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PubMed2005

Synthesis of alkyl and aryl C-pyranosides using organozinc reagents via a Ferrier-type rearrangement.

The reaction of 1,2-dihydropyranyl acetates with dimethylzinc, diethylzinc and diphenylzinc in the presence of CF3COOH gave the corresponding alky and aryl C-pyranosides via a Ferrier rearrangement in excellent yields. Use of the organozinc species, CF3CO2ZnPh, reacted with high stereoselectivity to give the phenyl C-glycosides. Arylzinc chlorides could also be successfully applied to this reaction in the presence of BF3.OEt2.

Alkanes↗
PubMed1997

Interaction of sodium chloroplatinate and iproplatin with metallothionein in vivo.

The abilities of platinum(IV) complexes to induce the biosynthesis of metallothionein (MT) were investigated in rabbits given injections s.c. of sodium chloroplatinate (Na2PtCl6) and iproplatin (cis-dichloro-bis-isopropylamine-trans-dihydroxylplatinum IV). It is revealed for the first time that both complexes can induce MT synthesis in the liver and the kidney, but the induction ability was weaker compared to Zn2+ compounds. The induced MT was purified and identified. The hepatic MT resulting from Na2PtCl6 injection only contained Zn, whereas the hepatic MT from iproplatin injection and the renal MT from injection of both complexes contained 4-5 Zn and 1-2 Pt per mole of protein, and the renal MT also contained 1-2 Cu per mole of protein. The oxidation state of platinum in the MT is +2 as determined by X-ray photoelectron spectroscopic measurements. Pretreatment with Zn(NO3)2 elevated the levels of MT, but the binding of Pt to MT was significantly less compared to that without Zn(NO3)2 pretreatment. The data obtained from the amino acid composition analysis were consistent with the theoretical values. Upon these bases, the role of MT in relation to its involvement in the metabolism of Pt(IV) complexes and the mechanism of drug resistance to the Pt(IV) complexes as antitumor agents are discussed.

Animals↗
PubMed1998

Metal chloride primers for bonding dentine with tri-n-butylborane-initiated luting agents.

OBJECTIVES: The bonding of resin to dentine is dependent largely on surface modifications. The purpose of the present study was to test the hypothesis that a role of the metal chlorides used as primers is to initiate polymerization of resin at the resin-dentine interface, thereby affecting bond strength. METHODS: Nine primers were evaluated, comprising aqueous 2-hydroxyethyl methacrylate (HEMA) solutions containing AICl3, CeCl3, CoCl2, CuCl2, FeCl3, NiCl2, MgCl2, SnCl2 or ZnCl2, respectively. One of the two luting agents (Super-Bond resin) consisted of methyl methacrylate (MMA), 4-methacryloyloxyethyl trimellitate anhydride (4-META) and tri-n-butylborane (TBB) initiator. The other luting agent (MMA-TBB resin) consisted of MMA and TBB without 4-META. Extracted bovine teeth were ground to expose the dentine, etched with an aqueous solution of 10% phosphoric acid, primed, and then bonded with stainless-steel rods; tensile bond strengths were determined after 1-day immersion in water. Data were analysed by ANOVA and Duncan's new multiple range test (P < 0.05). RESULTS: Four of the metal chlorides (CuCl2, FeCl3, MgCl2 and ZnCl2) enhanced the bond strengths of MMA-TBB resin to dentine. With Super-Bond resin, maximum bond strengths of 15.6 MPa and 19.0 MPa were recorded with primer containing 2.0 x 10(-5) mol g(-1) FeCl3 and 2.0 x 10(-6) mol g(-1) CuCl2, respectively. CONCLUSIONS: Bonding techniques, combining the use of either cupric primer or ferric primer with 10% phosphoric acid etchant may be suitable for application in seating resin-bonded prostheses with TBB-initiated luting materials.

Acid Etching, Dental↗
PubMed2006

Solution-phase single quantum dot fluorescence resonance energy transfer.

We present a single particle fluorescence resonance energy transfer (spFRET) study of freely diffusing self-assembled quantum dot (QD) bioconjugate sensors, composed of CdSe-ZnS core-shell QD donors surrounded by dye-labeled protein acceptors. We first show that there is direct correlation between single particle and ensemble FRET measurements in terms of derived FRET efficiencies and donor-acceptor separation distances. We also find that, in addition to increased sensitivity, spFRET provides information about FRET efficiency distributions which can be used to resolve distinct sensor subpopulations. We use this capacity to gain information about the distribution in the valence of self-assembled QD-protein conjugates and show that this distribution follows Poisson statistics. We then apply spFRET to characterize heterogeneity in single sensor interactions with the substrate/target and show that such heterogeneity varies with the target concentration. The binding constant derived from spFRET is consistent with ensemble measurements.

Cadmium Compounds↗
PubMed2005

Fluorescence resonance energy transfer in CdSe/ZnS-DNA conjugates: probing hybridization and DNA cleavage.

Nucleic-acid-functionalized CdSe/ZnS quantum dots (QDs) were hybridized with the complementary Texas-Red-functionalized nucleic acid. The hybridization was monitored by following the fluorescence resonance energy transfer from the QDs to the dye units. Treatment of the QD/dye DNA duplex structure with DNase I resulted in the cleavage of the DNA and the recovery of the fluorescence properties of the CdSe/ZnS QDs. The luminescence properties of the QDs were, however, only partially recovered due to the nonspecific adsorption of the dye onto the QDs. Similarly, nucleic-acid-functionalized Au nanoparticles (Au NPs) were hybridized with the complementary Texas-Red-labeled nucleic acid. The hybridization was followed by the fluorescence quenching of the dye by the Au NPs. Treatment of the Au NP/dye DNA duplex with DNase I resulted in the cleavage of the DNA and the partial recovery of the dye fluorescence. The incomplete recovery of the dye fluorescence originated from the nonspecific binding of the dye units to the Au NPs. The nonspecific binding of the dye to the CdSe/ZnS QDs and the Au NPs is attributed to nonprotected surface vacancies in the two systems.

Base Sequence↗
PubMed2006

In-situ encapsulation of quantum dots into polymer microspheres.

We have incorporated fluorescent quantum dots (QDs) into polystyrene microspheres using functionalized oligomeric phosphine (OP) ligands. We find that a uniform distribution of quantum dots is loaded inside each polymer bead. Some local close-packing of quantum dots in the beads is attributed to the self-polymerization of the functionalized ligands. The presence of quantum dots disturbs the nucleation and growth processes during the formation of polymer microspheres and results in a wider size distribution of the quantum dot-embedded polystyrene beads than for the control without dots. The change in quantum efficiency of the quantum dots before (approximately 20%) and after (12%) loading into the beads substantiates the protection of oligomeric phosphine ligands yet indicates that the properties of these quantum dots are still affected during processing.

Cadmium Compounds↗
PubMed2006

Synthesis of quantum dot-tagged submicrometer polystyrene particles by miniemulsion polymerization.

Submicrometer fluorescent polystyrene (PS) particles have been synthesized via miniemulsion polymerization using CdSe/ZnS core-shell quantum dots (QDs). The influence of QD concentration, QD coating (either trioctylphosphine oxide (TOPO)-coated or vinyl-functionalized), and surfactant concentration on the polymerization kinetics and the photoluminescence properties of the prepared particles has been analyzed. Polymerization kinetics were not altered by the presence of QDs, whatever their surface coating. Latexes exhibited particle sizes ranging from 100 to 350 nm, depending on surfactant concentration, and a narrow particle size distribution was obtained in all cases. The fluorescence signal of the particles increased with the number of incorporated TOPO-coated QDs. The slight red shift of the emission maximum was correlated with phase separation between PS and QDs, which occurred during the polymerization, locating the QDs in the vicinity of the particle/water interface. QD-tagged particles displayed higher fluorescence intensity with TOPO-coated QDs compared to those with the vinyl moiety. The obtained fluorescent particles open up new opportunities for a variety of applications in biotechnology.

Cadmium Compounds↗
PubMed2005

Cytotoxicity of colloidal CdSe and CdSe/ZnS nanoparticles.

Cytotoxicity of CdSe and CdSe/ZnS nanoparticles has been investigated for different surface modifications such as coating with mercaptopropionic acid, silanization, and polymer coating. For all cases, quantitative values for the onset of cytotoxic effects in serum-free culture media are given. These values are correlated with microscope images in which the uptake of the particles by the cells has been investigated. Our data suggest that in addition to the release of toxic Cd(2+) ions from the particles also their surface chemistry, in particular their stability toward aggregation, plays an important role for cytotoxic effects. Additional patch clamp experiments investigate effects of the particles on currents through ion channels.

Animals↗
PubMed2006

Continuous distribution of emission states from single CdSe/ZnS quantum dots.

The photoluminescence dynamics of colloidal CdSe/ZnS/streptavidin quantum dots were studied using time-resolved single-molecule spectroscopy. Statistical tests of the photon-counting data suggested that the simple "on/off" discrete state model is inconsistent with experimental results. Instead, a continuous emission state distribution model was found to be more appropriate. Autocorrelation analysis of lifetime and intensity fluctuations showed a nonlinear correlation between them. These results were consistent with the model that charged quantum dots were also emissive, and that time-dependent charge migration gave rise to the observed photoluminescence dynamics.

Cadmium Compounds↗
PubMed2006

Zero-phonon linewidth in CdSe/ZnS core/shell nanorods.

High-resolution spectral hole-burning studies of CdSe/ZnS core/shell nanorods reveal a sharp zero-phonon line, with a line width dependent on the measurement time scale. The zero-phonon line width is attributed to contributions from radiative decay, spectral diffusion induced by surface electric field fluctuations, and phonon-assisted migration of excitons localized in the nanorods. A decoherence rate as small as 4.5 GHz has been observed, when the effects of spectral diffusion are suppressed in the spectral hole-burning measurement. Comparison between zero-phonon line widths in nanorods and spherical nanocrystals also elucidates important differences in the decoherence process between the one- and zero-dimensional nanostructures.

Cadmium Compounds↗
PubMed2003

A new synthetic route to phomoidride B and its derivatives.

We have developed a new synthetic route to phomoidride B, which could also be applied to the synthesis of phomoidride B derivatives using Pd-catalyzed coupling reaction of a thiolester with an organozinc reagent. In addition, direct construction of the maleic anhydride moiety has been achieved by a Pd-catalyzed carbonylation reaction.

Catalysis↗
PubMed1990

Liposome- or LDL-administered Zn (II)-phthalocyanine as a photodynamic agent for tumours. I. Pharmacokinetic properties and phototherapeutic efficiency.

The pharmacokinetics of Zn-phthalocyanine (Zn-Pc) in mice bearing a transplanted MS-2 fibrosarcoma has been studied using dipalmitoyl-phosphatidylcholine (DPPC) liposomes and low density lipoproteins (LDL) as drug delivery systems. LDL induce a higher Zn-Pc uptake by the tumour and improve the selectivity of tumour targeting as compared to DPPC liposomes. Experimental photodynamic therapy (PDT) of the MS-2 fibrosarcoma has been performed using liposome-delivered Zn-Pc and the efficiency of tumour necrosis has been measured following four different irradiation protocols. We found that Zn-Pc doses as low as 0.07-0.35 mg kg-1 are sufficient for inducing an efficient tumour response that is linearly dependent on the injected dose. The amount of Zn-Pc in the tumour decreases very slowly as a function of time, hence PDT gives satisfactory results even if performed at relatively long time intervals after administration.

Animals↗
PubMed2002

Polaprezinc attenuates Helicobacter pylori-associated gastritis in Mongolian gerbils.

BACKGROUND: The ammonia-monochloramine system plays an important role in Helicobacter pylori-associated gastric mucosal injury. Polaprezinc, a new antiulcer agent, has a scavenging action against monochloramine. The aim of the experiment was to investigate the inhibitory effects of polaprezinc on the H. pylori-induced gastritis in Mongolian gerbils. MATERIALS AND METHODS: Mongolian gerbils fasting for 24 hours were orally given culture broth containing 2-4 x 10(8) colony-forming units of H. pylori ATCC 43054 per milliliter. From 4 hours after inoculation until the end of the experiment, gerbils were given chow pellets with or without 0.02% polaprezinc. All gerbils were killed 12 weeks later. The grades of H. pylori density and histologic features of gastritis were evaluated in accordance with the Updated Sydney System. The scavenging effect of polaprezinc on monochloramine was investigated spectrophotometrically. RESULTS: Polaprezinc had little or no influence on the H. pylori density in both pyloric and fundic mucosae. However, it significantly attenuated the development of polymorphonuclear neutrophil activity, mononuclear infiltration, and surface epithelial erosion in both pyloric and fundic mucosae compared with those of the control group. H. pylori inoculation significantly increased the heights of both pyloric and fundic mucosae (mainly due to the increased height of foveolar hyperplasia), but polaprezinc inhibited the increase of mucosal thickness in both pyloric and fundic mucasae. No intestinal metaplasia was detected in this study. Spectrophotometric examination revealed that polaprezinc scavenged monochloramine. CONCLUSIONS: Polaprezinc inhibited the development of H. pylori-induced gastritis through its scavenging action against monochloramine.

Animals↗
PubMed1978

Lymphocytic inflammation produced by intracerebral implantation of zinc and other metals.

Sxteen pure metals were implanted as pellets of powder or as wires into the brains of rats. Al, Be, Cr, Fe, Pb, Sn, and W were relatively innocuous. Mg and Mn produced local necrosis. Bi, Cd, Co, Cu and Ni produced more severe local necrosis. Viable tissue adjacent to Co and Ni necrotic lesions had some perivascular lymphocytic infiltrates. Zn implants caused very little necrosis but adjacent areas had prominent perivascular lymphocytic cuffs. The infiltrates persisted for at least 4 weeks but disappeared as soon as the zinc was removed. Some compounds of zinc were also capable of inducing infiltrates. The perivascular infiltrates resembled the lesions of allergic encephalomyelitis, but there was no correlation between the ability of metal powders to induce lymphocytic infiltrates after intracerebral implantation and their adjuvancy after intraperitoneal injection with neural antigen.

Adjuvants, Immunologic↗
PubMed1999

Parameterization of the temperature dependence of the Debye-Waller factors.

Parameterization has been made for the temperature dependence of the Debye-Waller factors of 68 elemental crystals and 17 compounds with the zinc-blende structure. The Debye-Waller factors of 46 elemental crystals were calculated based on the available phonon density of states, and those of the remaining 22 elemental crystals were estimated using the Debye approximation for the phonon density of states. The Debye-Waller factors of the zinc-blende compounds were obtained from the 14-parameter shell-model calculations of Reid [Acta Cryst. (1983), A39, 1-13].

Journal Article↗