Constructing modular separating invariants

We consider a finite dimensional modular representation V of a cyclic group of prime order p. We show that two points in V that are in different orbits can be separated by a homogeneous invariant polynomial that has degree one or p and that involves variables from at most two summands in the dual representation. Simultaneously, we describe an explicit construction for a separating set consisting of polynomials with these properties.     

Finding transition pathways using the string method with swarms of trajectories

An approach to find transition pathways in complex systems is presented. The method, which is related to the string method in collective variables of Maragliano et al. (J. Chem. Phys. 2006, 125, 024106), is conceptually simple and straightforward to implement. It consists of refining a putative transition path in the multidimensional space supported by a set of collective variables using the average dynamic drift of those variables. This drift is estimated on-the-fly via swarms of short unbiased trajectories started at different points along the path. Successive iterations of this algorithm, which can be naturally distributed over many computer nodes with negligible interprocessor communication, refine an initial trial path toward the most probable transition path (MPTP) between two stable basins. The method is first tested by determining the pathway for the C7eq to C7ax transition in an all-atom model of the alanine dipeptide in vacuum, which has been studied previously with the string method in collective variables. A transition path is found with a committor distribution peaked at 1/2 near the free energy maximum, in accord with previous results. Last, the method is applied to the allosteric conformational change in the nitrogen regulatory protein C (NtrC), represented here with a two-state elastic network model. Even though more than 550 collective variables are used to describe the conformational change, the path converges rapidly. Again, the committor distribution is found to be peaked around 1/2 near the free energy maximum between the two stable states, confirming that a genuine transition state has been localized in this complex multidimensional system.     

New Pt(0) Nanoparticles as Highly Active and Reusable Catalysts in the C1–C3 Alcohol Oxidation and the Room Temperature Dehydrocoupling of Dimethylamine-Borane (DMAB)

New Pt(0) nanoparticles were easily and reproducibly prepared by the simultaneous reduction method using 1-butylamine (BA) and tributylamine (TBA) for the first time as capturing ligands at room temperature. X-ray diffraction, X-ray photoelectron microscopy and transmission electron microscopy measurements verify the formation of well-dispersed Pt(0) nanoparticles [~3.63 and ~3.98 nm for catalysts prepared using BA (catalyst I) and TBA (catalyst II), respectively] on an activated carbon surface. The catalytic performances of these nanoparticles in terms of activity, isolability and reusability were investigated for both alcohol oxidation and the dehydrocoupling of dimethylamine-borane (DMAB). These nanoparticles were shown to be as active and reusable heterogeneous catalysts even at room temperature. The prepared catalysts can catalyze the dehydrogenation of DMAB with one of the highest known activities at room temperature and also C1–C3 alcohol oxidation with very high electrochemical activities.     

Vibrational spectra and structure of CH3Cl:(H2O)2 and CH3Cl:(D2O)2 complexes. IR matrix isolation and ab initio calculations

The infrared spectra of CH3Cl + H2O isolated in solid neon at low temperature have been investigated. High concentration studies of water (0.01%-4%) and subsequent annealing lead to the formation of the ternary CH3Cl:(H2O)2 complex. Detailed vibrational assignments were made on the observed spectra of water and deuterated water engaged in the complex. In parallel, structural, energetic, and vibrational properties of the complex have been studied at the second-order M?ller-Plesset perturbation theory using several basis sets. Anaharmonic correction to the vibrational frequencies has been done with the standard second-order perturbation approach. It was shown that the ground state of the complex has a cyclic form for which the nonadditive three-body contribution was found to be around 10% of the interaction energy.     

A new approach to liquid penetrant inspection: radiolabeled QDots

Penetrant technique is a sensitive non-destructive testing (NDT) method for detecting and locating the presence of cracks in sample surface. Today, NDT is used in a wide range of industries including aerospace, biotechnology, defence, marine, oil–gas and energy plants. This work focuses on potential use of radiolabeled ZnS coated CdTe quantum dots (QDots) as a penetrant for liquid penetrant testing. The synthesized QDots as a precursor were tested for surface defects detection in welded joints. The experimental results show the highest activities were found in defects on the sample surface. These finding are consistent with the sample NDT inspection test report.     

A mathematical model for personalized advertisement in virtual reality environments

We consider a personalized advertisement assignment problem faced by the manager of a virtual reality environment. In this online environment, users log in/out, and they spend time in different virtual locations while they are online. Every time a user visits a new virtual location, the site manager can show the ad of an advertiser. At the end of a fixed time horizon, the manager collects revenues from all of the advertisers, and the total revenue depends on the number of ads of different advertisers she displays to different users. In this setup, the objective of the manager is to find an optimal dynamic ad display policy in order to maximize her expected revenue. In the current paper, we formulate this problem as a continuous time stochastic optimization problem in which the actions of users are represented with two-state Markov processes and the manager makes display decisions at the transition times of these processes. To our best knowledge, no formal stochastic model and rigorous analysis has been given for this practical problem. Such a model and its analysis are the major contributions of this paper along with an optimal solution.     

Amperometric Lactate Biosensor Based on Carbon Paste Electrode Modified with Benzo[c]cinnoline and Multiwalled Carbon Nanotubes

Amperometric lactate biosensor based on a carbon paste electrode modified with benzo[c]cinnoline and multiwalled carbon nanotubes is reported. Incorporation of benzo[c]cinnoline acting as a mediator and multiwalled carbon nanotubes providing a conduction pathway to accelerate electron transfer due to their excellent conductivity into carbon paste matrix resulted in a high performance lactate biosensor. The resulting biosensor exhibited a fast response, high selectivity, good repeatability and storage stability. Under the optimal conditions, the enzyme electrode showed the detection limit of 7.0×10^?8 M with a linear range of 2.0×10^?7 M–1.1×10^?4 M. The usefulness of the biosensor was demonstrated in serum samples.     

Stability of high‐mass molecular libraries: the role of the oligoporphyrin core

Molecular beam techniques are a key to many experiments in physical chemistry and quantum optics. In particular, advanced matter‐wave experiments with high‐mass molecules profit from the availability of slow, neutral and mass‐selected molecular beams that are sufficiently stable to remain intact during laser heating and photoionization mass spectrometry. We present experiments on the photostability with molecular libraries of tailored oligoporphyrins with masses up to 25 000 Da. We compare two fluoroalkylsulfanyl‐functionalized libraries based on two different molecular cores that offer the same number of anchor points for functionalization but differ in their geometry and electronic properties. A pentaporphyrin core stabilizes a library of chemically well‐defined molecules with more than 1600 atoms. They can be neutrally desorbed with velocities as low as 20 m/s and efficiently analyzed in photoionization mass spectrometry. Copyright © 2015 John Wiley & Sons, Ltd.     

Spectroscopic Observation of Calcium‐Induced Reorientation of Cellobiose Dehydrogenase Immobilized on Electrodes and its Effect on Electrocatalytic Activity

Cellobiose dehydrogenase catalyzes the oxidation of various carbohydrates and is considered as a possible anode catalyst in biofuel cells. It has been shown that the catalytic performance of this enzyme immobilized on electrodes can be increased by presence of calcium ions. To get insight into the Ca²⁺‐induced changes in the immobilized enzyme we employ surface‐enhanced vibrational (SERR and SEIRA) spectroscopy together with electrochemistry. Upon addition of Ca²⁺ ions electrochemical measurements show a shift of the catalytic turnover signal to more negative potentials while SERR measurements reveal an offset between the potential of heme reduction and catalytic current. Comparing SERR and SEIRA data we propose that binding of Ca²⁺ to the heme induces protein reorientation in a way that the electron transfer pathway of the catalytic FAD center to the electrode can bypass the heme cofactor, resulting in catalytic activity at more negative potentials.