PubMed Journal Database 
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Showing PubMed Articles 1–25 of 430,000+
Role of Hot Singlet Excited States in Charge Generation at the Black Dye/TiO2 Interface.
Photoinduced electron transfer at low-band-gap ruthenium-based dye/TiO2 has been investigated by means of ultrafast transient absorption and DFT/TDDFT calculations. We demonstrate that although the charge generation mechanism is triplet mediated upon band gap excitation, as already proven in high band gap dyes such as the well-known N3 and N719, when excess energy is provided which allows to reach high energy singlet states still in the visible spectral range, ultrafast electron transfer takes place. No int...
Suitable design of periodic metal/polymer composite materials is shown to facilitate resonant tunneling of light at absorbing wavelengths and to provide a means to significantly reduce optical absorption losses in polymer-based metallodielectric composite structures. The conditions for resonant tunneling are established based on the concept of "photonic band edge alignment" in 1D-periodic systems. For the particular case of a four-layer gold/polystyrene laminate structure, it is shown that the matching of t...
Toward the Molecular Mechanism(s) by Which EGCG Treatment Remodels Mature Amyloid Fibrils.
Protein misfolding and/or aggregation has been implicated as the cause of several human diseases, such as Alzheimer's and Parkinson's diseases and familial amyloid polyneuropathy. These maladies are referred to as amyloid diseases, named after the cross-β-sheet amyloid fibril aggregates or deposits common to these disorders. Epigallocatechin-3-gallate (EGCG), the principal polyphenol present in green tea, has been shown to be effective at preventing aggregation and is able to remodel amyloid fibrils compri...
The high-k gate dielectric structures in stacked (HfO2/Al2O3) and nanolaminated (HfAlOx) forms with a similar apparent accumulation capacitance were atomic-layer-deposited on n-type In0.53Ga0.47As substrates, and their electrical properties were investigated in comparison with a single-layered HfO2 film. Al-oxide interface passivation in both forms proved to be effective in preventing a significant In incorporation in the high-k film and reducing the interface state density. The measured valence band spectr...
Mycotoxins in foods have long been recognized as potential health hazards due to their toxic and carcinogenic properties. A simple and rapid method was developed to detect 26 mycotoxins (aflatoxins, ochratoxins, fumonisins, trichothecenes, and ergot alkaloids) in corn, rice, wheat, almond, peanut, and pistachio products using high-performance liquid chromatography-triple-quadrupole mass spectrometry. Test portions of homogenized grain or nut products were extracted with acetonitrile/water (85:15, v/v), foll...
The sensitive detection of cancer biomarkers in urine could revolutionize cancer diagnosis and treatment. Such detectors must be inexpensive, easy to interpret, and sensitive. This report describes a bioaffinity matrix of viruses integrated into PEDOT films for electrochemical sensing of prostate-specific membrane antigen (PSMA), a prostate cancer biomarker. High sensitivity to PSMA resulted from synergistic action by two different ligands to PSMA on the same phage particle. One ligand was genetically encod...
An original extraction method using water as an extractant has been established for environmentally friendly sample preparation procedures for hydrophilic pesticides (acetamiprid, clothianidin, dinotefuran, flonicamid, imidacloprid, methomyl, pymetrozine, thiacloprid, and thiamethoxam) in agricultural samples with conventional HPLC. Water-based extraction and cleanup with two solid-phase extraction cartridges can recover target hydrophilic pesticides quantitatively. The matrix effects of tested samples on t...
Mechanism-Based Triarylphosphine-Ester Probes for Capture of Endogenous RSNOs.
Nitrosothiols (RSNOs) have been proposed as important intermediates in nitric oxide (NO(•)) metabolism, storage, and transport as well as mediators in numerous NO-signaling pathways. RSNO levels are finely regulated, and dysregulation is associated with the etiology of several pathologies. Current methods for RSNO quantification depend on indirect assays that limit their overall specificity and reliability. Recent developments of phosphine-based chemical probes constitute a promising approach for the dire...
Near-IR absorbing zinc fluorenocyanine complexes 1-3 were designed and synthesized as a cosensitizer for bulk-heterojunction solar cells. Fusing fluorene rings with the porphyrazine rings resulted in narrower band gap and stabilization of both the HOMO and LUMO energy levels compared with a zinc phthalocyanine complex. The synthesized fluorenocyanines 1-3 were incorporated into bulk-heterojunction solar cells based on regioregular poly(3-hexylthiophene) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61. Th...
Pd(II)-Catalyzed ortho- or meta-C-H Olefination of Phenol Derivatives.
A combination of weakly coordinating auxiliaries and ligand acceleration allows for the development of both ortho- and meta-selective C-H olefination of phenol derivatives. These reactions demonstrate the feasibility of directing C-H functionalizations when functional groups are distal to target C-H bonds. The meta-C-H functionalization of electron-rich phenol derivatives is unprecedented and orthogonal to previous electrophilic substitution of phenols in terms of regioselectivity. These methods are also ap...
A highly water-soluble BODIPY dye bearing electron-rich o-diaminophenyl groups at 2,6-positions was prepared as a highly sensitive and selective fluorescent probe for detection of nitric oxide (NO) in living cells. The fluorescent probe displays an extremely weak fluorescence with fluorescence quantum yield of 0.001 in 10 mM phosphate buffer (pH 7.0) in the absence of NO as two electron-rich o-diaminophenyl groups at 2,6-positions significantly quench the fluorescence of the BODIPY dye via photoinduced elec...
Reaction of 1 with B(C6F5)3 under 1 bar of CO2 led to the instantaneous formation of the frustrated Lewis pair (FLP)-type species [ReHBr(NO)(PR3)2(η(2)-O═C═O-B(C6F5)3)] (2, R = iPr a, Cy b) possessing two cis-phosphines and OCO2-coordinated B(C6F5)3 groups as verified by NMR spectroscopy and supported by DFT calculations. The attachment of B(C6F5)3 in 2a,b establishes cooperative CO2 activation via the Re-H/B(C6F5)3 Lewis pair, with the Re-H bond playing the role of a Lewis base. The Re(I) η(1)-format...
Interfacial and perimeter sites have been known for their high activity in various reactions on supported gold nanoparticles. We find that the higher activity of interfacial sites in Au13/TiO2(110) toward methanol decomposition originates from charge-transfer-induced Coulomb interaction among the gold, reactant, and reducible TiO2 support, brought about through the formation of an ionic O-Au bond between gold and methoxy in such sites, which turns the participating perimeter gold atom cationic. A direct res...
Cobalt phosphate-modified nanocrystalline TiO2 (nc-TiO2) films were prepared by a doctor blade method using homemade nc-TiO2 paste, followed by the post-treatments first with monometallic sodium orthophosphate solution and then with cobalt nitrate solution. The modification with an appropriate amount of cobalt phosphate could greatly enhance the activity for photoelectrochemical (PEC) water oxidation of nc-TiO2, superior to the modification only with the phosphate anions. It is clearly demonstrated that the...
Epitaxial (La0.7Sr0.3MnO3)1-x:(ZnO)x (LSMO:ZnO) in vertically aligned nanocomposite (VAN) form was integrated on STO/TiN-buffered silicon substrates by pulsed-laser deposition. Their magnetotransport properties have been investigated and are systematically tuned through controlling the ZnO concentration. The composite film with 70% ZnO molar ratio exhibits a maximum magnetoresistance (MR) value of 55% at 70 K and 1 T. The enhanced tunable low-field MR properties are attributed to structural and magnetic dis...
We report a double-layer architecture for a photoanode of quantum-dot-sensitized solar cells (QDSSCs), which consists of a ZnO nanorod array (NR) underlayer and a ZnO nanotetrapod (TP) top layer. Such double-layer and branching strategies have significantly increased the power conversion efficiency (PCE) to as high as 5.24%, nearly reaching the record PCE of QDSSCs based on TiO2. Our systematic studies have shown that the double-layer strategy could significantly reduce charge recombination at the interface...
Marine corrosion protective coatings of hexagonal boron nitride thin films on stainless steel.
Recently, two-dimensional, layered materials such as graphene and hexagonal boron nitride (h-BN) have been identified as interesting materials for a range of applications. Here, we demonstrate the corrosion prevention applications of h-BN in marine coatings. The performance of h-BN/polymer hybrid coatings, applied on stainless steel, were evaluated using electrochemical techniques in simulated seawater media [marine media]. h-BN/polymer coating shows an efficient corrosion protection with a low corrosion cu...
Satellite muscle cells play an important role in regeneration of skeletal muscle. However, they are particularly vulnerable to oxidative stress. Herein, we address our efforts on the cytoprotective activities of carboxyfullerenes with different cage size (C60 vs C70) and adduct number on postmitotic muscle cell (C2C12 cell). The correlation of the structural effect on the cytoprotective capability of carboxyfullerenes was evaluated. We find that quadri-malonic acid C70 fullerene (QF70) exhibits higher capab...
Synthesis of Photoluminescent Au ND-PNIPAM Hybrid Microgel for the Detection of Hg(2+).
Poly(N-isopropylacrylamide) microgels (PNIPAM MGs) incorporated with photoluminescent gold nanodots (Au NDs) have been prepared and employed for the detection of mercury ions (Hg(2+)). Each of the PNIPAM MGs (hydrodynamic diameter 615 ± 15 nm) contains several Au NDs (diameter 1.8 ± 0.2 nm) in the Au ND-PNIPAM MGs. Like Au NDs, Au ND-PNIPAM MGs exhibit an absorption band at 375 nm that is assigned for ligand to metal charge transfer mixed with metal centered (ds/dp) states and photoluminescence at 520 nm...
Gadolinium-Based CuInS2/ZnS Nanoprobe for Dual-Modality Magnetic Resonance/Optical Imaging.
A new magnetic resonance/optical nanoprobe with specific cellular targeting capabilities based on nontoxic CuInS2/ZnS quantum dots (QDs) with direct covalent attachment of a Gd(III)-complex for tumor-specific imaging is reported. We introduce amphiphilic poly(maleic anhydride-alt-1-octadecene) to interdigitate with hydrophobic, protective agents on the surface of CuInS2/ZnS QDs that allows phase transfer of hydrophobic QDs from the organic into aqueous phase. Carbodiimide chemistry is used to covalently cou...
Catabolism of (+)-catechin and (-)-epicatechin by rat intestinal microbiota.
Catabolism of (+)-catechin (+C) and (-)-epicatechin (EC) by rat intestinal microbiota was examined in vitro. +C and EC metabolites isolated were identified by LC-MS and NMR analyses. As a result, 4-hydroxy-5-(3-hydroxyphenyl)valeric acid (C-5 and EC-5), 4-oxo-5-(3,4-dihydorxyphenyl)valeric acid (EC-7), 4-oxo-5-(3-hydorxyphenyl)valeric acid (EC-8), and 1-(4-hydroxyphenyl)-3-(2,4,6-trihydroxyphenyl)propan-2-ol (EC-13) were identified as new metabolites of +C or EC. From the measurement of optical rotation, ea...
Differential centrifugation and synchrotron radiation X-ray fluorescence spectroscopy (SRXRF) microprobe were used to study the distribution of the elements in tissue cross sections of pakchoi ( Brassica chinensis L.) under stress of elevated Pb and Cr. Subcellular fractionation of the different tissues grown in a nutrient solution containing 200 mg L(-1) Pb or 5 mg L(-1) Cr showed that 86.7 and 76.3% of the Pb that accumulated in the roots and shoots, respectively, was contained in the cell wall and vacuol...
We report the synthesis of CuO material by molten salt method at a temperature range, 280 to 950 °C for 3 h in air. This report includes studies on the effect of morphology, crystal structure and electrochemical properties of CuO prepared at different temperatures. Obtained CuO was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area methods. Samples prepared at ≥410 °C showed a single-phase material with a lattice parameter value of...
In this paper, we report chemical vapor phase polymerization (VPP) deposition of novel poly(3,4-ethylenedioxythiophene) (PEDOT)/graphene nanocomposites as solid tantalum electrolyte capacitor cathode films. The PEDOT/graphene films were successfully prepared on porous tantalum pentoxide surface as cathode films through the VPP procedure. The results indicated that the high conductivity nature of PEDOT/graphene leads to the decrease of cathode films resistance and contact resistance between PEDOT/graphene an...
Fungal secondary metabolites (SMs) are an important source of medically valuable compounds. Genome projects have revealed that fungi have many SM biosynthetic gene clusters that are not normally expressed. To access these potentially valuable, cryptic clusters, we have developed a heterologous expression system in Aspergillus nidulans . We have developed an efficient system for amplifying genes from a target fungus, placing them under control of a regulatable promoter, transferring them into A. nidulans , a...
