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Rotational and translational diffusion of peptide-coated CdSe/CdS/ZnS nanorods studied by fluorescence correlation spectroscopy.

CdSe/CdS/ZnS nanorods (NRs) of three aspect ratios were coated with phytochelatin-related peptides and studied using fluorescence correlation spectroscopy (FCS). Theoretical predictions of the NRs' rotational diffusion contribution to the correlation curves were experimentally confirmed. We monitored rotational and translational diffusion of NRs and extracted hydrodynamic radii from the extracted diffusion constants. Translational and rotational diffusion constants (D(trans) and D(rot)) for NRs were in good agreement with Tirado and Garcia de la Torre's as well as with Broersma's theories when accounting for the ligand dimensions. NRs fall in the size range where rotational diffusion can be monitored with higher sensitivity than translational diffusion due to a steeper length dependence, D(rot) approximately L(-)(3) versus D(trans) approximately L(-)(1). By titrating peptide-coated NRs with bovine serum albumin, we monitored (nonspecific) binding through rotational diffusion and showed that D(rot) is an advantageous observable for monitoring binding. Monitoring rotational diffusion of bioconjugated NRs using FCS might prove to be useful for observing binding and conformational dynamics in biological systems.

Amino Acid Sequence↗

Recognition-directed orthogonal self-assembly of polymers and nanoparticles on patterned surfaces.

We demonstrate the patterning of silica substrates with thymine (Thy-PS) and positively charged N-methylpyridinium (PVMP) polymers using photolithography and the subsequent orthogonal modification of these surfaces using diaminopyridine-functionalized polystyrene (DAP-PS) and carboxylate-derivatized CdSe/ZnS core-shell nanoparticles (COO-NP) through diamidopyridine-thymine three-point hydrogen bonding and pyridinium-carboxylate electrostatic interactions, respectively. This two-component orthogonal surface modification was accomplished in a self-sorting, single-step fashion, providing a versatile tool for the rapid and efficient creation of complex materials.

Cadmium Compounds↗

Large enhancement of fluorescence efficiency from CdSe/ZnS quantum dots induced by resonant coupling to spatially controlled surface plasmons.

Nanoengineered fluorescent response is reported from semiconductor core-shell (CdSe/ZnS) quantum dots in proximity to the surface plasmon polariton field of periodic Ag nanoparticle arrays. Tuning the surface plasmon polariton resonance to the quantum dot exciton emission band results in an enhancement of up to approximately 50-fold in the overall fluorescence efficiency, in a design where each Ag nanoparticle is interconnected by a continuous Ag thin film. Propagating modes of surface plasmon resonances have a direct impact on the fluorescence enhancement.

Cadmium Compounds↗

Photophysical, photochemical and antibacterial photosensitizing properties of a novel octacationic Zn(II)-phthalocyanine.

A novel Zn(II)-phthalocyanine (1). peripherally substituted with four bis(N,N,N-trimethyl)amino-2-propyloxy groups prepared by chemical synthesis is shown to be an efficient photodynamic sensitizer with a quantum yield of 0.6 for singlet oxygen generation in neat water, which is reduced to about 0.3 in phosphate-buffered saline. The physicochemical properties of 1 in both the ground and the electronically excited states strongly depend on the nature of the medium; in particular, aggregation of 1 was favoured by polar media of high ionic strength. Compound 1 exhibited an appreciable affinity for a typical Gram-positive bacterium (Staphylococcus aureus) and a typical Gram-negative bacterium (Escherichia coli). Both bacterial strains were extensively inactivated upon 5 min-irradiation with 675 nm light in the presence of 1 microM photosensitizer, even though the binding of 1 to the two bacterial cells appears to occur according to different pathways. In particular, E. coli cells underwent initial photodamage at the level of specific proteins in the outer wall, thus promoting the penetration of the photosensitizer to the cytoplasmic membrane where some enzymes critical for cell survival were inactivated.

Anti-Bacterial Agents↗

Rapid and effective labeling of brain tissue using TAT-conjugated CdS:Mn/ZnS quantum dots.

TAT (a cell penetrating peptide)-conjugated CdSratioMn/ZnS quantum dots (Qdots), intra-arterially delivered to a rat brain, rapidly (within a few minutes) labeled the brain tissue without manipulating the blood-brain-barrier (BBB). Qdot loading was sufficiently high that it allowed a gross fluorescent visualization of the whole rat brain using a low power hand-held UV lamp. Histological data clearly showed that TAT-conjugated Qdots migrated beyond the endothelial cell line and reached the brain parenchyma. Qdots without TAT did not label the brain tissue confirming the fact that TAT peptide was necessary to overcome the BBB. The present study clearly demonstrated the possibility of delivering a large amount of Qdot-based imaging agents to the brain tissue.

Animals↗

Nitric oxide-dependent pro-oxidant and pro-apoptotic effect of metallothioneins in HL-60 cells challenged with cupric nitrilotriacetate.

Intracellular safeguarding functions of metallothioneins (MTs) include sequestering transition and heavy metals, scavenging free radicals and protecting against electrophiles. We report that MT protection against Cu-induced cytotoxicity can be reversed and pro-oxidant and pro-apoptotic effects can be induced in HL-60 cells exposed to NO. We demonstrate that in ZnCl(2)-pretreated HL-60 cells loaded with copper nitrilotriacetate (Cu-NTA), exposure to an NO donor, S-nitroso-N-acetyl penicillamine, resulted in S-nitrosylation and oxidation of MT cysteines. This disruption of MT Cu-binding thiolate clusters caused loosening and release of redox-active Cu, enhanced redox-cycling activity of Cu and increased peroxidation of major classes of membrane phospholipids. We also found that Cu-induced oxidative stress in ZnCl(2)-pretreated/Cu-NTA-loaded HL-60 cells was accompanied by apoptosis documented by characteristic changes of nuclear morphology, internucleosomal DNA cleavage, externalization of phosphatidylserine, release of cytochrome c from mitochondria into cytosol and activation of caspase-3. We conclude that in Cu-challenged cells, NO can reverse the protective role of MTs and convert them into pro-oxidant, pro-apoptotic implements.

Annexin A5↗

A comparison of fluorescence methods used in the pharmacokinetic studies of Zn(II)phthalocyanine in mice.

The pharmacokinetics of Zn phthalocyanine (ZnPc) encapsulated in dipalmitoyl-phosphatidylcholine (DPPC) liposomes, injected intravenously in Skh:HR-1 nude mice, was monitored by two in vitro techniques and one in vivo technique, all based on fluorescence spectroscopy. The in vitro methods involve either fluorescence measurements on thin tissue sections or on extracts from these tissues. The in vivo method involves the fluorescence measurement at the skin surface. Both in vitro techniques gave similar results which are consistent with previous findings on the pharmacokinetic behavior of ZnPc. The liver and spleen showed rapid ZnPc concentration increases, reaching a maximum level in 30 min. or less post drug administration. Relatively little ZnPc was detected in the skin, fat or muscle, the maximum concentration occurring at 12 h. In vivo fluorescence reached a maximum intensity approx. 6 h post injection at the mid-chest analysis site and at 12 h in the thigh. The in vivo measurements at two different anatomical sites showed pharmacokinetic behavior that reflects an overall integrated fluorescence originating from several tissue sites.

1,2-Dipalmitoylphosphatidylcholine↗

Virus-based toolkit for the directed synthesis of magnetic and semiconducting nanowires.

We report a virus-based scaffold for the synthesis of single-crystal ZnS, CdS, and freestanding chemically ordered CoPt and FePt nanowires, with the means of modifying substrate specificity through standard biological methods. Peptides (selected through an evolutionary screening process) that exhibit control of composition, size, and phase during nanoparticle nucleation have been expressed on the highly ordered filamentous capsid of the M13 bacteriophage. The incorporation of specific, nucleating peptides into the generic scaffold of the M13 coat structure provides a viable template for the directed synthesis of semiconducting and magnetic materials. Removal of the viral template by means of annealing promoted oriented aggregation-based crystal growth, forming individual crystalline nanowires. The unique ability to interchange substrate-specific peptides into the linear self-assembled filamentous construct of the M13 virus introduces a material tunability that has not been seen in previous synthetic routes. Therefore, this system provides a genetic toolkit for growing and organizing nanowires from semiconducting and magnetic materials.

Alloys↗

[The gastric mucosal adhesiveness of Z-103 in rats with chronic ulcer].

The gastric mucosal adhesiveness of Z-103 in rats with acetic acid ulcer was studied macroscopically, histologically, and biochemically. From macroscopical observations, when Z-103 was orally administered to an acetic acid ulcer model, there was adhesion of Zn to the normal mucosa as well as the ulcerous site under both the fasting condition and after feeding. It was also proven that the strength and duration of adhesiveness were increased dose-dependently under fasting conditions. In addition, histological localization of Zn was noted from the covering epithelial cell layer to the gastric lamina propria mucosae in the normal tissue and in the most superficial ulcerous layer and the granulous layer of the ulcerous site. Measurement of the gastric tissue Zn content after oral administration of 100 mg/kg of Zn showed that the Zn content was significantly increased for 6 hr at the normal site and for 24 hr at the ulcerous site. On the other hand, although ZnSO4 and ZnSO4+carnosine combination macroscopically produced generally the same level of adhesiveness as Z-103, when the gastric tissue Zn content for Z-103 and ZnSO4 were compared, the Zn content of ZnSO4 was lower than that for Z-103 at both the normal and ulcerous site. In summary, Z-103 shows a long-term adhesive and permeable action on the gastric mucosa in acetic acid ulcer rats, and it has a comparable high affinity at the ulcerous site.

Acetates↗

Polaprezinc protects human colon cells from oxidative injury induced by hydrogen peroxide: relevant to cytoprotective heat shock proteins.

AIM: To investigate the effect of polaprezinc on cellular damage induced by hydrogen peroxide (H(2)O(2)) in human colon CaCo2 cells. METHODS: CaCo2 cells were treated with polaprezinc (10-100 micromol/L) for 6 h. After polaprezinc treatment, the cells were incubated with H(2)O(2) (20 micromol/L) for 1 h. Cell viability was measured by MTT assay. Western blot analysis for heat shock protein (HSP) 27 and HSP72 in the cells was performed. Moreover, cells were pretreated with quercetin (200 micromol/L), an inhibitor of HSP synthesis, 2 h before polaprezinc treatment, and cell viability and the expression of HSP27 and 72 were assessed in these cells. RESULTS: Polaprezinc significantly protected CaCo2 cells from cell damage induced by H(2)O(2), and up-regulated the expressions of HSP27 and HSP72 in the cells (10, 30 and 100 micromol/L of polaprezinc; 35.0% +/- 7.7%, 58.3% +/- 14.6% and 64.2% +/- 8.2%, respectively. P < 0.01 versus polaprezinc-nontreated cells; 6.0% +/- 4.4%). Quercetin inhibited the up-regulation of HSP27 and HSP72 by polaprezinc and diminished the protective effect of polaprezinc against H(2)O(2)-caused injury in the cells. CONCLUSION: Polaprezinc is a useful therapeutic agent for treatment of colitis and its effects depend on the function of cytoprotective HSP in colon.

Anti-Ulcer Agents↗

Extracellular heavy-metal ions stimulate Ca2+ mobilization in hepatocytes.

Populations of hepatocytes in primary culture were loaded with fura 2 and the effects of extracellular heavy-metal ions were examined under conditions that allowed changes in fura 2 fluorescence (R340/360, the ratio of fluorescence recorded at 340 and 360 nm) to be directly attributed to changes in cytosolic free [Ca2+] ([Ca2+]i). In Ca2+-free media, Ni2+ [EC50 (concentration causing 50% stimulation) approximately 24+/-9 microM] caused reversible increases in [Ca2+]i that resulted from mobilization of the same intracellular Ca2+ stores as were released by [Arg8]vasopressin. The effects of Ni2+ were not mimicked by increasing the extracellular [Mg2+], by addition of MnCl2, CoCl2 or CdCl2 or by decreasing the extracellular pH from 7.3 to 6.0; nor were they observed in cultures of smooth muscle, endothelial cells or pituitary cells. CuCl2 (80 microM), ZnCl2 (80 microM) and LaCl3 (5 mM) mimicked the ability of Ni2+ to evoke Ca2+ mobilization. The response to La3+ was sustained even in the absence of extracellular Ca2+, probably because La3+ also inhibited Ca2+ extrusion. Although Ni2+ entered hepatocytes, from the extent to which it quenched fura 2 fluorescence the free cytosolic [Ni2+] ([Ni2+]i) was estimated to be <5 nM at the peak of the maximal Ni2+-evoked Ca2+ signals and there was no correlation between [Ni2+]i and the amplitude of the evoked increases in [Ca2+]i. We conclude that extracellular Ni2+, Zn2+, Cu2+ and La3+, but not all heavy-metal ions, evoke an increase in [Ca2+]i in hepatocytes by stimulating release of the hormone-sensitive intracellular Ca2+ stores and that they may do so by interacting with a specific cell-surface ion receptor. This putative ion receptor may be important in allowing hepatocytes to contribute to regulation of plasma heavy-metal ions and may mediate responses to Zn2+ released into the portal circulation with insulin.

Adenosine Triphosphate↗

[Effect of carbostimulin on reparative osteogenesis in rabbits of different ages].

Rate of reparative osteogenesis was studied after partial resection of rabbit radius bone. Within 15 days of the restoration period the content of dry residue was increased by 26%, 17% and 35% in regenerate of 2-months old animals, treated with their mixtures as compared with 6-months old rabbits. Content of calcium was increased 1.5-fold in callus of all the 2-months old animals as compared with that in the 6-months old rabbits.

Animals↗

[Effect of carbostimulin on metabolism in rats with deep burns].

It is established that at early stages of the burn disease (deep burn of III-B degree, 20% of body surface) in rats there appears metabolic acidosis, the content of urea increases in the liver and blood serum, a pronounced hydration of the liver and muscles is observed in the burn zone. Administration per os of carbostimulin just a day after burn removes symptoms of metabolic acidosis. When the preparation is fed to rats during 7 days after burn the intensity of radioactive label incorporation into proteins, lipid and glycogen of the liver as well as in proteins and lipids of kidneys and spleen increases.

Acidosis↗

Effect of zinc sulfate and acetylcysteine on experimental gastric ulcer: in vitro study.

A small ulcer produced in vitro by monopolar electrocoagulation on endoscopically obtained human antral biopsies and incubated in Trowel T-8 medium at 37 degrees C for 8 h has many histologic features of chronic gastric ulcer in man. Zinc sulfate and acetylcysteine in low concentrations had a significant healing effect in this ulcer model. Since the beneficial effect of zinc sulfate and acetylcysteine was counteracted by N-ethylmaleimide, a known blocker of sulfhydryl compounds, the beneficial effect of these two compounds probably was mediated through sulfhydryl compounds. Using special stain, N-(4-aminophenyl)maleimide, the sulfhydryl groups were localized in the epithelial cells of the surface layer and gastric glands.

Acetylcysteine↗

Dentine hypersensitivity: effect of interactions between metal salts, fluoride and chlorhexidine on the uptake by dentine.

A large number of compounds may be applied to the teeth for preventive or therapeutic purposes, most notably in dentine hypersensitivity. The uptake of any one compound by tooth substances may clearly be affected by another to produce synergistic, additive or antagonistic effects. This study determined whether uptake interactions occurred between fluoride, chlorhexidine, strontium, tin and zinc. All compounds, in particular tin, showed considerable affinity for dentine. Fluoride reduced the uptake of zinc but not tin, strontium or chlorhexidine. Chlorhexidine increased the uptake of zinc, but not tin, strontium or fluoride. Zinc and tin decreased fluoride uptake but strontium had no such effect. Finally, chlorhexidine uptake was increased by zinc and tin but not by fluoride or strontium. Based on the theories proposed for the reaction of these various compounds with calcified tissues, explanations for the interactions can be made. The results appear relevant to some reported clinical effects of combinations of these compounds and indicate that such interactions may have advantageous or disadvantageous consequences depending on the basis for treatment.

Chlorhexidine↗