization mass spectrometry as a clinical laboratory test

Serum transferrin precipitated with specific antisera was analyzed by matrix-assisted laser desorption ionization/time-of-flight mass spectrometry (MALDI/TOF-MS) and electrospray ionization-mass spectrometry (ESI-MS). When analyzed by MALDI, transferrin showed signal peaks that clearly could be separated from ions of IgG present in the immunoprecipitate. By ESI-MS, when the immunoprecipitates were loaded through a microcapillary polymeric reversed-phase column connected to the electrospray ionization probe, the mass spectra of transferrin were observed with a high signal-to-noise ratio and good resolution. By MALDI/TOF-MS, the observed molecular weight of normal transferrin was ～ 1.2 ku smaller when analyzed in the reflectron mode than in the linear mode. The observed molecular weight of transferrin treated with sialidase was approximately the same in both modes. A comparison between the results obtained in both modes may help to estimate the number of sialic acids on the protein molecule. A transferrin isoform with a molecular weight of ～2.2 ku less than the normal species was identified in the serum of patients with a carbohydrate-deficient glycoprotein syndrome as well as in heavy alcohol consumers.     

Transfer of photoenergy in pi-conjugated polymers. Two types of photoluminescence that involve energy transfer along a polymer chain

Two types of energy transfer in pi-conjugated polymers have been investigated using time-resolved photoluminescence (PL) techniques: type i, perpendicular-type energy transfer from the 2,3-di(p-tolyl)quinoxaline unit to the pi-conjugated main chain of poly[2,3-di(p-tolyl)quinoxaline-5,8-diyl], and type ii, parallel-type energy transfer from the oligo(pyridine-2,5-diyl) (O-Py) unit to the oligo(selenophene-2,5-diyl) (O-Se) unit in a block-type copolymer of O-Py and O-Se. Both types of energy transfer were very fast with a time constant shorter than approximately 0.1 ns; in particular, the type ii energy transfer took place with a time constant of approximately 5 ps. Both pi-conjugated polymers were considered to contain segments with various effective pi-conjugation lengths, and the energy transfer to the segment with a larger effective pi-conjugation length and a smaller pi-pi* transition energy required a longer transition time. A polarizing film was obtained by utilizing the perpendicular-type energy transfer.     

Synthesis and properties of polymers containing sprio(indoline-isoxazoline)

Polymers containing spiro(indoline-isoxazoline) nuclei were prepared by 1,3-dipolar cycloaddition reactions of N,N′-alkylene-bis-3,3-dimethyl-2-methyleneindolines with bis-hydroxamic chlorides. Irradiation of the polymers with UV in solution resulted in novel skeletal rearrangements and resulted in polymers containing benzo-1,5-diazocine-2-one nuclei. Photoconductivities of the polymers were also studied.     

Direct-reading, time-resolving technique in emission spectroscopy and its application to the analysis of iron, steel and iron ores

Summary An attempt of the time-resolution of emission spectra was carried out using a simple pulse generator by impressing a gate pulse on the dynodes of a photomultiplier tube in the direct-reading spectrometer. Examinations were made on the variation of the intensity of spectral line with time in various atmospheres and it was confirmed that the after-glow is the longest in an argon atmosphere.The possibility of avoiding the effect of an interfering spectral line lying close to the analytical line was examined and this was proved to be possible with the analytical line of Si I 2881.58 å and the interfering line of Cr II 2881.93 å. The analytical line of calcium, Ca II 3933.67 å, is interfered by Fe I 3933.61 å and the effect of the spectral line of iron was avoided by the use of the time-resolving technique. This permitted the rapid determination of 0.0010.1% of calcium in iron ores by the direct-reading spectrographic analysis.

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Zusammenfassung Ein Versuch der zeitlichen Auflösung von Emissionsspektren wurde durchgeführt unter Verwendung eines einfachen Impulsgenerators, indem man den Eröffnungsimpuls auf die Dynoden eines Photovervielfachers in einem direktschreibenden Spektrometer überlagert. Untersucht wurde die VerÄnderung der LinienintensitÄt in verschiedenartigen AtmosphÄren. Man konnte bestÄtigen, da\ das Nachglimmen in ArgonatmosphÄre am lÄngsten dauert.Auch die Möglichkeit der Vermeidung der Störung durch benachbarte Spektrallinien wurde untersucht und gefunden, da\ die Vermeidung der Störung bei der Linie Si I 2881,58 å und der Störlinie Cr II 2881,93 å möglich ist. Die Analysenlinie Ca II 3933,67 å wird durch die Linie Fe I 3933,61 å gestört, was durch die Zeitauflösungstechnik vermieden wird. Dadurch wird es möglich, 0,001–0,1% Calcium in Eisenerzen durch direktschreibende spektrographische Analyse zu bestimmen.

     

Preparation and properties of electron donor acceptor complexes of the compounds having capto-dative substituents

In order to examine the “capto-dative” substitution-effect on the electrical conductivity, five compounds which have capto-dative substituents were prepared. Electron withdrawing (capto) group was nitro- or cyano-substituted phenyl and electron donating (dative) one was 5-methyl-5,10-dihydrophenazinyl moiety. The character of intramolecular electron donor acceptor complex of the five compounds were demonstrated by their uv spectra. Electron donor acceptor complexes of them with tetracyanoquinodimethane were prepared and their electrical resistivities were measured.     

Preparation of dithiocarbamatecellulose derivatives and their adsorption properties for trace elements

Tosylcellulose was treated separately with aniline, benzylamine, n-butylamine and piperazine to give four different aminocelluloses which were further treated with carbon disulfide to furnish four dithiocarbamatecelluloses (AND, BZD, BUD and PID). A comparative study was made of their performance as adsorbents for several kinds of metal ions. PID, which has the highest degree of substitution of the dithiocarbamate group of the four derivatives obtained, was investigated for its adsorption behavior towards Ag⁺, As⁵⁺, Cd²⁺, Co²⁺, Cr³⁺, Cr⁶⁺, Cu²⁺, Fe³⁺, Hg²⁺, Mn²⁺, Pb²⁺, Sb⁵⁺; Se⁴⁺, Te⁴⁺ and Zn²⁺. PID showed good adsorption characteristics with relatively large capacities for Ag⁺, Cr⁶⁺, Cu²⁺, Hg²⁺, Pb²⁺ and Se⁴⁺ ranging from 9.5 to 370 mg g^-1 of resin.