Coordination-driven self-assembly of 2D-metallamacrocycles using a shape-selective Pt(2)(II)-organometallic 90 degrees acceptor: design, synthesis and sensing study

Synthesis of a series of two-dimensional metallamacrocycles via coordination-driven self-assembly of a shape-selective Pt(2)(II)-molecular building unit incorporating carbazole-ethynyl functionality is described. An equimolar (1 : 1) combination of a Pt(2)(II)-organometallic 90 degrees acceptor, 1, with rigid linear ditopic donors (L(a) and L(b)) afforded [4 + 4] self-assembled octanuclear molecular squares, 2 and 3, in quantitative yields, respectively [L(a) = 4,4'-bipyridine; L(b) = trans-1,2-bis(4-pyridyl)ethylene]. Conversely, a similar treatment of 1 with an amide-based unsymmetrical flexible ditopic donor, L(c), resulted in the formation of a [2 + 2] self-sorted molecular rhomboid (4a) as a single product [L(c) = N-(4-pyridyl)isonicotinamide]. Despite the possibility of several linkage isomeric macrocycles (rhomboid, triangle and square) due to the different connectivity of L(c), the formation of a single and symmetrical molecular rhomboid (4a) as the only product is an interesting observation. All the self-assembled macrocycles (2, 3 and 4a) were fully characterized by multinuclear NMR ((1)H and (31)P) and ESI-MS analysis. Further structural insights about the size and shape of the macrocycles were obtained through energy minimization using density functional theory (DFT) calculations. Decoration of the starting carbazole building unit with Pt-ethynyl functionality enriches the assemblies to be more p-electron rich and luminescent in nature. Macrocycles 2 and 3 could sense the presence of electron deficient nitroaromatics in solution by quenching of the initial intensity upon gradual addition of picric acid (PA). They exhibited the largest quenching response with high selectivity for nitroaromatics compared to several other electron deficient aromatics tested.

Laser damage threshold studies on urea L-malic acid: A nonlinear optical crystal

A detailed study of surface laser damage performed on a nonlinear optical crystal, urea L-malic acid, using 7 ns laser pulses at 10 Hz repetition rate from a Q-switched Nd:YAG laser at wavelengths of 532 and 1064 nm is reported. The single shot and multiple shot surface laser damage threshold values are determined to be 26.64±0.19 and 20.60±0.36 GW cm−2 at 1064 nm and 18.44±0.31 and 7.52±0.22 GW cm−2 at 532 nm laser radiation, respectively. The laser damage anisotropy is consistent with the Vickers mechanical hardness measurement performed along three crystallographic directions. The Knoop polar plot also reflects the damage morphology. Our investigation reveals a direct correlation between the laser damage profile and hardness anisotropy. Thermal breakdown of the crystal is identified as the possible mechanism of laser induced surface damage.

Classification of road damage due to earthquakes

Earthquakes cause massive road damage which in turn causes adverse effects on the society. Previous studies have quantified the damage caused to residential and commercial buildings; however, not many studies have been conducted to quantify road damage caused by earthquakes. In this study, an attempt has been made to propose a new scale to classify and quantify the road damage due to earthquakes based on the data collected from major earthquakes in the past. The proposed classification for road damage due to earthquake is called as road damage scale (RDS). Earthquake details such as magnitude, distance of road damage from the epicenter, focal depth, and photographs of damaged roads have been collected from various sources with reported modified Mercalli intensity (MMI). The widely used MMI scale is found to be inadequate to clearly define the road damage. The proposed RDS is applied to various reported road damage and reclassified as per RDS. The correlation between RDS and earthquake parameters of magnitude, epicenter distance, hypocenter distance, and combination of magnitude with epicenter and hypocenter distance has been studied using available data. It is observed that the proposed RDS correlates well with the available earthquake data when compared with the MMI scale. Among several correlations, correlation between RDS and combination of magnitude and epicenter distance is appropriate. Summary of these correlations, their limitations, and the applicability of the proposed scale to forecast road damages and to carry out vulnerability analysis in urban areas is presented in the paper.

Monitoring Himalayan cryosphere using remote sensing techniques

In the Himalayas, large area is covered by glaciers, seasonal snow and changes in its extent can influence availability of water in the Himalayan Rivers. In this paper, changes in glacial extent, glacial mass balance and seasonal snow cover have been discussed. Field and satellite based investigations suggest, most of the Himalayan glaciers are retreating though the rate of retreat is varying from glacier to glacier, ranging from few meters to almost 50 meters per year, depending upon the numerous glacial, terrain and meteorological parameters. Retreat was estimated for 1868 glaciers in eleven basins distributed across the Indian Himalaya since 1962 to 2001/02. Estimates show an overall reduction in glacier area from 6332 to 5329 sq km, an overall deglaciation of 16 percent.Snow line at the end of ablation season on the Chhota Shigri glacier suggests a change in altitude from 4900 to 5200 m from late 1970’s to the present. Seasonal snow cover monitoring of the Himalaya has shown large amounts of snow cover depletion in early part of winter, i.e. from October to December. For many basins located in lower altitude and in south of Pir Panjal range, snow ablation was observed through out the winter season. In addition, average stream runoff of the Baspa basin during the month of December shows an increase by 75 per cent. This combination of glacial retreat, negative mass balance, early melting of seasonal snow cover and winter time increase in stream runoff suggest an influence of climate change on the Himalayan cryosphere.

Genetic Algorithm for Damage Assessment

Genetic Algorithms (GAs) are recognized as an alternative class of computational model, which mimic natural evolution to solve problems in a wide domain including machine learning, music generation, genetic synthesis etc. In the present study Genetic Algorithm has been employed to obtain damage assessment of composite structural elements. It is considered that a state of damage can be modeled as reduction in stiffness. The task is to determine the magnitude and location of damage. In a composite plate that is discretized into a set of finite elements, if a jth element is damaged, the GA based technique will predict the reduction in Ex and Ey and the location j. The fact that the natural frequency decreases with decrease in stiffness is made use of in the method. The natural frequency of any two modes of the damaged plates for the assumed damage parameters is facilitated by the use of Eigen sensitivity analysis. The Eigen value sensitivities are the derivatives of the Eigen values with respect to certain design parameters. If ωiu is the natural frequency of the ith mode of the undamaged plate and ωid is that of the damaged plate, with δωi as the difference between the two, while δωk is a similar difference in the kth mode, R is defined as the ratio of the two. For a random selection of Ex,Ey and j, a ratio Ri is obtained. A proper combination of Ex,Ey and j which makes Ri−R=0 is obtained by Genetic Algorithm.

Distinct Roles of FANCO/RAD51C Protein in DNA Damage Signaling and Repair Implications for Fanconi Anemia and Breast Cancer Susceptibility

RAD51C, a RAD51 paralog, has been implicated in homologous recombination (HR), and germ line mutations in RAD51C are known to cause Fanconi anemia (FA)-like disorder and breast and ovarian cancers. The role of RAD51C in the FA pathway of DNA interstrand cross-link (ICL) repair and as a tumor suppressor is obscure. Here, we report that RAD51C deficiency leads to ICL sensitivity, chromatid-type errors, and G(2)/M accumulation, which are hallmarks of the FA phenotype. We find that RAD51C is dispensable for ICL unhooking and FANCD2 monoubiquitination but is essential for HR, confirming the downstream role of RAD51C in ICL repair. Furthermore, we demonstrate that RAD51C plays a vital role in the HR-mediated repair of DNA lesions associated with replication. Finally, we show that RAD51C participates in ICL and double strand break-induced DNA damage signaling and controls intra-S-phase checkpoint through CHK2 activation. Our analyses with pathological mutants of RAD51C that were identified in FA and breast and ovarian cancers reveal that RAD51C regulates HR and DNA damage signaling distinctly. Together, these results unravel the critical role of RAD51C in the FA pathway of ICL repair and as a tumor suppressor.

Monitoring of seasonal snow cover in Bhutan using remote sensing technique

All major rivers in Bhutan depend on snowmelt for discharge. Therefore, changes in snow cover due to climate change can influence distribution and availability of water. However, information about distribution of seasonal snow cover in Bhutan is not available. The MODIS snow product was used to study snow cover status and trends in Bhutan. Average snow cover area (SCA) of Bhutan estimated for the period 2002 to 2010 was 9030 sq. km, about 25.5% of the total land area. SCA trend of Bhutan for the period 2002-2010 was found to decrease (-3.27 +/- 1.28%). The average SCA for winter was 14,485 sq. km (37.7%), for spring 7411 sq. km (19.3%), for summer 4326 sq. km (11.2%), and for autumn 7788 sq. km (20.2%), mostly distributed in the elevation range 2500-6000 m amsl. Interannual and seasonal SCA trend both showed a decline, although it was not statistically significant for all sub-basins. Pho Chu sub-basin with 19.5% of the total average SCA had the highest average SCA. The rate of increase of SCA for every 100 m elevation was the highest (2.5%) in the Pa Chu sub-basin. The coefficient of variance of 1.27 indicates high variability of SCA in winter.

A novel ``pro-sensitizer'' based sensing of enzymes using Tb(III) luminescence in a hydrogel matrix

Chemically synthesized ``pro-sensitizers'' release the sensitizer in the presence of lipase or beta-glucosidase, triggering a significant luminescence response from a lanthanide based hydrogel.

Micromechanisms of damage nucleation during contact deformation of columnar multilayer nitride coatings

In order to resolve some missing micromechanistic details regarding contact deformation in nitride multilayer coatings we report here observations from cross-sectional transmission electron microscopy and focused ion beam studies of the Vickers indentations on TiN/TiAlN multilayer films of various total thicknesses as well as bilayer periods. The study of damage induced by contact deformation in a nitride multilayer coating is complemented by stress calculated using an analytical model. Kinked boundaries of sliding columns give rise to cracks which propagate at an angle to the indentation axis under a combination of compressive and shear stresses. It is seen that multilayers provide more distributed columnar sliding, thereby reducing the stress intensity factor for shear cracking, while interfacial dislocations provide a stress relief mechanism by enabling lateral movement of material. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Ultrasonic Guided Wave Characterization and Damage Detection in Foam-core Sandwich Panel using PWAS and LDV

Lamb wave type guided wave propagation in foam core sandwich structures and detectability of damages using spectral analysis method are reported in this paper. An experimental study supported by theoretical evaluation of the guided wave characteristics is presented here that shows the applicability of Lamb wave type guided ultrasonic wave for detection of damage in foam core sandwich structures. Sandwich beam specimens were fabricated with 10 mm thick foam core and 0.3 mm thick aluminum face sheets. Thin piezoelectric patch actuators and sensors are used to excite and sense guided wave. Group velocity dispersion curves and frequency response of sensed signal are obtained experimentally. The nature of damping present in the sandwich panel is monitored by measuring the sensor signal amplitude at various different distances measured from the center of the linear phased array. Delaminations of increasing width are created and detected experimentally by pitch-catch interrogation with guided waves and wavelet transform of the sensed signal. Signal amplitudes are analyzed for various different sizes of damages to differentiate the damage size/severity. A sandwich panel is also fabricated with a planer dimension of 600 mm x 400 mm. Release film delamination is introduced during fabrication. Non-contact Laser Doppler Vibrometer (LDV) is used to scan the panel while exciting with a surface bonded piezoelectric actuator. Presence of damage is confirmed by the reflected wave fringe pattern obtained from the LDV scan. With this approach it is possible to locate and monitor the damages by tracking the wave packets scattered from the damages.

Guided Wave based Damage Detection in a Composite T-joint using 3D Scanning Laser Doppler Vibrometer

Composite T-joints are commonly used in modern composite airframe, pressure vessels and piping structures, mainly to increase the bending strength of the joint and prevents buckling of plates and shells, and in multi-cell thin-walled structures. Here we report a detailed study on the propagation of guided ultrasonic wave modes in a composite T-joint and their interactions with delamination in the co-cured co-bonded flange. A well designed guiding path is employed wherein the waves undergo a two step mode conversion process, one is due to the web and joint filler on the back face of the flange and the other is due to the delamination edges close to underneath the accessible surface of the flange. A 3D Laser Doppler Vibrometer is used to obtain the three components of surface displacements/velocities of the accessible face of the flange of the T-joint. The waves are launched by a piezo ceramic wafer bonded on to the back surface of the flange. What is novel in the proposed method is that the location of any change in material/geometric properties can be traced by computing a frequency domain power flow along a scan line. The scan line can be chosen over a grid either during scan or during post-processing of the scan data off-line. The proposed technique eliminates the necessity of baseline data and disassembly of structure for structural interrogation.

Carbon Nanotube based Composite Fibers for Strain Sensing, Signal Processing and Computing

Carbon nanotubes dispersed in polymer matrix have been aligned in the form of fibers and interconnects and cured electrically and by UV light. Conductivity and effective semiconductor tunneling against reverse to forward bias field have been designed to have differentiable current-voltage response of each of the fiber/channel. The current-voltage response is a function of the strain applied to the fibers along axial direction. Biaxial and shear strains are correlated by differentiating signals from the aligned fibers/channels. Using a small doping of magnetic nanoparticles in these composite fibers, magneto-resistance properties are realized which are strong enough to use the resulting magnetostriction as a state variable for signal processing and computing. Various basic analog signal processing tasks such as addition, convolution and filtering etc. can be performed. These preliminary study shows promising application of the concept in combined analog-digital computation in carbon nanotube based fibers. Various dynamic effects such as relaxation, electric field dependent nonlinearities and hysteresis on the output signals are studied using experimental data and analytical model.

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.

Differential Diffractive Reflectance Modulation Sensing

We fabricated a reflectance based sensor which relies on the diffraction pattern generated from a bio-microarray where an underlying thin film structure enhances the diffracted intensity from molecular layers. The zero order diffraction represents the background signal and the higher orders represent the phase difference between the array elements and the background. By taking the differential ratio of the first and zero order diffraction signals we get a quantitative measure of molecular binding while simultaneously rejecting common mode fluctuations. We improved the signal-to-noise ratio by an order of magnitude with this ratiometric approach compared to conventional single channel detection. In addition, we use a lithography based approach for fabricating microarrays which results in spot sizes as small as 5 micron diameter unlike the 100 micron spots from inkjet printing and is therefore capable of a high degree of multiplexing. We will describe the real-time measurement of adsorption of charged polymers and bulk refractometry using this technique. The lack of moving parts for point scanning of the microarray and the differential ratiometric measurements using diffracted orders from the same probe beam allows us to make real-time measurements in spite of noise arising from thermal or mechanical fluctuations in the fluid sample above the sensor surface. Further, the lack of moving parts leads to considerable simplification in the readout hardware permitting the use of this technique in compact point of care sensors.