Temperature dependence of charge recombination in Heliobacillus mobilis

Transient absorption difference spectroscopy was used to study the temperature dependence of the P798+ decay kinetics in heliobacteria. For membrane samples, two components were obtained from the fitting of kinetic traces in the temperature range of 4-29 degrees C. A 3-9 ms component representing the cytochrome (cyt) c oxidation has an activation energy of 33.0 +/- 2.8 kJ/mol. A 12-22 ms component representing either P798+FX- or P798+FA/B- recombination has an activation energy of 15.3 +/- 2.4 kJ/mol. In isolated reaction centers (RC), only one 14 ms component due to P798+FX- recombination was obtained in this temperature range. The Arrhenius plot shows that the recombination rate of this P798+FX- state is temperature independent in the near room temperature range. For RC in the temperature range of 60-298 K, a 12-15 ms decay was obtained at temperatures greater than 240 K. Biphasic decay traces (12-15 ms and 2-4 ms components) were obtained at temperatures between 170 K and 230 K. Only one 2-4 ms component was found at temperatures lower than 160 K. The gradual switchover from the 12-15 ms to the 2-4 ms component upon cooling may indicate the shift of the P798+FX- recombination state to a state that is prior to P798+FX-, although other interpretations can not be excluded. The absorption difference spectrum (delta A @ 160 K - delta A @ 240 K) in the blue region shows a positive amplitude below 405 nm and a negative amplitude above 405 nm implying that the 2-4 ms decay component may be due to the recombination of P798+A1-, where A1 is a quinone-type acceptor.     

Structure and Reactivity of Iron(0)-Phenyltellurolate [PPN][PhTeFe(CO)4]

Anionic iron(0) tetracarbonyl with terminal phenyltellurolate ligand PhTe^?, [PhTeFe(CO)₄]^?, has been synthesized and characterized. The title compound was obtained by addition of (PhTe)₂ to [PPN][HFe(CO)₄] THF solution dropwise. [PPN][PhTeFe(CO)₄] crystallizes in the monoclinic space group C c, with a = 16.119(4) Å, b = 13.141(3) Å, c = 19.880(8) Å, β = 93.04(3)°, V = 4205(2) ų, and Z = 4. The [PhTeFe(CO)₄]^? anion is a trigonal-bipyramidal complex in which the phenyltellurolate ligand occupies an axial position with Fe-Te bond length 2.630(5) Å and the Fe-Te-C(Ph) angle is 103.4(5)°. The neutral iron(0)-telluroether compound, (PhTeMe)Fe(CO)₄, was prepared by alkylation of the [PhTeFe(CO)₄]^?. Protonation of [PhTeFe(CO)₄]^?and reaction of H₂Fe(CO)₄ and PhTe)₂ ultimately lead to formation of the known dimer Fe₂(μ-TePh)₂(CO)₆ and H₂.     

From Chemistry to Translational Medicine: The Application of Proteomics to Cancer Biomarker Discovery and Diagnosis

The study of complex protein mixtures and their interactions in cells and tissues has been difficult due to the tedious process involved in their characterization and analysis. The recent emergence of fast‐evolving and state‐of‐the‐art proteomics methodologies has provided a rapid and scalable platform for understanding the comprehensive proteome profiles from complex whole tissues or cells of various biological sources. Therefore, proteomics has been increasingly valuable to examine real‐time changes in protein expression of various tissues or body fluids from patients with various diseases, especially cancer, resulting in the identification of clinically useful biomarkers for diagnosis, prognosis and disease staging. In this review, we focus on potential biomarkers for (1) Helicobacter pylori‐associated gastric cancer, (2) hepatocellular carcinoma (HCC), and (3) renal cell carcinoma (RCC). In addition to the conventional gel‐based proteomics (1‐D or 2‐D gels), we have utilized a more advanced proteomic approach by incorporating stable isotope dimethyl labelling and shotgun proteomics strategy in combination with nanoliquid chromatography and tandem mass spectrometry (nanoLC‐MS/MS) to better characterize the biomarkers in several cancer tissues. By establishing a high‐throughput proteomics platform based on multiple reaction monitoring (MRM), we have successfully detected and analyzed potential protein markers at low concentrations in various normal and tumor tissues. This platform not only highlights the utility of proteomics for biomarker discovery but also can be uniquely applied to disease‐oriented translational medicine for diagnosis of diverse types of cancers and other diseases.     

Charge‐transfer‐to‐solvent absorption spectra of I−(H2O)3–5 at a finite temperature via simulation

Ground‐state equilibrium Born–Oppenheimer molecular dynamics on I^?(H₂O)_3–5 clusters at ～200 K are performed to sample configurations for calculating the charge‐transfer‐to‐solvent (CTTS) absorption spectra for these clusters. When there are more water molecules in clusters, the calculated CTTS spectra are found to become more intense with the absorption maxima shifting to higher energies, which is in agreement with experimental results. In addition, compared with the findings for optimized structures, the absorption energies of the iodide 5p orbitals are red‐shifted at ～200 K because, on average, the distances between the iodide and the dangling hydrogen atoms are increased at finite temperatures which weakens the interactions between the iodide and water molecules in the clusters. Moreover, the number of ionic hydrogen bonds in the clusters are also reduced. However, it is found that all dangling hydrogen atoms must be considered to obtain a good correlation between the CTTS excitation energy and the average distance between the iodide and the dangling hydrogen atoms, which indicates the existence of the strong interactions of the CTTS electron with all of the dangling hydrogen atoms.     

Development of a Dinitrosyl Iron Complex Molecular Catalyst into a Hydrogen Evolution Cathode

Despite extensive efforts, the electrocatalytic reduction of water using homogeneous/heterogeneous Fe, Co, Ni, Cu, W, and Mo complexes remains challenging because of issues involving the development of efficient, recyclable, stable, and aqueous‐compatible catalysts. In this study, evolution of the de novo designed dinitrosyl iron complex DNIC‐PMDTA from a molecular catalyst into a solid‐state hydrogen evolution cathode, considering all the parameters to fulfill the electronic and structural requirements of each step of the catalytic cycle, is demonstrated. DNIC‐PMDTA reveals electrocatalytic reduction of water at neutral and basic media, whereas its deposit on electrode preserves exceptional longevity, 139 h. This discovery will initiate a systematic study on the assembly of [Fe(NO)₂] motif into current collector for mass production of H₂, whereas the efficiency remains tailored by its molecular precursor [(L)Fe(NO)₂].     

Characterization of Nano‐porous TiO2 Film Prepared by Sol‐gel Process and Its Application to Dye‐sensitized Solar Cell

In this paper, effects of ethylene glycol (EG) and indium tin oxide (ITO) solution on the morphology, porosity, and roughness of TiO₂ film prepared by sol‐gel process were investigated and discussed. Initially, the addition of EG were used to control the viscosity of the solution and it was found to increase the pore size of TiO₂ film. The various TiO₂ films were investigated and characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM) and then assembled to dye‐sensitized solar cell (DSSC) to measure the photoelectric conversion efficiency. The optimum efficiencies of 1.32% with J_sc and V_oc of 2.99 mA/cm² and 0.80 V, respectively, were obtained by the TiO₂ film prepared from a solution containing 20 wt% EG.     

Influences of material source,wafer process and location on silicon die fracture strength

Experimental Techniques -     

Laminar film condensation on a horizontal disk

Heat and Mass Transfer - The problem of two-dimensional, steady film condensation on a finite-size, isothermal horizontal disk is studied for the case in which a cold plate faces upwards. The...     

A novel titanium dioxide-polydimethylsiloxane plate for phosphopeptide enrichment and mass spectrometry analysis

The phosphorylation of proteins is a major post-translational modification that is required for the regulation of many cellular processes and activities. Mass spectrometry signals of low-abundance phosphorylated peptides are commonly suppressed by the presence of abundant non-phosphorylated peptides. Therefore, one of the major challenges in the detection of low-abundance phosphopeptides is their enrichment from complex peptide mixtures. Titanium dioxide (TiO₂) has been proven to be a highly efficient approach for phosphopeptide enrichment and is widely applied. In this study, a novel TiO₂ plate was developed by coating TiO₂ particles onto polydimethylsiloxane (PDMS)-coated MALDI plates, glass, or plastic substrates. The TiO₂-PDMS plate (TP plate) could be used for on-target MALDI-TOF analysis, or as a purification plate on which phosphopeptides were eluted out and subjected to MALDI-TOF or nanoLC-MS/MS analysis. The detection limit of the TP plate was ∼10-folds lower than that of a TiO₂-packed tip approach. The capacity of the ∼2.5 mm diameter TiO₂ spots was estimated to be ∼10 μg of β-casein. Following TiO₂ plate enrichment of SCC4 cell lysate digests and nanoLC-MS/MS analysis, ∼82% of the detected proteins were phosphorylated, illustrating the sensitivity and effectiveness of the TP plate for phosphoproteomic study.     

Low-frequency noise characteristics of GaN-based UV photodiodes with AlN/GaN buffer layers prepared on Si substrates

Nitride-based metal–semiconductor–metal ultraviolet (UV) photodetectors prepared on Si (1 1 1) substrate with stacked buffer layers were proposed and prepared. With 5 V applied bias, it was found that dark current of the fabricated device was only 7.95×10⁻¹² A. With an applied bias of 10 V, it was found that peak responsivity was 0.06 A/W, corresponding to quantum efficiency of 21.2% while UV/visible rejection ratio was 244. With 5 V applied bias, it was found that noise equivalent power, NEP and detectivity, D*, of our detector were 1.70×10⁻¹³ W and 1.18×10¹³ cm Hz^0.5 W⁻¹, respectively.