Tuning Optical Properties of Si Quantum Dots by π‐Conjugated Capping Molecules

The absorption and photoluminescence (PL) properties of silicon quantum dots (QDs) are greatly influenced by their size and surface chemistry. Herein, we examined the optical properties of three Si QDs with increasing σ–π conjugation length: octyl‐, (trimethylsilyl)vinyl‐, and 2‐phenylvinyl‐capped Si QDs. The PL photon energy obtained from as‐prepared samples decreased by 0.1–0.3 eV, while the PL excitation (PLE) extended from 360 nm (octyl‐capped Si QDs) to 400 nm (2‐phenylvinyl‐capped Si QDs). A vibrational PL feature was observed in all samples with an energy separation of about 0.192±0.013 eV, which was explained based on electron–phonon coupling. After soft oxidization through drying, all samples showed blue PL with maxima at approximately 410 nm. A similar high‐energy peak was observed with the bare Si QD sample. The changes in the optical properties of Si QDs were mainly explained by the formation of additional states arising from the strong σ–π conjugation and QD oxidation.     

Limits for the central production of Theta+ and Xi(--)pentaquarks in 920-GeV pA collisions

We have searched for Theta+(1540) and Xi(--)(1862) pentaquark candidates in proton-induced reactions on C, Ti, and W targets at midrapidity and square root of s = 41.6 GeV. In 2 x 10(8) inelastic events we find no evidence for narrow (sigma approximately 5 MeV) signals in the Theta+ --> pK0(S) and Xi(--) --> Xi- pi- channels; our 95% C.L. upper limits (UL) for the inclusive production cross section times branching fraction B dsigma/dy/(y approximately 0) are (4-16) mub/N for a Theta+ mass between 1521 and 1555 MeV, and 2.5 mub/N for the Xi(--). The UL of the yield ratio of Theta+/Lambda(1520) < (3-12)% is significantly lower than model predictions. Our UL of B Xi(--)/Xi(1530)0 < 4% is at variance with the results that have provided the first evidence for the Xi(--).     

Tetrathiafulvalene hydrazone an efficient precursor of various chelating electroactive ligands

Novel bidentate electroactive ligands containing one or two tetrathiafulvalene (TTF) cores as redox active unit have been synthesized thanks to the condensation of various carbonyl derivatives with TTF hydrazone. The electron donating ability of these redox active ligands determined by cyclic voltammetry is described together with the investigations of their molecular structures by X-ray diffraction studies. The chelating ability of these ligands has been exemplified through the coordination to molybdenum carbonyl fragment or the complexation to difluoroboron moiety.     

Universal state-selective corrections to multi-reference coupled-cluster theories with single and double excitations

The recently proposed universal state-selective (USS) corrections [K. Kowalski, J. Chem. Phys. 134, 194107 (2011)] to approximate multi-reference coupled-cluster (MRCC) energies can be commonly applied to any type of MRCC theory based on the Jeziorski-Monkhorst [B. Jeziorski and H. J. Monkhorst, Phys. Rev. A 24, 1668 (1981)] exponential ansatz. In this paper we report on the performance of a simple USS correction to the Brillouin-Wigner and Mukherjee's MRCC approaches employing single and double excitations (USS-BW-MRCCSD and USS-Mk-MRCCSD). It is shown that the USS-BW-MRCCSD correction, which employs the manifold of single and double excitations, can be related to a posteriori corrections utilized in routine BW-MRCCSD calculations. In several benchmark calculations we compare the USS-BW-MRCCSD and USS-Mk-MRCCSD results with the results obtained with the full configuration interaction method.     

Optimization of photo-polymerized sol–gel monolithic stationary phases prepared in polyacrylate-coated fused-silica capillaries for capillary electrochromatography

The preparation of photo-polymerized sol–gel monolithic stationary phases (MSP) within 100 μm internal diameter polyacrylate-coated fused-silica capillaries for use in capillary electrochromatography (CEC) was optimized. Eight mixtures containing different amounts of methacryloxypropyltrimethoxysilane (MPTMS) as the polymeric precursor, hydrochloric acid solution as the catalyst, toluene as the porogen and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819) as the photo-initiator were irradiated at 370 nm inside the capillaries in order to complete the MSP polymerization, according to a fractional factorial experimental design 2_IV^4-1. All the preparation procedure, from capillary pretreatment until the MSP is ready to use in CEC, were made in less than four hours in mild conditions. A high pressurization injection device (HPID) useful for micro-volume syringes was built in order to achieve practical, controlled and precise injections of sols, solvents and electrolytes in the capillaries. The eight MSP were equally washed, conditioned and submitted to CEC procedures via short-end injection, which showed higher efficiency and peak height taking shorter analysis time. Electrochromatographic behaviors of the MSP were corroborated with morphological characterizations by scanning electron microscopy. The optimum condition, which allowed the separation of standard mixture containing thiourea (marker compound), naphthalene, acenaphthene, fluorene, phenanthrene and anthracene in twelve minutes without external pressure assistance, showed efficiencies up to 51,460 N/m, relative standard deviation from 0.05 to 3.3% for migration/retention time and from 0.14 to 1.6% for relative area (considering thiourea as an internal standard) and also showed no statistical evidence that three MSP prepared at the same condition are different within 95% confidence interval.     

Purification and Partial Characterization of an Exo-polygalacturonase from Paecilomyces variotii Liquid Cultures

An extracellular polygalacturonase (PG) produced from Paecilomyces variotii was purified to homogeneity through two chromatography steps using DEAE-Fractogel and Sephadex G-100. The molecular weight of P. variotii PG was 77,300 Da by gel filtration and SDS-PAGE. PG had isoelectric point of 4.37 and optimum pH 4.0. PG was very stable from pH 3.0 to 6.0. The extent of hydrolysis of different pectins by the purified enzyme was decreased with an increase in the degree of esterification. PG had no activity toward non-pectic polysaccharides. The apparent K _m and V _max values for hydrolyzing sodium polypectate were 1.84 mg/mL and 432 μmol/min/mg, respectively. PG was found to have temperature optimum at 65 °C and was totally stable at 45 °C for 90 min. Half-life at 55 °C was 50.6 min. Almost all the examined metal cations showed partial inhibitory effects under enzymatic activity, except for Na⁺¹, K⁺¹, and Co⁺² (1 mM) and Cu⁺² (1 and 10 mM).     

On the stability of a variety of organic photovoltaic devices by IPCE and in situ IPCE analyses - the ISOS-3 inter-laboratory collaboration

This work is part of the inter-laboratory collaboration to study the stability of seven distinct sets of state-of-the-art organic photovoltaic (OPV) devices prepared by leading research laboratories. All devices have been shipped to and degraded at RIS?-DTU up to 1830 hours in accordance with established ISOS-3 protocols under defined illumination conditions. In this work, we apply the Incident Photon-to-Electron Conversion Efficiency (IPCE) and the in situ IPCE techniques to determine the relation between solar cell performance and solar cell stability. Different ageing conditions were considered: accelerated full sun simulation, low level indoor fluorescent lighting and dark storage. The devices were also monitored under conditions of ambient and inert (N(2)) atmospheres, which allows for the identification of the solar cell materials more susceptible to degradation by ambient air (oxygen and moisture). The different OPVs configurations permitted the study of the intrinsic stability of the devices depending on: two different ITO-replacement alternatives, two different hole extraction layers (PEDOT:PSS and MoO(3)), and two different P3HT-based polymers. The response of un-encapsulated devices to ambient atmosphere offered insight into the importance of moisture in solar cell performance. Our results demonstrate that the IPCE and the in situ IPCE techniques are valuable analytical methods to understand device degradation and solar cell lifetime.     

Nitric oxide flow tagging in unseeded air

A scheme for molecular tagging velocimetry is presented that can be used in air flows without any kind of seeding. The method is based on the local and instantaneous creation of nitric oxide (NO) molecules from N(2) and O(2) in the waist region of a focused ArF excimer laser beam. This NO distribution is advected by the flow and can be visualized any time later by laser-induced fluorescence in the gamma bands. The creation of NO is confirmed by use of an excitation spectrum. Two examples of the application of the new scheme for air-flow velocimetry are given in which single laser pulses are used for creation and visualization of NO.     

Ultrafast Dynamics of Solvation and Charge Transfer in a DNA‐Based Biomaterial

Charge migration along DNA molecules is a key factor for DNA‐based devices in optoelectronics and biotechnology. The association of a significant amount of water molecules in DNA‐based materials for the intactness of the DNA structure and their dynamic role in the charge‐transfer (CT) dynamics is less documented in contemporary literature. In the present study, we have used a genomic DNA–cetyltrimethyl ammonium chloride (CTMA) complex, a technological important biomaterial, and Hoechest 33258 (H258), a well‐known DNA minor groove binder, as fluorogenic probe for the dynamic solvation studies. The CT dynamics of CdSe/ZnS quantum dots (QDs; 5.2 nm) embedded in the as‐prepared and swollen biomaterial have also been studied and correlated with that of the timescale of solvation. We have extended our studies on the temperature‐dependent CT dynamics of QDs in a nanoenvironment of an anionic, sodium bis(2‐ethylhexyl)sulfosuccinate reverse micelle (AOT RMs), whereby the number of water molecules and their dynamics can be tuned in a controlled manner. A direct correlation of the dynamics of solvation and that of the CT in the nanoenvironments clearly suggests that the hydration barrier within the Arrhenius framework essentially dictates the charge‐transfer dynamics.     

Simulation of Redox‐Cycling Phenomena at Interdigitated Array (IDA) Electrodes: Amplification and Selectivity

We present Finite Element Method (FEM) simulations of interdigitated array (IDA) electrode geometries to study and verify redox selectivity and redox cycling amplification factor. The simulations provide an adequate explanation of an earlier found, but poorly understood, high amplification factor (65×) in a 1 μm‐spaced IDA microdevice. Moreover, using the FEM calculations we present selectivity measurements with IDA electrodes in a mixture of two redox species, as for example dopamine and ferricyanide. We show that it is possible to electrochemically detect dopamine in presence of the stronger reductor ferricyanide, which is impossible with direct amperometric detection, with the use of IDA electrodes with proper polarization potential of the collector electrode. Using our simulations, we show that a theoretical selectivity of dopamine over ferricyanide of 11 can be achieved.