Computational tools for mechanistic discrimination in the reductive and metathesis coupling reactions mediated by titanium(IV) isopropoxide

A theoretical study has been carried out at the B3LYP/LANL2DZ level to compare the reactivity of phenyl isocyanate and phenyl isothiocyanate towards titanium(IV) alkoxides. Isocyanates are shown to favour both mono insertion and double insertion reactions. Double insertion in a head-to-tail fashion is shown to be more exothermic than double insertion in a head-to-head fashion. The head-to-head double insertion leads to the metathesis product, a carbodiimide, after the extrusion of carbon dioxide. In the case of phenyl isothiocyanate, calculations favour the formation of only mono insertion products. Formation of a double insertion product is highly unfavourable. Further, these studies indicate that the reverse reaction involving the metathesis of N,N-'-diphenyl carbodiimide with carbon dioxide is likely to proceed more efficiently than the metathesis reaction with carbon disulphide. This is in excellent agreement with experimental results as metathesis with carbon disulphide fails to occur. In a second study, multilayer MM/QM calculations are carried out on intermediates generated from reduction of titanium(IV) alkoxides to investigate the effect of alkoxy bridging on the reactivity of multinuclear Ti species. Bimolecular coupling of imines initiated by Ti(III) species leads to a mixture of diastereomers and not diastereoselective coupling of the imine. However if the reaction is carried out by a trimeric biradical species, diastereoselective coupling of the imine is predicted. The presence of alkoxy bridges greatly favours the formation of the d,l (+/-) isomer, whereas the intermediate without alkoxy bridges favours the more stable meso isomer. As a bridged trimeric species, stabilized by bridging alkoxy groups, correctly explains the diastereoselective reaction, it is the most likely intermediate in the reaction.

Low-pass filters and differential tympanal tuning in a paleotropical bushcricket with an unusually low frequency call

Low-frequency sounds are advantageous for long-range acoustic signal transmission, but for small animals they constitute a challenge for signal detection and localization. The efficient detection of sound in insects is enhanced by mechanical resonance either in the tracheal or tympanal system before subsequent neuronal amplification. Making small structures resonant at low sound frequencies poses challenges for insects and has not been adequately studied. Similarly, detecting the direction of long-wavelength sound using interaural signal amplitude and/or phase differences is difficult for small animals. Pseudophylline bushcrickets predominantly call at high, often ultrasonic frequencies, but a few paleotropical species use lower frequencies. We investigated the mechanical frequency tuning of the tympana of one such species, Onomarchus uninotatus, a large bushcricket that produces a narrow bandwidth call at an unusually low carrier frequency of 3.2. kHz. Onomarchus uninotatus, like most bushcrickets, has two large tympanal membranes on each fore-tibia. We found that both these membranes vibrate like hinged flaps anchored at the dorsal wall and do not show higher modes of vibration in the frequency range investigated (1.5-20. kHz). The anterior tympanal membrane acts as a low-pass filter, attenuating sounds at frequencies above 3.5. kHz, in contrast to the high-pass filter characteristic of other bushcricket tympana. Responses to higher frequencies are partitioned to the posterior tympanal membrane, which shows maximal sensitivity at several broad frequency ranges, peaking at 3.1, 7.4 and 14.4. kHz. This partitioning between the two tympanal membranes constitutes an unusual feature of peripheral auditory processing in insects. The complex tracheal shape of O. uninotatus also deviates from the known tube or horn shapes associated with simple band-pass or high-pass amplification of tracheal input to the tympana. Interestingly, while the anterior tympanal membrane shows directional sensitivity at conspecific call frequencies, the posterior tympanal membrane is not directional at conspecific frequencies and instead shows directionality at higher frequencies.

Simulating grasping behavior of people using the relational description scheme

This paper presents an enhanced relational description for the prescription of the grasp requirement and evolution of the posture of a digital human hand towards satisfaction of this requirement. Precise relational description needs anatomical segmentation of the hand geometry into palmar, dorsal and lateral patches using the palm-plane and joint locations information, and operational segmentation of the object geometry into pull,push and lateral patches with due consideration to the effect of friction. Relational description identifies appropriate patches for a desired grasp condition. Satisfaction of this requirement occurs in two discrete stages,namely,contact establishment and post-contact force exertion for object capturing. Contact establishment occurs in four potentially overlapping phases,namely,re-orientation,transfer,pre- shaping,and closing-in. The novel h and re-orientation phase,enables the palm to face the object in a task sequence scenario, transfer takes the wrist to the ball park ; pre-shaping and close-in finally achieves the contact. In this paper, an anatomically pertinent closed-form formulation is presented for the closing-in phase for identification of the point of contact on the patches ,prescribed by the relational description. Since mere contact does not ensure grasp and slip phenomenon at the point of contact on application of force is a common occurrence, the effect of slip in presence of friction has been studied for 2D and 3D object grasping endeavours and a computational generation of the slip locus is presented.A general slip locus is found to be a non-linear curve even on planar faces.Two varieties of slip phenomena,namely,stabilizing and non-stabilizing slips, and their local characteristics have been identified.Study of the evolution of this slip characteristic over the slip locus exhibited diverse grasping behaviour possibilities. Thus, the relational description paradigm not only makes the requirement specification easy and meaningful but also enables high fidelity hand object interaction studies possible.

A new species of Duttaphrynus (Anura : Bufonidae) from Northeast India

A new species of montane toad Duttaphrynus is described from Nagaland state of Northeast India. The new species is diagnosable based on following combination of characters: absence of preorbital, postorbital and orbitotympanic ridges, elongated and broad parotid gland, first finger longer than second and presence of a mid-dorsal line. The tympanum is hidden under a skin fold (in male) or absent (in female). The species is compared with its congers from India and Indo-China. We propose to consider Duttaphrynus wokhaensis as junior synonym of Duttaphrynus melanostictus.

Large scale features and assessment of spatial scale correspondence between TMPA and IMD rainfall datasets over Indian landmass

Daily rainfall datasets of 10 years (1998-2007) of Tropical Rainfall Measuring Mission (TRMM) Multi-satellite Precipitation Analysis (TMPA) version 6 and India Meteorological Department (IMD) gridded rain gauge have been compared over the Indian landmass, both in large and small spatial scales. On the larger spatial scale, the pattern correlation between the two datasets on daily scales during individual years of the study period is ranging from 0.4 to 0.7. The correlation improved significantly (similar to 0.9) when the study was confined to specific wet and dry spells each of about 5-8 days. Wavelet analysis of intraseasonal oscillations (ISO) of the southwest monsoon rainfall show the percentage contribution of the major two modes (30-50 days and 10-20 days), to be ranging respectively between similar to 30-40% and 5-10% for the various years. Analysis of inter-annual variability shows the satellite data to be underestimating seasonal rainfall by similar to 110 mm during southwest monsoon and overestimating by similar to 150 mm during northeast monsoon season. At high spatio-temporal scales, viz., 1 degrees x1 degrees grid, TMPA data do not correspond to ground truth. We have proposed here a new analysis procedure to assess the minimum spatial scale at which the two datasets are compatible with each other. This has been done by studying the contribution to total seasonal rainfall from different rainfall rate windows (at 1 mm intervals) on different spatial scales (at daily time scale). The compatibility spatial scale is seen to be beyond 5 degrees x5 degrees average spatial scale over the Indian landmass. This will help to decide the usability of TMPA products, if averaged at appropriate spatial scales, for specific process studies, e.g., cloud scale, meso scale or synoptic scale.

Lizard Wears Shades. A Spectacled Sphenomorphus (Squamata: Scincidae), from the Sacred Forests of Mawphlang, Meghalaya, North-east India

A new species of lygosomatine scincid lizard is described from the sacred forests of Mawphlang, in Meghalaya, northeastern India. Sphenomorphus apalpebratus sp. nov. possesses a spectacle or brille, an unusual feature within the Scincidae, and a first for the paraphyletic genus Sphenomorphus. The new species is compared with other members of the genus to which it is here assigned, as well as to members of the lygosomatine genera Lipinia and Scincella from mainland India, the Andaman and Nicobar Islands, and south-east Asia, to which it also bears resemblance. The new taxon is diagnosable in exhibiting the following combination of characters: small body size (SVL to 42.0 mm); moveable eyelids absent; auricular opening scaleless, situated in a shallow depression; dorsal scales show a line of demarcation along posterior edge of ventral pes; midbody scale rows 27-28; longitudinal scale rows between parietals and base of tail 62-64; lamellae under toe IV 8-9; supraoculars five; supralabials 5-6; infralabials 4-5; subcaudals 92; and dorsum golden brown, except at dorsal margin of lateral line, which is lighter, with four faintly spotted lines, two along each side of vertebral row of scales, that extend to tail base. The new species differs from its congeners in the lack of moveable eyelids, a character shared with several distantly related scincid genera.

Linear and nonlinear optical properties of expanded porphyrins: a DMRG study

We study absorption spectra and two photon absorption coefficient of expanded porphyrins (EPs) by the density matrix renormalization group (DMRG) technique. We employ the Pariser-Parr-Pople (PPP) Hamiltonian which includes long-range electron-electron interactions. We find that, in the 4n+2 EPs, there are two prominent low-lying one-photon excitations, while in 4n EPs, there is only one such excitation. We also find that 4n+2 EPs have large two-photon absorption cross sections compared to 4n EPs. The charge density rearrangement in the one-photon excited state is mostly at the pyrrole nitrogen site and at the meso carbon sites. In the two-photon states, the charge density rearrangement occurs mostly at the aza-ring sites. In the one-photon state, the C-C bond length in aza rings shows a tendency to become uniform. In the two-photon state, the bond distortions are on C-N bonds of the pyrrole ring and the adjoining C-C bonds which connect the pyrrole ring to the aza or meso carbon sites.

Effect of myonuclear number and mitochondrial fusion on Drosophila indirect flight muscle organization and size

Mechanisms involved in establishing the organization and numbers of fibres in a muscle are not completely understood. During Drosophila indirect flight muscle (IFM) formation, muscle growth is achieved by both incorporating hundreds of nuclei, and hypertrophy. As a result, IFMs provide a good model with which to understand the mechanisms that govern overall muscle organization and growth. We present a detailed analysis of the organization of dorsal longitudinal muscles (DLMs), a subset of the IFMs. We show that each DLM is similar to a vertebrate fascicle and consists of multiple muscle fibres. However, increased fascicle size does not necessarily change the number of constituent fibres, but does increase the number of myofibrils packed within the fibres. We also find that altering the number of myoblasts available for fusion changes DLM fascicle size and fibres are loosely packed with myofibrils. Additionally, we show that knock down of genes required for mitochondrial fusion causes a severe reduction in the size of DLM fascicles and fibres. Our results establish the organization levels of DLMs and highlight the importance of the appropriate number of nuclei and mitochondrial fusion in determining the overall organization, growth and size of DLMs. (C) 2013 Elsevier Inc. All rights reserved.

Effect of substituent position on optical properties of boron-dipyrromethane isomers

Three isomeric meso-SiMe3C6H4 substituted BODIPYs have been synthesized and their optical properties studied. The constitutional isomers show similar absorption properties but vastly different emissive properties as a result of their different conformational flexibility. Fluorine-19 NMR study is used to unravel the conformational state of the BODIPY isomers at a molecular level. (C) 2013 Elsevier B. V. All rights reserved.

Simulations and experiments in punching spring-steel devices with sub-millimeter features

This work demonstrates the feasibility of mesoscale (100 μm to mm) punching of multiple holes of intricate shapes in metals. Analytical modeling, finite element (FE)simulation, and experimentations are used in this work. Two dimensional FE simulations in ABAQUS were done with an assumed material modeling and plane-strain condition. A known analytical model was used and compared with the ABAQUS simulation results to understand the effects of clearance between the punch and the die. FE simulation in ABAQUS was done for different clearances and corner radii at punch, die, and holder. A set of punches and dies were used to punch out a miniature spring-steel gripper. Comparison of compliant grippers manufactured by wire-cut electro discharge machining(EDM) and punching shows that realizing sharp interior and re-entrant corners by punching is not easy to achieve. Punching of circular holes with 5 mm and 2.5 mm diameter is achieved. The possibility of realizing meso-scale parts with complicated shapes through punching is demonstrated in this work; and some strategies are suggested for improvement.

Revalidation of Natrix clerki Wall, 1925, an overlooked species in the genus Amphiesma Dumeril, Bibron & Dumeril, 1854 (Squamata: Natricidae)

Natrix clerki Wall, 1925, previously known from its sole holotype and considered a synonym of Amphiesma parallelum (Boulenger, 1890), is resurrected in the genus Amphiesma on the basis of the analysis of morphological variation in 28 specimens of ``Amphiesma parallelum'' auctorum, plus six living, unvouchered specimens discovered in Arunachal Pradesh and Nagaland, India, and one vouchered specimen from Talle Valley in Arunachal Pradesh. Specimens from northeast India (Nagaland), northern Myanmar, and China (Yunnan), previously identified as Amphiesma parallelum either in the literature or in museum's catalogues, are also here referred to A. clerki. The holotype of Amphiesma clerki is redescribed. As a consequence, the definition of Amphiesma parallelum is modified. A. parallelum inhabits the Khasi Hills and Naga Hills in Northeast India, whereas A. clerki has a wider range in the Eastern Himalayas, northern Myanmar and Yunnan (China). Amphiesma clerki differs from A. parallelum by its longer tail, dorsal scales more strongly keeled, scales of the first dorsal scale row strongly keeled vs. smooth, a postocular streak not interrupted at the level of the neck, and a much more vivid pattern on a darker background colour. Characters of species of the Amphiesma parallelum group, i.e. A. clerki, A. parallelum, A. bitaeniatum, A. platyceps and A. sieboldii are compared. A key to this group is provided.

Lobe-specific Expression of Phosphodiesterase 5 in Rat Prostate

OBJECTIVE To investigate the level and location of phosphodiesterase 5 (PDE5) expression in rat prostate. METHODS The ventral, dorsal, and lateral lobes of rat prostate were examined for PDE5 expression by Western blotting. Intact rat urogenital complex, including the urinary bladder and accessory reproductive glands, was examined for PDE5 expression by immunohistochemistry. Individual prostatic lobes were further examined by immunofluorescence for expression of PDE5, alpha-smooth muscle actin, and rat endothelial cell antigen. RESULTS Western blot analysis showed that PDE5 was expressed at a significantly lower level in dorsal lobe (DL) than in ventral lobe (VL) or lateral lobe (LL). Immunohistochemistry and immunofluorescence analyses showed that PDE5 was expressed in both acinar epithelium and periacinar smooth muscle. However, although similar levels of smooth muscle PDE5 expression were observed in all 3 prostatic lobes, significantly lower level of epithelial PDE5 expression was found in DL compared with VL or LL. In prostatic blood vessels, PDE5 expression was clearly visible in the endothelium but not as easily detectable in the smooth muscle. CONCLUSION PDE5 was expressed in the acinar epithelium and periacinar smooth muscle of rat prostate. However, the epithelial PDE5 expression was significantly less in DL than in VL or LL. Regardless, the acinar wall, not the blood vessel wall, is the predominant PDE5 expression site in rat prostate. (C) 2015 Elsevier Inc.

A Disulfide Stabilized beta-Sandwich Defines the Structure of a New Cysteine Framework M-Superfamily Conotoxin

The structure of a new cysteine framework (-C-CC-C-C-C) ``M''-superfamily conotoxin, Mo3964, shows it to have a beta-sandwich structure that is stabilized by inter-sheet cross disulfide bonds. Mo3964 decreases outward K+ currents in rat dorsal root ganglion neurons and increases the reversal potential of the Na(V)1.2 channels. The structure of Mo3964 (PDB ID: 2MW7) is constructed from the disulfide connectivity pattern, i.e., 1-3, 2-5, and 4-6, that is hitherto undescribed for the ``M''-superfamily conotoxins. The tertiary structural fold has not been described for any of the known conus peptides. NOE (549), dihedral angle (84), and hydrogen bond (28) restraints, obtained by measurement of (h3)J(NC') scalar couplings, were used as input for structure calculation. The ensemble of structures showed a backbone root mean square deviation of 0.68 +/- 0.18 angstrom, with 87% and 13% of the backbone dihedral (phi, psi) angles lying in the most favored and additional allowed regions of the Ramachandran map. The conotoxin Mo3964 represents a new bioactive peptide fold that is stabilized by disulfide bonds and adds to the existing repertoire of scaffolds that can be used to design stable bioactive peptide molecules.

Factors affecting distribution of fish within a tidally drained mangrove forest in the Andaman and Nicobar Islands, India

Mangrove forests in meso-tidal areas are completely drained during low tides, forming only temporary habitats for fish. We hypothesised that in such temporary habitats, where stranding risks are high, distance from tidal creeks that provided access to inundated areas during receding tides would be the primary determinant of fish distribution. Factors such as depth, root density and shade were hypothesised to have secondary effects. We tested these hypotheses in a tidally drained mangrove patch in the Andaman Islands, India. Using stake nets, we measured fish abundance and species richness relative to distance from creeks, root density/m(2), shade, water depth and size (total length) of fish. We also predicted that larger fish (including potential predators) would be closer to creeks, as they faced a greater chance of mortality if stranded. Thus we conducted tethering trials to examine if predation would be greater close to the creeks. Generalised linear mixed effects models showed that fish abundance was negatively influenced by increasing creek distance interacting with fish size and positively influenced by depth. Quantile regression analysis showed that species richness was limited by increasing creek distance. Proportion of predation was greatest close to the creeks (0-25 m) and declined with increasing distance. Abundance was also low very close to the creeks, suggesting that close to the creeks predation pressure may be an important determinant of fish abundance. The overall pattern however indicates that access to permanently inundated areas, may be an important determinant of fish distribution in tidally drained mangrove forests.

Archean tectonics and crustal evolution of the Biligiri Rangan Block, southern India

The Southern Granulite Terrain in India is a collage of crustal blocks ranging in age from Archean to Neoproterozoic. This study investigate the tectonic evolution of one of the northernmost block- the Biligiri Block (BRB) through a multidisciplinary approach involving field investigation, petrographic studies, LA-ICPMS zircon U-Pb geochronology, Hf isotopic analyses, metamorphic P-T phase diagram computations, and crustal thickness modeling. The garnet bearing quartzofeldspathic gneiss from the central BRB preserve Mesoarchean magmatic zircons with ages between 3207 and 2806 Ma and positive epsilon Hf value (+2.7) which possibly indicates vestiges of a Mesoarchean primitive continental crust. The occurrence of quartzite-iron formation intercalation as well as ultramafic lenses along the western boundary of the BRB is interpreted to indicate that the Kollegal structural lineament is a possible paleo-suture. Phase diagram computation of a metagabbro from the southwestern periphery of the Kollegal suture zone reveals high-pressure (similar to 18.5 kbar) and medium-temperature (similar to 840 degrees C) metamorphism, likely during eastward subduction of the Western Dharwar oceanic crust beneath the Mesoarchean BRB. In the model presented here, slab subduction, melting and underplating processes generated arc magmatism and subsequent charnockitization within the BRB between ca. 2650 Ma and ca. 2498 Ma. These results thus reveal Meso- to Neoarchean tectonic evolution of the BRB. The spatial variation of crustal thickness, derived from flexure inversion technique, provides additional constraints on the tectonic linkage of the BRB with its surrounding terrains. In conjunction with published data, the Moyar and the Kollegal suture zones are considered to mark the trace of ocean closure along which the Nilgiri and Biligiri Rangan Blocks accreted on to the Western Dharwar Craton. (C) 2016 Elsevier B.V. All rights reserved.