18‐Crown‐6 Catalyzed Microwave‐mediated Synthesis of Symmetric Bis‐Heterocyclic Compounds under Solvent‐free Condition

An efficient, solvent‐free and 18‐crown‐6 catalyzed method for the synthesis of N‐alkyl‐4‐(4‐(5‐(2‐(alkyl‐amino)thiazol‐4‐yl)pyridin‐3‐yl)phenyl)thiazol‐2‐amine, N‐alkyl‐4‐(5‐(2‐alkyamino)thiazol‐4‐yl)pyridine‐3‐yl)thiazol‐2‐amine, and 4,4′‐bis‐{2‐[amino]‐4‐thiazolyl}biphenyl bis‐heterocyclic derivatives via microwave accelerated cyclization is presented.     

Screening the optical properties of Ag-Au alloy gradients formed by bipolar electrodeposition using surface enhanced Raman spectroscopy

We report the synthesis of Ag-Au alloy gradients on stainless steel substrates using bipolar electrodeposition (BP-ED), a technique based on the existence of a potential gradient at the interface of a bipolar electrode (BPE) and an electrolytic solution. The interfacial potential gradient causes the rates of electrodeposition of Ag and Au to vary along the length of the BPE, leading to the electrodeposition of a chemical concentration gradient. The surface morphology of the electrodeposits was characterized using scanning electron microscopy (SEM), and their chemical composition was determined using energy dispersive X-ray spectroscopy (EDX). Self-assembled monolayers of a Raman-active probe molecule (benzene thiol) were allowed to form on the surface of the alloy gradients, and confocal Raman microscopy was employed to determine the alloy composition that resulted in the maximum surface enhanced Raman scattering (SERS) intensity. An alloy composition of ca. 70% Ag/30% Au was found to be optimum for SERS excited using 514.5 nm radiation, and it is explained on the basis of composition-dependent changes in the local surface plasmon resonance (LSPR) of the electrodeposited Ag-Au alloy.     

The characterisation of coumarins from selected structural classes by electrospray ionisation quadrupole time-of-flight tandem mass spectrometry

Electrospray ionisation quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS) has been used for characterisation of a selection of naturally occurring and synthetic coumarins from different structural classes. The product ions, suggested in earlier studies by electrospray ionisation ion trap mass spectrometry (ESI-MS(n)), are unequivocally established for the representative coumarins by virtue of accurate mass measurement. Synthetic coumarins that are unsubstituted in the heterocyclic ring give rise to a major product ion by loss of CO(2), whereas those substituted in the heterocyclic ring generally undergo alternative fragmentation releasing neutral species such as ketene or methyl ketene. Naturally occurring coumarins, unsubstituted in the heterocyclic ring and substituted in the benzene ring with chains or rings of hydrocarbons and oxygen, principally fragment at the side chain releasing unsaturated hydrocarbons. The ESI-QTOF-MS/MS behaviour of some naturally occurring and synthetic quinolines which are structurally similar or fragment similarly are included where appropriate.     

Semiclassical study of quantum coherence and isotope effects in ultrafast electron transfer reactions coupled to a proton and a phonon bath

The linearized semiclassical initial value representation is employed to describe ultrafast electron transfer processes coupled to a phonon bath and weakly coupled to a proton mode. The goal of our theoretical investigation is to understand the influence of the proton on the electronic dynamics in various bath relaxation regimes. More specifically, we study the impact of the proton on coherences and analyze if the coupling to the proton is revealed in the form of an isotope effect. This will be important in distinguishing reactions in which the proton does not undergo significant rearrangement from those in which the electron transfer is accompanied by proton transfer. Unlike other methodologies widely employed to describe nonadiabatic electron transfer, this approach treats the electronic and nuclear degrees of freedom consistently. However, due to the linearized approximation, quantum interference effects are not captured accurately. Our study shows that at small phonon bath reorganization energies, coherent oscillations and isotope effect are observed in both slow and fast bath regimes. The coherences are more substantially damped by deuterium in comparison to the proton. Further, in contrast to the dynamics of the spin-boson model, the coherences are not long-lived. At large bath reorganization energies, the decay is incoherent in the slow and fast bath regimes. In this case, the extent of the isotope effect depends on the relative relaxation timescales of the proton mode and the phonon bath. The isotope effect is magnified for baths that relax on picosecond timescales in contrast to baths that relax in femtoseconds.     

Single-molecule conductance through multiple π-π-stacked benzene rings determined with direct electrode-to-benzene ring connections

Understanding electron transport across π-π-stacked systems will help to answer fundamental questions about biochemical redox processes and benefit the design of new materials and molecular devices. Herein we employed the STM break-junction technique to measure the single-molecule conductance of multiple π-π-stacked aromatic rings. We studied electron transport through up to four stacked benzene rings held together in an eclipsed fashion via a paracyclophane scaffold. We found that the strained hydrocarbons studied herein couple directly to gold electrodes during the measurements; hence, we did not require any heteroatom binding groups as electrical contacts. Density functional theory-based calculations suggest that the gold atoms of the electrodes bind to two neighboring carbon atoms of the outermost cyclophane benzene rings in η(2) fashion. Our measurements show an exponential decay of the conductance with an increasing number of stacked benzene rings, indicating a nonresonant tunneling mechanism. Furthermore, STM tip-substrate displacement data provide additional evidence that the electrodes bind to the outermost benzene rings of the π-π-stacked molecular wires.     

Synthesis, structure, chemical stability, and electrical properties of Nb-, Zr-, and Nb-codoped BaCeO3 perovskites

We report the effect of donor-doped perovskite-type BaCeO(3) on the chemical stability in CO(2) and boiling H(2)O and electrical transport properties in various gas atmospheres that include ambient air, N(2), H(2), and wet and dry H(2). Formation of perovskite-like BaCe(1-x)Nb(x)O(3±δ) and BaCe(0.9-x)Zr(x)Nb(0.1)O(3±δ) (x = 0.1; 0.2) was confirmed using powder X-ray diffraction (XRD) and electron diffraction (ED). The lattice constant was found to decrease with increasing Nb in BaCe(1-x)Nb(x)O(3±δ), which is consistent with Shannon's ionic radius trend. Like BaCeO(3), BaCe(1-x)Nb(x)O(3±δ) was found to be chemically unstable in 50% CO(2) at 700 °C, while Zr doping for Ce improves the structural stability of BaCe(1-x)Nb(x)O(3±δ). AC impedance spectroscopy was used to estimate electrical conductivity, and it was found to vary with the atmospheric conditions and showed mixed ionic and electronic conduction in H(2)-containing atmosphere. Arrhenius-like behavior was observed for BaCe(0.9-x)Zr(x)Nb(0.1)O(3±δ) at 400-700 °C, while Zr-free BaCe(1-x)Nb(x)O(3±δ) exhibits non-Arrhenius behavior at the same temperature range. Among the perovskite-type oxides investigated in the present work, BaCe(0.8)Zr(0.1)Nb(0.1)O(3±δ) showed the highest bulk electrical conductivity of 1.3 × 10(-3) S cm(-1) in wet H(2) at 500 °C, which is comparable to CO(2) and H(2)O unstable high-temperature Y-doped BaCeO(3) proton conductors.     

Bacteria-based AND logic gate: a decision-making and self-powered biosensor

We developed a bacteria-based AND logic gate using a Pseudomonas aeruginosa lasI/rhlI double mutant with two quorum-sensing signaling molecules as the input signals. We showed a distinct electrical output signal, despite the complexity and continuous regulation of metabolic reactions of living cells.     

Symmetry breaking in quantum chaotic systems

We show, using semiclassical methods, that as a symmetry is broken, the transition between universality classes for the spectral correlations of quantum chaotic systems is governed by the same parametrization as in the theory of random matrices. The theory is quantitatively verified for the kicked rotor quantum map. We also provide an explicit substantiation of the random matrix hypothesis, namely that in the symmetry-adapted basis the symmetry-violating operator is random.     

Phase transitions of a feedback amplifier

The phase transition behaviour of an amplifier with positive feedback is experimentally studied. The results are interpreted using catastrophe theory language. Zero (in Gilmore’s classification), first and second-order transitions are demonstrated by driving the system along appropriate trajectories in control parameter space and the cusp and the spinodal are mapped. The fluctuations of the order parameter are investigated and their relationship to system response time established. Quench experiments analogous to those familiar in condensed matter have also been performed and with similar results.