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151.
The aggregation of alpha-synuclein in dopaminergic neurons of the substantia nigra is a critical step in the pathogenesis of Parkinson's disease. We show that the antibiotic rifampicin inhibited alpha-synuclein fibrillation and disaggregated existing fibrils in a concentration-dependent manner. Size-exclusion chromatography data indicated that rifampicin stabilized alpha-synuclein as both a monomer and soluble oligomers comprised of partially folded alpha-synuclein. Experiments using aged samples of rifampicin indicated that the most active species in inhibiting fibrillation and disaggregating fibrils is an oxidation product of rifampicin, which was confirmed in experiments under anaerobic conditions. These results indicate that rifampicin-mediated inhibition of alpha-synuclein fibrillation and disaggregation of fibrils involves preferential stabilization of monomeric and soluble oligomeric forms, and that rifampicin potentially may have therapeutic application for Parkinson's disease. 相似文献
152.
We obtained a long-time-storage mechanism for spectral features in thulium ions doped into YAG by applying a magnetic field that splits the electronic ground state. We show experimentally that the storage time can be more than 30 s, which is 3 orders of magnitude longer than that of the metastable state that normally is used for information storage in this material. Level splitting and storage lifetimes for various magnetic field strengths of as much as 5 T were investigated. This storage mechanism will be relevant in the many coherent transient-based signal-processing schemes in which Tm:YAG is being used, and we demonstrate long-time storage in a basic data storage application. 相似文献
153.
We describe the implementation of an adaptive umbrella sampling method, making use of the weighted histogram analysis method, for computing multidimensional potential of mean force for chemical reaction in solution. The approach is illustrated by investigating the effect of aqueous solution on the free energy surface for the proton transfer reaction of [H(3)N-H-NH(3)](+) using a combined quantum mechanical and molecular mechanical AM1/TIP3P potential. 相似文献
154.
Shultz DA Fico RM Bodnar SH Kumar RK Vostrikova KE Kampf JW Boyle PD 《Journal of the American Chemical Society》2003,125(38):11761-11771
A magnetostructural correlation (conformational electron spin exchange modulation) within an isostructural series of biradical complexes is presented. X-ray crystal structures, variable-temperature electron paramagnetic resonance spectroscopy, zero-field splitting parameters, and variable-temperature magnetic susceptibility measurements were used to evaluate molecular conformation and electron spin exchange coupling in this series of molecules. Our combined results indicate that the ferromagnetic portion of the exchange couplings occurs via the cross-conjugated pi-systems, while the antiferromagnetic portion occurs through space and is equivalent to incipient bond formation. Thus, molecular conformation controls the relative amounts of ferro- and antiferromagnetic contributions to exchange coupling. In fact, the exchange parameter correlates with average semiquinone ring torsion angles via a Karplus-Conroy-type relation. Because of the natural connection between electron spin exchange coupling and electronic coupling related to electron transfer, we also correlate the exchange parameters in the biradical complexes to mixed valency in the corresponding quinone-semiquinone radical anions. Our results suggest that delocalization in the cross-conjugated, mixed-valent radical anions is proportional to the ferromagnetic contribution to the exchange coupling in the biradical oxidation states. 相似文献
155.
A.B. Weerasekara M.B.M. Rinzan S.G. Matsik A.G.U. Perera M. Buchanan H.C. Liu G. von Winckel A. Stintz S. Krishna 《Infrared Physics & Technology》2007,50(2-3):194-198
Terahertz detection capability of an n-type heterojunction interfacial work function internal photoemission (HEIWIP) detector is demonstrated. Threshold frequency, f0, of 3.2 THz (93 μm) was obtained by using n-type GaAs emitter doped to 1 × 1018 cm−3 and Al0.04Ga0.96As single barrier structure. The detector shows a broad spectral response from 30 to 3.2 THz (10–93 μm) with peak responsivity of 6.5 A/W at 7.1 THz under a forward bias field of 0.7 kV/cm at 6 K. The peak quantum efficiency and peak detectivity are 19% and 5.5 × 108 Jones, respectively under a bias field of 0.7 kV/cm at 6 K. In addition, the detector can be operated up to 25 K. 相似文献
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157.
Krishna Dan Priya Rajdev Jolly Deb Siddhartha S. Jana Suhrit Ghosh 《Journal of polymer science. Part A, Polymer chemistry》2013,51(22):4932-4943
Synthesis of a library of amphiphilic random copolymers from a single reactive pre‐polymer and their self‐assembly is reported. Post‐polymerization modifications of the parent polymer containing pendant N‐hydroxy succinimide (NHS) ester groups with various oligooxyethylene (OE) amines produce amphiphilic random copolymers with same degree of polymerization and equal extent of randomness. 1H‐NMR and FT‐IR data indicate quantitative substitution in all cases. The critical aggregation concentration (CAC) for all the polymers is estimated to be in the range of 10?5 M. Stability of these nano‐aggregates is studied by photoluminescence using time dependent F—rster Resonance Energy Transfer (FRET) between co‐encapsulated lipophilic dyes namely DiO and DiI in the hydrophobic pocket of the aggregates. These studies suggest remarkably high stability for all systems. However those with shorter hydrophilic pendant chains are found to be even more robust. Morphology is examined by high resolution transmission electron microscopy (HRTEM) which reveals multi‐micellar clusters and vesicles for polymers containing short and longer OE segments, respectively. Encapsulation efficacy is tested with both hydrophobic and hydrophilic guest molecules. All of them can encapsulate hydrophobic guest pyrene while a hydrophilic dye Calcein can be sequestered only in vesicle forming polymers. Lower critical solution temperature (LCST) is exhibited by only one polymer that contains the shortest OE chains. All polymers exhibit excellent cell viability as determined by MTT assay. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4932–4943 相似文献
158.
Harihara Padhy Duryodhan Sahu Dhananjaya Patra Murali Krishna Pola Jen‐Hsien Huang Chih‐Wei Chu Kung‐Hwa Wei Hong‐Cheu Lin 《Journal of polymer science. Part A, Polymer chemistry》2011,49(15):3417-3425
Two β‐cyano‐thiophenevinylene‐based polymers containing cyclopentadithiophene ( CPDT‐CN ) and dithienosilole ( DTS‐CN ) units were synthesized via Stille coupling reaction with Pd(PPh3)4 as a catalyst. The effects of the bridged atoms (C and Si) and cyano‐vinylene groups on their thermal, optical, electrochemical, charge transporting, and photovoltaic properties were investigated. Both polymers possessed the highest occupied molecular orbital (HOMO) levels of about ?5.30 eV and the lowest unoccupied molecular orbital (LUMO) levels of about ?3.60 eV, and covered broad absorption ranges with narrow optical band gaps (ca. 1.6 eV). The bulk heterojunction polymer solar cell (PSC) devices containing an active layer of electron‐donor polymers ( CPDT‐CN and DTS‐CN ) blended with an electron‐acceptor, that is, [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC61BM) or [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM), in different weight ratios were explored under 100 mW/cm2 of AM 1.5 white‐light illumination. The PSC device based on DTS‐CN: PC71BM (1:2 w/w) exhibited a best power conversion efficiency (PCE) value of 2.25% with Voc = 0.74 V, Jsc = 8.39 mA/cm2, and FF = 0.36. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011. 相似文献
159.
160.