C-13-H-1 dipolar couplings for probing rod-like hydrogen bonded mesogens

Hydrogen bonding is the most important non-covalent interaction utilised in building supramolecular assemblies and is preferred often as a means of construction of molecular, oligomeric as well as polymeric materials that show liquid crystalline properties. In this work, a pyridine based nematogenic acceptor has been synthesized and mixed with non-mesogenic 4-methoxy benzoic acid to get a hydrogen bonded mesogen. The existence of hydrogen bonding between the pyridyl unit and the carboxylic acid was established using FT-IR spectroscopy from the observation of characteristic stretching vibrations of unionized type at 2425 and 1927 cm(-1). The mesogenic acceptor and the complex have been investigated using C-13 NMR in solution, solid and liquid crystalline states. Together with the 2D separated local field NMR experiments, the studies confirm the molecular structure in the mesophase and yield the local orientational order parameters. It is observed that the insertion of 4-methoxy benzoic acid not only enhances the mesophase stability but also induces a smectic phase due to an increase in the core length of the hydrogen bonded mesogen.

Ionothermal synthesis of TiO2 nanoparticles: Photocatalytic hydrogen generation

Rutile phase TiO2 nanoparticles have been successfully prepared at 120 degrees C for one day via the ionothermal method using imidazolium based functionalized ionic liquid. The obtained products have been characterized by various techniques. XRD pattern shows rutile phase with crystallite size similar to 15 nm. FTIR shows a band at similar to 410 cm(-1) assigned to Ti-O-Ti stretching vibrations and few other bands due to the presence of ionic liquid. UV-vis studies show maximum absorbance at similar to 215 nm due to the imidazolium moiety and a band at 316 nm due to TiO2 nanoparticles. TEM images show that the size of particle is similar to 30 nm. TG-DTA shows weight loss corresponding to the formation of stable TiO2 nanoparticles. The rutile TiO2 nanoparticle is a promising material for hydrogen generation through photocatalysis. (C) 2013 Elsevier B.V. All rights reserved.

C-H center dot center dot center dot O-nitrate synthon assisted molecular assembly of hydrogen bonded Ni(II) and Cu(II) complexes

Two Schiff base metal complexes Cu-SPETNNO3 (1) and Ni-SPETNNO3 (2) SPETN=2,2-propane,1,3-diylbis(nitrilomethyldyne)pyridyl,phenolate] ] with hydrogen bonding groups have been synthesized and characterized by single-crystal X-ray diffraction. In both of the compounds nitrates occupy a crystallographic general position. In 1 the lattice nitrates are on the 2(1) screw axis while in 2 they are at the crystallographic inversion center. C-HOnitrate synthons (formed by the nitrate anions and peripheral hydrogen bonding groups of the metal complexes) are non-covalent building blocks in molecular-assembly and packing of the cationic Schiff base metal complexes (M=Ni2+, Cu2+), resulting in 2-D hydrogen bonded networks. The CuCu non-bonding contact in 1 is 3.268 angstrom while the Ni-Ni bonding distance in 2 is 3.437 angstrom.

A nearly constant switching frequency current hysteresis controller with generalized parabolic boundaries using 12-sided polygonal voltage space vectors for IM drives

In this paper, a current hysteresis controller with parabolic boundaries for a 12-sided polygonal voltage space vector inverter fed induction motor (IM) drive is proposed. Parabolic boundaries with generalized vector selection logic, valid for all sectors and rotational direction, is used in the proposed controller. The current error space phasor boundary is obtained by first studying the drive scheme with space vector based PWM (SVPWM) controller. Four parabolas are used to approximate this current error space phasor boundary. The system is then run with space phasor based hysteresis PWM controller by limiting the current error space vector (CESV) within the parabolic boundary. The proposed controller has simple controller implementation, nearly constant switching frequency, extended modulation range and fast dynamic response with smooth transition to the over modulation region.

A Medium-Voltage Inverter-Fed IM Drive Using Multilevel 12-Sided Polygonal Vectors, With Nearly Constant Switching Frequency Current Hysteresis Controller

In this paper, a current error space vector (CESV)-based hysteresis current controller for a multilevel 12-sided voltage space vector-based inverter-fed induction motor (IM) drive is proposed. The proposed controller gives a nearly constant switching frequency operation throughout different speeds in the linear modulation region. It achieves the elimination of 6n +/- 1, n = odd harmonics from the phase voltages and currents in the entire modulation range, with an increase in the linear modulation range. It also exhibits fast dynamic behavior under different transient conditions and has a simple controller implementation. Nearly constant switching frequency is obtained by matching the steady-state CESV boundaries of the proposed controller with that of a constant switching frequency SVPWM-based drive. In the proposed controller, the CESV reference boundaries are computed online, using the switching dwell time and voltage error vector of each applied vector. These quantities are calculated from estimated sampled reference phase voltages. Vector change is decided by projecting the actual current error along the computed hysteresis space vector boundary of the presently applied vector. The estimated reference phase voltages are found from the stator current error ripple and the parameters of the IM.

Renewable Energy via Photocatalysis

The generation of renewable energy through photocatalysis is an attractive option to utilize the abundantly available solar radiation for a sustainable future. Photocatalysis refers to charge-carrier, i.e. electron and hole, mediated reactions occurring on a semiconductor surface in presence of ultraviolet or visible light radiation. Photocatalysis is a well established advanced oxidation technique for the decontamination of toxic organic pollutants to CO2 and H2O. However, the generation of energy in the form of hydrogen, hydrocarbon fuels and electricity via photocatalysis is an upcoming field with great many technical challenges towards practical implementation. This review will describe the fundamental reaction mechanism of (i) photocatalytic water splitting, (ii) photocatalytic H-2 generation in presence of different sacrificial agents, (iii) H-2 and electricity generation in a photofuel cell, (iv) photocatalytic reduction of CO2 to hydrocarbons and useful chemicals, and (v) photocatalytic water-gas shift reaction. A historic and recent perspective of the above conversion techniques, especially with regard to the development of TiO2-based and non-TiO2 materials is provided. The activity of different materials for the above reactions based on quantifiers like reaction rate, quantum yield and incident-photon-to-current efficiency is compared, and key design considerations of the ``best'' photocatalyst or photoelectrode is outlined. An overall assessment of the research area indicates that the presently achieved quantum efficiencies for the above reactions are rather moderate in the visible region, and the goal is to develop a catalyst that absorbs visible radiation, provides good charge-carrier separation, and exhibits high stability for long periods of usage.

Steric and Electronic Interactions Controlling the cis/trans Isomer Equilibrium at X-Pro Tertiary Amide Motifs in Solution

A systematic understanding of the noncovalent interactions that influence the structures of the cis conformers and the equilibrium between the cis and the trans conformers, of the X-Pro tertiary amide motifs, is presented based on analyses of H-1-, C-13-NMR and FTIR absorption spectra of two sets of homologous peptides, X-Pro-Aib-OMe and X-Pro-NH-Me (where X is acetyl, propionyl, isobutyryl and pivaloyl), in solvents of varying polarities. First, this work shows that the cis conformers of any X-Pro tertiary amide motif, including Piv-Pro, are accessible in the new motifs X-Pro-Aib-OMe, in solution. These conformers are uniquely observable by FTIR spectroscopy at ambient temperatures and by NMR spectroscopy from temperatures as high as 273 K. This is made possible by the persistent presence of n(i-1i)* interactions at Aib, which also influence the disappearance of steric effects at these cis X-Pro rotamers. Second, contrary to conventional understanding, the energy contribution of steric effects to the cis/trans equilibrium at the X-Pro motifs is found to be nonvariant (0.54 +/- 0.02 kcal/mol) with increase in steric bulk on the X group. Third, the current studies provide direct evidence for the weak intramolecular interactions namely the n(i-1i)*, the N-Pro center dot center dot center dot Hi+1 (C(5)a), and the C-7 hydrogen bond that operate and influence the structures, stabilities, and dynamics between different conformational states of X-Pro tertiary amide motifs. NMR and IR spectral data suggest that the cis conformers of X-Pro motifs are ensembles of short-lived rotamers about the C-X-N-Pro bond. (c) 2013 Wiley Periodicals, Inc. Biopolymers 101: 66-77, 2014.

Numerical simulations of bubble formation from submerged needles under non-uniform direct current electric field

In several chemical and space industries, small bubbles are desired for efficient interaction between the liquid and gas phases. In the present study, we show that non-uniform electric field with appropriate electrode configurations can reduce the volume of the bubbles forming at submerged needles by up to three orders of magnitude. We show that localized high electric stresses at the base of the bubbles result in slipping of the contact line on the inner surface of the needle and subsequent bubble formation occurs with contact line inside the needle. We also show that for bubble formation in the presence of highly non-uniform electric field, due to high detachment frequency, the bubbles go through multiple coalescences and thus increase the apparent volume of the detached bubbles. (C) 2013 AIP Publishing LLC.

New insights into designing metallacarborane based room temperature hydrogen storage media

Metallacarboranes are promising towards realizing room temperature hydrogen storage media because of the presence of both transition metal and carbon atoms. In metallacarborane clusters, the transition metal adsorbs hydrogen molecules and carbon can link these clusters to form metal organic framework, which can serve as a complete storage medium. Using first principles density functional calculations, we chalk out the underlying principles of designing an efficient metallacarborane based hydrogen storage media. The storage capacity of hydrogen depends upon the number of available transition metal d-orbitals, number of carbons, and dopant atoms in the cluster. These factors control the amount of charge transfer from metal to the cluster, thereby affecting the number of adsorbed hydrogen molecules. This correlation between the charge transfer and storage capacity is general in nature, and can be applied to designing efficient hydrogen storage systems. Following this strategy, a search for the best metallacarborane was carried out in which Sc based monocarborane was found to be the most promising H-2 sorbent material with a 9 wt.% of reversible storage at ambient pressure and temperature. (C) 2013 AIP Publishing LLC.

CHARACTERIZATION AND HARDNESS OF Co-P COATINGS OBTAINED FROM DIRECT CURRENT ELECTRODEPOSITION USING GLUCONATE BATH

Direct current electrodeposition of Co-P alloy coatings were carried out using gluconate bath and they were characterized by employing techniques like XRD, FESEM, DSC and XPS. Broad XRD lines demonstrate the amorphous nature of Co-P coatings. Spherical and rough nodules are observed on the surface of coatings as seen from FESEM images. Three exothermic peaks around 290, 342 and 390 degrees C in DSC profiles of Co-P coatings could be attributed to the crystallization and formation of Co2P phase in the coatings. As-deposited coatings consist of Co metal and oxidized Co species as revealed by XPS studies. Bulk alloy P (P delta-) as well as oxidized P (P5+) are present on the surface of coatings. Concentrations of Co metal and P delta- increase with successive sputtering of the coating. Observed microhardness value is 1005 HK when Co-P coating obtained from 10 g L-1 NaH2PO2 is heated at 400 degrees C that is comparable with hard chromium coatings.

Compensator Design for Closed Loop Hall-Effect Current Sensors

Closed loop current sensors used in power electronics applications are expected to have high bandwidth and minimal measurement transients. In this paper, a closed loop compensated Hall-effect current sensor is modeled. The model is used to tune the sensor's compensator. Analytical expression of step response is used to evaluate the performance of the PI compensator in the current sensor. This analysis is used to devise a procedure to design parameters of the PI compensator for fast dynamic response and for small dynamic error. A prototype current sensor is built in the laboratory. Simulations using the model are compared with experimental results to validate the model and to study the variation in performance with compensator parameters. The performance of the designed PI compensator for the sensor is compared with a commercial current sensor. The measured bandwidth of the designed current sensor is above 200 kHz, which is comparable to commercial standards. Implementation issues of PI compensator using operational amplifiers are also addressed.

Electronic transport in patterned graphene nanoroads

Graphane, hydrogenated graphene, can be patterned into electronic devices by selectively removing hydrogen atoms. The most simple of such devices is the so-called nanoroad, analogous to the graphene nanoribbon, where confinement-and the opening of a gap-is obtained without the need for breaking the carbon bonds. In this work we address the electronic transport properties of such systems considering different hydrogen impurities within the conduction channel. We show, using a combination of density functional theory and non-equilibrium Green's functions, that hydrogen leads to significant changes in the transport properties and in some cases to current polarization.

Harmonic Analysis of DC-Link Capacitor Current in Sinusoidally Modulated Neutral-Point-Clamped Inverter

The voltage ripple and power loss in the DC-capacitor of a voltage source inverter depend on the harmonic currents flowing through the capacitor. This paper presents double Fourier series based harmonic analysis of DC capacitor current in a three-level neutral point clamped inverter, modulated with sine-triangle PWM. The analytical results are validated experimentally on a 5-kVA three-level inverter prototype. The results of the analysis are used for predicting the power loss in the DC capacitor.