Experimental and Theoretical Studies of Unusual Four-Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)-acetylene Complexes with the Sulfurdiimide Me3SiN=S=NSiMe3

The use of the sulfurdiimide RN=S=NR' (R = R' = SiMe3, 3) in reactions with group 4 metallocene bis(trimethylsilyl)-acetylene complexes of the type [Cp2M(L (eta(2)-Me3Si-C2SiMe3)] (1: M = Ti, no L; 2: M = Zr, L = pyridine) has led to the formation of four-membered metallacycles 4M containing the group 4 metal, nitrogen and sulfur. DFT calculations performed on compound 4Ti indicate that this complex is best described as a sigma-complex with cyclic delocalisation of the ring electrons. Moreover, pseudo-Jahn-Teller distortion plays a significant role in stabilising this complex.

Measurement and Applications of Long-Range Heteronuclear Scalar Couplings: Recent Experimental and Theoretical Developments

The use of long-range heteronuclear couplings, in association with 1H1H scalar couplings and NOE restraints, has acquired growing importance for the determination of the relative stereochemistry, and structural and conformational information of organic and biological molecules. However, the routine use of such couplings is hindered by the inherent difficulties in their measurement. Prior to the advancement in experimental techniques, both long-range homo- and heteronuclear scalar couplings were not easily accessible, especially for very large molecules. The development of a large number of multidimensional NMR experimental methodologies has alleviated the complications associated with the measurement of couplings of smaller strengths. Subsequent application of these methods and the utilization of determined J-couplings for structure calculations have revolutionized this area of research. Problems in organic, inorganic and biophysical chemistry have also been solved by utilizing the short- and long-range heteronuclear couplings. In this minireview, we discuss the advantages and limitations of a number of experimental techniques reported in recent times for the measurement of long-range heteronuclear couplings and a few selected applications of such couplings. This includes the study of medium- to larger-sized molecules in a variety of applications, especially in the study of hydrogen bonding in biological systems. The utilization of these couplings in conjunction with theoretical calculations to arrive at conclusions on the hyperconjugation, configurational analysis and the effect of the electronegativity of the substituents is also discussed.

Evaluation of damage in reinforced concrete bridge beams using acoustic emission technique

Acoustic emission (AE) testing is a well-known method for damage identification of various concrete structures including bridges. This article presents a method to assess damage in reinforced concrete (RC) bridge beams subjected to incremental cyclic loading. The specifications in the standard NDIS-2421 were used to classify the damage in RC bridge beams. Earlier researchers classified the damage occurring in bridge beams by using crack mouth opening displacement (CMOD) and AE released and proposed a standard (NDIS-2421: the Japanese Society for NonDestructive Inspection). In general, multiple cracks take place in RC beams under bending; therefore, utilisation of CMOD for crack detection may not be appropriate. In the present study, the damage in RC beams is classified by using the AE released, deflection, strains in steel and concrete, because the measurement of the strains in steel and concrete is easy and the codes of practice are specified for different limit states (IS-456:2000). The observations made in the present experimental study have some important practical applications in assessing the state of damage of concrete structural members.

Structural landscape of benzoic acid: using experimental crystal structures of fluorobenzoic acids as a probe

Experimental crystal structures of mono and polyfluorinated benzoic acids correspond to high energy computed crystal structures of benzoic acid itself, thereby permitting access to its structural landscape.

DFT study of structure and vibrational spectra of ceramide 3: comparison to experimental data

The Fourier transform Raman and infrared (IR) spectra of the Ceramide 3 (CER3) have been recorded in the regions 200-3500 cm(-1) and 680-4000 cm(-1), respectively. We have calculated the equilibrium geometry, harmonic vibrational wavenumbers, electrostatic potential surfaces, absolute Raman scattering activities and IR absorption intensities by the density functional theory with B3LYP functionals having extended basis set 6-311G. This work is undertaken to study the vibrational spectra of CER3 completely and to identify the various normal modes with better wavenumber accuracy. Good consistency is found between the calculated results and experimental data for the IR and Raman spectra.

Novel De-Acylative Ring Opening of 3-Acetyl and 3-Bromo Acetyl Coumarins

Reaction of 3-acetyl and 3-bromoacetyl coumarins with hydrazine hydrate has resulted in the ring opening of the coumarin moiety. The reaction was attempted with a view to obtain some new pyridazinones and pyrazolones. The reaction did not proceed via the expected pathway instead led to the formation of salicyl azines, the structure of which has been confirmed by single crystal X-ray studies.

Ultrasound modulation of coherent light in a multiple-scattering medium: experimental verification of nonzero average phase carried by light

We demonstrate the phase fluctuation introduced by oscillation of scattering centers in the focal volume of an ultrasound transducer in an optical tomography experiment has a nonzero mean. The conditions to be met for the above are: (i) the frequency of the ultrasound should be in the vicinity of the most dominant natural frequency of vibration of the ultrasound focal volume, (ii) the corresponding acoustic wavelength should be much larger than l(n)*, a modified transport mean-free-path applicable for phase decorrelation and (iii) the focal volume of the ultrasound transducer should not be larger than 4 - 5 times (l(n)*)(3). We demonstrate through simulations that as the ratio of the ultrasound focal volume to (l(n)*)(3) increases, the average of the phase fluctuation decreases and becomes zero when the focal volume becomes greater than around 4(l(n)*)(3); and through simulations and experiments that as the acoustic frequency increases from 100 Hz to 1 MHz, the average phase decreases to zero. Through experiments done in chicken breast we show that the average phase increases from around 110 degrees to 130 degrees when the background medium is changed from water to glycerol, indicating that the average of the phase fluctuation can be used to sense changes in refractive index deep within tissue.

Experimental Investigation on the Effect of Advanced Bus-Clamping Pulsewidth Modulation on Motor Acoustic Noise

Voltage source inverters (VSIs) supply nonsinusoidal voltages to induction motor drives, leading to line current distortion and torque pulsation. Conventional space vector pulsewidth modulation (PWM) techniques are widely used in VSIs on the account of good waveform quality and high dc bus utilization. In a conventional space vector PWM technique, the switching sequence begins with one zero state and ends with the other zero state in a subcycle. Some novel switching sequences have been proposed, which employ only one zero state but apply one of the two active states twice in a subcycle. One pair of such special switching sequences has recently been shown to reduce the pulsating torque considerably. In this paper, the conventional and special switching sequences are compared experimentally in terms of acoustic noise. In the low-and medium-speed ranges, the special switching sequence is seen to reduce the amplitude of the tonal component of noise at the switching frequency considerably and is also found to result in spread spectrum.

Differential Activities of the Two Closely Related Withanolides, Withaferin A and Withanone: Bioinformatics and Experimental Evidences

Background and Purpose: Withanolides are naturally occurring chemical compounds. They are secondary metabolites produced via oxidation of steroids and structurally consist of a steroid-backbone bound to a lactone or its derivatives. They are known to protect plants against herbivores and have medicinal value including anti-inflammation, anti-cancer, adaptogenic and anti-oxidant effects. Withaferin A (Wi-A) and Withanone (Wi-N) are two structurally similar withanolides isolated from Withania somnifera, also known as Ashwagandha in Indian Ayurvedic medicine. Ashwagandha alcoholic leaf extract (i-Extract), rich in Wi-N, was shown to kill cancer cells selectively. Furthermore, the two closely related purified phytochemicals, Wi-A and Wi-N, showed differential activity in normal and cancer human cells in vitro and in vivo. We had earlier identified several genes involved in cytotoxicity of i-Extract in human cancer cells by loss-of-function assays using either siRNA or randomized ribozyme library. Methodology/Principal Findings: In the present study, we have employed bioinformatics tools on four genes, i.e., mortalin, p53, p21 and Nrf2, identified by loss-of-function screenings. We examined the docking efficacy of Wi-N and Wi-A to each of the four targets and found that the two closely related phytochemicals have differential binding properties to the selected cellular targets that can potentially instigate differential molecular effects. We validated these findings by undertaking parallel experiments on specific gene responses to either Wi-N or Wi-A in human normal and cancer cells. We demonstrate that Wi-A that binds strongly to the selected targets acts as a strong cytotoxic agent both for normal and cancer cells. Wi-N, on the other hand, has a weak binding to the targets; it showed milder cytotoxicity towards cancer cells and was safe for normal cells. The present molecular docking analyses and experimental evidence revealed important insights to the use of Wi-A and Wi-N for cancer treatment and development of new anti-cancer phytochemical cocktails.

Damage limit states of reinforced concrete beams subjected to incremental cyclic loading using relaxation ratio analysis of AE parameters

This paper presents an experimental study on damage assessment of reinforced concrete (RC) beams subjected to incremental cyclic loading. During testing acoustic emissions (AEs) were recorded. The analysis of the AE released was carried out by using parameters relaxation ratio, load ratio and calm ratio. Digital image correlation (DIC) technique and tracking with available MATLAB program were used to measure the displacement and surface strains in concrete. Earlier researchers classified the damage in RC beams using Kaiser effect, crack mouth opening displacement and proposed a standard. In general (or in practical situations), multiple cracks occur in reinforced concrete beams. In the present study damage assessment in RC beams was studied according to different limit states specified by the code of practice IS-456:2000 and AE technique. Based on the two ratios namely load ratio and calm ratio and when the deflection reached approximately 85% of the maximum allowable deflection it was observed that the RC beams were heavily damaged. The combination of AE and DIC techniques has the potential to provide the state of damage in RC structures.

Topological electron density analysis and electrostatic properties of aspirin: an experimental and theoretical study

The topological and the electrostatic properties of the aspirin drug molecule were determined from high-resolution X-ray diffraction data at 90 K, and the corresponding results are compared with the theoretical calculations. The electron density at the bond critical point of all chemical bonds induding the intermolecular interactions of aspirin has been quantitatively described using Bader's quantum theory of ``Atoms in Molecules''. The electrostatic potential of the molecule emphasizes the preferable binding sites of the drug and the interaction features of the molecule, which are crucial for drug-receptor recognition. The topological analysis of hydrogen bonds reveals the strength of intermolecular interactions.

Development of experimental setup for study of adsorption characteristics of porous materials down to 4.2 K

The knowledge of adsorption characteristics of activated carbon (porous material) in the temperature range from 5 to 20 K is essential when used in cryosorption pumps for nuclear fusion applications. However, such experimental data are very scarce in the literature, especially below 77 K. So, an experimental system is designed and fabricated to measure the adsorption characteristics of porous materials under variable cryogenic temperatures (from 5 K to 100 K). This is based on the commercially available micropore-analyser coupled to a closed helium cycle two-stage Gifford McMahon (GM) Cryocooler, which allows the sample to be cooled to 4.2 K. The sample port is coupled to the Cryocooler through a heat switch, which isolates this port from the cold head of the Cryocooler. By this, the sample temperature can now be varied without affecting the Cryocooler. The setup enables adsorption studies in the pressure range from atmospheric down to 10(-4) Pa. The paper describes the details of the experimental setup and presents the results of adsorption studies at 77 K for activated carbon with nitrogen as adsorbate. The system integration is now completed to enable adsorption studies at 4.2 K.

Reactions of Titanocene Bis(trimethylsilyl)acetylene Complexes with Carbodiimides: An Experimental and Theoretical Study of Complexation versus C-N Bond Activation

The reaction of the low valent metallocene(II) sources Cp'Ti-2(eta(2)-Me3SiC2SiMe3) (Cp' = eta(5)-cyclopentadienyl, 1a or eta(5)-pentamethylcyclopentadienyl, 1b) with different carbodiimide substrates RN=C=NR' 2-R-R' (R = t-Bu; R' = Et; R = R' = i-Pr; t-Bu; SiMe3; 2,4,6-Me-C6H2 and 2,6-i-Pr-C6H3) was investigated to explore the frontiers of ring strained, unusual four-membered heterometallacycles 5-R. The product complexes show dismantlement, isomerization, or C-C coupling of the applied carbodiimide substrates, respectively, to form unusual mono-, di-, and tetranuclear titanium(III) complexes. A detailed theoretical study revealed that the formation of the unusual complexes can be attributed to the biradicaloid nature of the unusual four-membered heterometallacycles 5-R, which presents an intriguing situation of M-C bonding. The combined experimental and theoretical study highlights the delicate interplay of electronic and steric effects in the stabilization of strained four-membered heterometallacycles, accounting for the isolation of the obtained complexes.

Fracture Analysis of High strength and Ultra high strength Concrete beams by using Finite Element Method

This paper presents the details of nonlinear finite element analysis (FEA) of three point bending specimens made up of high strength concrete (HSC, HSC1) and ultra high strength concrete (UHSC). Brief details about characterization and experimentation of HSC, HSC1 and UHSC have been provided. Cracking strength criterion has been used for simulation of crack propagation by conducting nonlinear FEA. The description about FEA using crack strength criterion has been outlined. Bi-linear tension softening relation has been used for modeling the cohesive stresses ahead of the crack tip. Numerical studies have been carried out on fracture analysis of three point bending specimens. It is observed from the studies that the computed values from FEA are in very good agreement with the corresponding experimental values. The computed values of stress vs crack width will be useful for evaluation of fracture energy, crack tip opening displacement and fracture toughness. Further, these values can also be used for crack growth study, remaining life assessment and residual strength evaluation of concrete structural components.

Experimental and theoretical investigation of thermoacoustic prime mover

The thermoacoustic prime mover is part of an interesting class of prime movers that can be used to generate clean energy and to drive cryogenic refrigeration systems. A thermoacoustic prime mover has been built based on the linear thermoacoustic model, which consumes thermal energy and produces acoustic energy. The objective of this article is to design a thermoacoustic prime mover that can be used as a drive for a thermoacoustic refrigerator. It is found that stack plate length and its distance from the closed end have a significant effect on the thermal efficiency of the prime mover. For different stack center positions, there is an optimum length of stack plate that has a significant effect on the performance of the thermoacoustic prime mover in terms of temperature gradient, frequency, and pressure amplitude. In this study, the experiments have been done on the thermoacoustic prime mover by varying stack position and its length with constant blockage ratio and resonator length. The results obtained from the experiments have been compared to the theoretical results acquired from DeltaEc Software.