TDDFT Investigation of the Electronic Structures and Photophysical Properties of Fluorescent Extended Styryl Push-Pull Chromophores Containing Carbazole Unit

Push-pull chromophores attached to carbazole based π-conjugating spacers bearing N-alkylamino donors, cyanovinyl and carbethoxy acceptors have been studied by the means of UV-Visible measurements. The intramolecular charge transfer (ICT) of these π-conjugated systems has also been tested by investigating the ability of the solute molecules to undergo shifts in their fluorescence emission maxima with increasing solvent polarity. Density Functional Theory [B3LYP/6-31G(d)] and Time Dependent Density Functional Theory [TD-B3LYP/6-31G(d)] computations have been used to have more understanding of the structural, molecular, electronic and photophysical parameters of push-pull dyes. The largest wavelength difference between the experimental and computed electronic absorption maxima was 45 nm. For emission, a largest difference of 61 nm was observed. The ground state and excited state dipole moments in different solvents were determined using experimental solvatochromic data and computed Onsager radii. The dipole moments of the molecules in the excited state were observed to be higher than in the ground state.     

Nonlinear programming without differentiability in banach spaces: necessary and sufficient constraint qualification

The problem under consideration is a maximization problem over a constraint set defined by a finite number of inequality and equality constraints over an arbitrary set in a reflexive Banach space. A generalization of the Kuhn-Tucker necessary conditions is developed where neither the objective function nor the constraint functions are required to be differentiable. A new constraint qualification is imposed in order to validate the optimality criteria. It is shown that this qualification is the weakest possible in the sense that it is necessary for the optimality criteria to hold at the point under investigation for all families of objective functions having a constrained local maximum at this point     

Coherent States and Modified de Broglie-Bohm Complex Quantum Trajectories

This paper examines the nature of classical correspondence in the case of coherent states at the level of quantum trajectories. We first show that for a harmonic oscillator, the coherent state complex quantum trajectories and the complex classical trajectories are identical to each other. This congruence in the complex plane, not restricted to high quantum numbers alone, illustrates that the harmonic oscillator in a coherent state executes classical motion. The quantum trajectories we consider are those conceived in a modified de Broglie-Bohm scheme. Though quantum trajectory representations are widely discussed in recent years, identical classical and quantum trajectories for coherent states are obtained only in the present approach. We may note that this result for standard harmonic oscillator coherent states is not totally unexpected because of their holomorphic nature. The study is extended to coherent states of a particle in an infinite potential well and that in a symmetric Poschl-Teller potential by solving for the trajectories numerically. For the Gazeau-Klauder coherent state of the infinite potential well, almost identical classical and quantum trajectories are obtained whereas for the Poschl-Teller potential, though classical trajectories are not regained, a periodic motion results as t→∞. Similar features were found for the SUSY quantum mechanics-based coherent states of the Poschl-Teller potential too, but this time the pattern of complex trajectories is quite different from that of the previous case. Thus we find that the method is a potential tool in analyzing the properties of generalized coherent states.     

Significance of plaque morphology in modifying flow characteristics in a diseased coronary artery: Numerical simulation using plaque measurements from intravascular ultrasound imaging

The paper deals with numerical investigation of the effect of plaque morphology on the flow characteristics in a diseased coronary artery using realistic plaque morphology. The morphological information of the lumen and the plaque is obtained from intravascular ultrasound imaging measurements of 42 patients performed at Cleveland Clinic Foundation, Ohio. For this data, study of Bhaganagar et al. (2010) [1] has revealed the stenosis for 42 patients can be categorized into four types – type I (peak-valley), type II (ascending), type III (descending), and type IV (diffuse). The aim of the present study is to isolate the effect of shape of the stenosis on the flow characteristics for a given degree of the stenosis. In this study, we conduct fluid dynamic simulations for the four stenosis types (type I–IV) and analyze the differences in the flow characteristics between these types. Finely refined tetrahedral mesh for the 3-D solid model of the artery with plaques has been generated. The 3-D steady flow simulations were performed using the turbulence (k–ε) model in a finite volume based computational fluid dynamics solver. The axial velocity, the radial velocity, turbulence kinetic energy and wall shear stress profiles of the plaque have been analyzed. From the axial and radial velocity profiles results the differences in the velocity patterns are significantly visible at proximal as well as distal to the throat, region of maximum stenosis. Turbulent kinetic energy and wall shear stress profiles have revealed significant differences in the vicinity of the plaque. Additional unsteady flow simulations have been performed to validate the hypothesis of the significance of plaque morphology in flow alterations in diseased coronary artery. The results revealed the importance of accounting for plaque morphology in addition to plaque height to accurately characterize the turbulent flow in a diseased coronary artery.     

High-field NMR using resistive and hybrid magnets

Resistive and resistive-superconducting hybrid magnets can generate dc magnetic fields much higher than conventional superconducting NMR magnets but the field spatial homogeneity and temporal stability are usually not sufficient for high-resolution NMR experiments. Hardware and technique development addressing these issues are presented for high-resolution NMR at magnetic fields up to 40T. Passive ferromagnetic shimming and magic-angle spinning are used effectively to reduce the broadening from inhomogeneous magnetic field. A phase correction technique based on simultaneous heteronuclear detection is developed to compensate magnetic field fluctuations to achieve high spectral resolution.     

Synthesis and Characterization of Novel 1‐Methyl‐3‐(4‐phenyl‐4H‐1,2,4‐triazol‐3‐yl)‐1H‐indazole Derivatives

A series of novel 1‐methyl‐3‐(4‐phenyl‐4H‐1,2,4‐triazol‐3‐yl)‐1H‐indazoles was synthesized in three steps from 5‐(1‐methyl‐1H‐indazol‐3‐yl)‐4‐phenyl‐2H‐1,2,4‐triazole‐3(4H)‐thiones. 5‐(1‐Methyl‐1H‐indazol‐3‐yl)‐4‐phenyl‐2H‐1,2,4‐triazole‐3(4H)‐thiones were converted into 1‐methyl‐3‐(5‐(methylsulfonyl)‐4‐phenyl‐4H‐1,2,4‐triazol‐3‐yl)‐1H‐indazoles upon methylation followed by treatment with aq. KMnO₄. The reaction of 1‐methyl‐3‐(5‐(methylsulfonyl)‐4‐phenyl‐4H‐1,2,4‐triazol‐3‐yl)‐1H‐indazoles with Raney nickel resulted in desulphonylation to afford corresponding 1‐methyl‐3‐(4‐phenyl‐4H‐1,2,4‐triazol‐3‐yl)‐1H‐indazoles. All the new synthesized compounds were characterized by spectral techniques.     

Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit

The structurally precise Cu‐rich hydride nanoclusters [PdCu₁₄H₂(dtc/dtp)₆(C≡CPh)₆] (dtc: di‐butyldithiocarbamate ( 1 ); dtp: di‐isopropyl dithiophosphate ( 2 )) were synthesized from the reaction of polyhydrido copper clusters [Cu₂₈H₁₅(S₂CNⁿBu₂)₁₂]⁺ or [Cu₂₀H₁₁{S₂P(OⁱPr)₂}₉] with phenyl acetylene in the presence of Pd(PPh₃)₂Cl₂. Their structures and compositions were determined by single‐crystal X‐ray diffraction and the results supported by ESI‐mass spectrometry. Hydride positions in 1 were confirmed by single‐crystal neutron diffraction. Each hydride is connected to one Pd⁰ and four Cu^I atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH₂]^2? unit and its Cu₁₄ bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.     

Nanopore Sequencing Accurately Identifies the Mutagenic DNA Lesion O6‐Carboxymethyl Guanine and Reveals Its Behavior in Replication

O⁶‐carboxymethylguanine (O⁶‐CMG) is a highly mutagenic alkylation product of DNA, triggering transition mutations relevant to gastrointestinal cancer. However, precise localization of a single O⁶‐CMG with conventional sequencing platforms is challenging. Here nanopore sequencing (NPS), which directly senses single DNA bases according to their physiochemical properties, was employed to detect O⁶‐CMG. A unique O⁶‐CMG signal was observed during NPS and a single‐event call accuracy of >95 % was achieved. Moreover, O⁶‐CMG was found to be a replication obstacle for Phi29 DNA polymerase (Phi29 DNAP), suggesting this lesion could cause DNA sequencing biases in next generation sequencing (NGS) approaches.     

Design,Synthesis, and Biological Activity of New Bis-1,2,3-triazole Derivatives Bearing Thiophene-Chalcone Moiety

Russian Journal of General Chemistry - A series of novel 1,4-substituted bis-aralkyl and aryl 1,2,3-triazoles bearing thiophene chalcones are synthesized via the Claisen condensation of bis...     

Efficient electrode material for electrochemical energy storage from organic waste

Journal of Solid State Electrochemistry - Heteroatom functionalities in activated carbons have a positive effect on their electrochemical properties. High surface area, reasonable heteroatom...