Hybrid microgels photoresponsive in the near-infrared spectral range

We report for the first time a photothermally responsive composite material based on polymer microgel particles doped with gold nanorods. We used the dependence of the longitudinal surface plasmon of the gold nanorods on their aspect ratio to synthesize nanoparticles with strong absorption in the near-IR spectral range (in the "water window"). The nanoparticles were incorporated in the interior of temperature-responsive poly(N-isopropylacrylamide-acrylic acid) microgels. Upon irradiation at lambda = 810 nm, hybrid microgel particles doped with Au nanorods underwent a strong deswelling phase transition. These photothermally responsive microgels can be used to carry and release small molecules (e.g., small protein molecules and drugs).     

Topological effect on MO energies,IV. The total π-electron energy ofS- andT-isomers

A novel general property of theS- andT-isomers (a concept which has been introduced and elaborated elsewhere^{1, 2}) of alternant hydrocarbons is demonstrated, namely that due to the HMO total -electron energy theS-isomer should always be more stable than theT-isomer. Some other classes of conjugated isomers are also constructed, for which similar inequalities are derived.

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Topologischer Effekt bei MO-Energien, 4. Mitt.: Die -Elektronen-Gesamtenergie vonS- undT-Isomeren

Zusammenfassung Es wird allgemein gezeigt, daß bei einemS-T-Isomerenpaar (beschrieben in^{1, 2}) eines alternierenden Kohlenwasserstoffes infolge der HMO -Elektronen-Gesamtenergie dasS-Isomere stets stabiler sein sollte als dasT-Isomere. Weitere Klassen konjugierter Isomere werden konstruiert und ähnliche Ungleichungen angegeben.

     

Water-soluble meroterpenes containing an aminoglyceride fragment with geraniol residues: synthesis and membranotropic properties

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Gold nanoparticles: catalyst for the oxidation of NADH to NAD(+)

Nicotinamide adenine dinucleotide is an important coenzyme involved in the production of ATP, the fuel of energy, in every cell. It alternates between the oxidized form NAD(+) and the reduced form dihydronicotinamide adenine dinucleotide (NADH) and serves as a hydrogen and electron carrier in the cellular respiratory processes. In the present work, the catalytic effect of gold nanoparticles on the oxidization of NADH to NAD(+) was investigated. The addition of gold nanoparticles was found to quench the NADH fluorescence intensities but had no effect on the fluorescence lifetime. This suggested that the fluorescence quenching was not due to coupling with the excited state, but due to changing the ground state of NADH. The intensity of the 340 nm absorption band of NADH was found to decrease while that of the 260 nm band of NAD(+) was found to increase as the concentration of gold nanoparticles increased. This conversion reaction was further supported by nuclear magnetic resonance and mass spectroscopy. The effect of the addition of NADH was found to slightly red shift and increase the intensity of the surface plasmon absorption band of gold nanoparticles at 520 nm. This gives a strong support that the conversion of NADH to NAD(+) is occurring on the surface of the gold nanoparticles, i.e. NADH is surface catalyzed by the gold nanoparticles. The catalytic property of this important reaction might have important future applications in biological and medical fields.     

Electrochemical generation of manganese(III) and behaviour of the generated oxidant in acetic acid in the presence of perchlorate ions

Summary Research was carried out to determine conditions for the anodic generation of manganese(III) with high current efficiency in solutions of sodium perchlorate in acetic acid, and to examine the behaviour of the oxidant thus generated. The effects of water and acetic anhydride on current efficiency in the generation of the oxidant was also examined. The formal redox potential of the Mn(III)/ Mn(II) system is decreased with increasing concentrations of sodium acetate in the solution. The effect of sodium perchlorate and perchloric acid concentrations is the reverse. Procedures for coulometric titrations of a number of substances with the generated oxidant were developed, end point being detected using biamperometric and potentiometric methods. Perchloric acid accelerates the oxidation of certain substances with manganese(III) in acetic acid and increases the sensitivity of end-point detection using the potentiometric method.

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Elektrochemische Erzeugung von Mangan(III) und das Verhalten dieses Oxydationsmittels in Essigsäure bei Gegenwart von Perchlorat

Zusammenfassung Die Bedingungen der anodischen Erzeugung von Mangan(III) mit hoher Stromausbeute in Essigsäure, nach Zugabe von Natriumperchlorat wurden untersucht; das elektrochemische Verhalten des so dargestellten Oxydationsmittels wurde ebenfalls untersucht. Der Einfluß von Wasser und Essigsäureanhydrid auf die prozentuelle Stromausbeute des erwähnten Oxydationsmittels wurde verfolgt. Das Formalredoxpotential des Systems Mn(III)/ Mn(II) sinkt bei Erhöhung der Konzentration an Natriumacetat in der Lösung. Perchlorsäure wie auch Natriumperchlorat üben eine entgegengesetzte Wirkung aus und führen zur Steigerung des Formalredoxpotentials bei Erhöhung ihrer Konzentration. Verfahren zur coulometrischen Titration verschiedener Substanzen mittels biamperometrischer oder potentiometrischer Erfassung des Titrationsendpunktes wurden ausgearbeitet. In Gegenwart von Perchlorsäure wächst die Geschwindigkeit der Oxydation einiger Substanzen in Essigsäure in Gegenwart von Mn(III) und auch die Empfindlichkeit der Endpunktbestimmung verbessert sich.

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Presented at the 9th International Symposium on Microchemical Techniques, Amsterdam, August 28–September 2, 1983.     

Geometry changes of a Cu(I) phenanthroline complex on photoexcitation in a confining medium by time-resolved X-ray diffraction

Using a stroboscopic technique, in which the molecule is repeatedly excited and the structural change is probed more than 5000 times per second immediately after excitation, we performed a 16 K time-resolved single-crystal study of the microsecond lifetime triplet state of the Cu(I)phenanthroline derivative[Cu(I)(dmp)(dppe)][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane). The geometry changes on excitation differ for the two symmetry-independent molecules, but are in the same direction as calculated for an isolated reference molecule, although the flattening distortion in the crystal is significantly smaller, implying that the reorganization energy is greatly affected by the confining medium.     

Facile and efficient synthesis of 6-(hydroxymethyl)purines

[reaction: see text] A facile and efficient methodology of the synthesis of 6-(hydroxymethyl)purine derivatives (bases and nucleosides) was developed based on Pd-catalyzed cross-coupling reactions of 6-halopurines with acyloxymethylzinc iodides followed by deprotection. Several title compounds are inhibitors of adenosine deaminase and exert cytostatic activity.     

Hydroxyapatite-poly(d,l-lactide) Nanografts. Synthesis and Characterization as Bone Cement Additives

This paper reports the creation of hydroxyapatite/polyester nanografts by “graft-from” polymerization of d,l-lactide with [Ca₅(OH)(PO₄)₃]₂ as the initiator and tin(II)-2-ethylhexanoate as the catalyst. Model polymerizations were performed with cyclooctanol as initiator to confirm the grafting on the surface of the hydroxyapatite nanocrystals. Polymers with the highest molecular mass (M_n) between 4250 Da (cyclooctanol) and 6100 Da (hydroxyapatite) were produced. In both cases the molecular mass distributions of the polymers formed were monomodal. The materials obtained were characterized by size-exclusion chromatography, NMR and FT-IR spectroscopy, and thermal methods. Their suitability as additives for commercial bone cement (Simplex P Speedset, Stryker Orthopaedics) has been confirmed by thermal analysis techniques and mechanical testing. The results obtained show that addition of the hydroxyapatite/ polyester nanografts improved both thermal and mechanical properties of the bone cement.