The Nature of Bond Critical Points in Dinuclear Copper(I) Complexes

Closed-shell contacts between two copper(I) ions are expected to be repulsive. However, such contacts are quite frequent and are well documented. Crystallographic characterization of such contacts in unsupported and bridged multinuclear copper(I) complexes has repeatedly invited debates on the existence of cuprophilicity. Recent developments in the application of Baders theory of atoms-in-molecules (AIM) to systems in which weak hydrogen bonds are involved suggests that the copper(I)copper(I) contacts would benefit from a similar analysis. Thus the nature of electron-density distributions in copper(I) dimers that are unsupported, and those that are bridged, have been examined. A comparison of complexes that are dimers of symmetrical monomers and those that are dimers of two copper(I) monomers with different coordination spheres has also been made. AIM analysis shows that a bond critical point (BCP) between two Cu atoms is present in most cases. The nature of the BCP in terms of the electron density, ?, and its Laplacian is quite similar to the nature of critical points observed in hydrogen bonds in the same systems. The ? is inversely correlated to Cu?Cu distance. It is higher in asymmetrical systems than what is observed in corresponding symmetrical systems. By examining the ratio of the local electron potential-energy density (Vc) to the kinetic energy density (Gc), |Vc|/Gc at the critical point suggests that these interactions are not perfectly ionic but have some shared nature. Thus an analysis of critical points by using AIM theory points to the presence of an attractive metallophilic interaction similar to other well-documented weak interactions like hydrogen bonding.

Fatigue de-bond growth in adhesively bonded single lap joints

The fatigue de-bond growth studies have been conducted on adhesively bonded lap joint specimens between aluminium and aluminium with Redux-319A adhesive with a pre-defined crack of 3 mm at the bond end. The correlations between fracture parameters and the de-bond growth data are established using both numerical and experimental techniques. In the numerical method, geometrically non-linear finite element analyses were carried out on adhesively bonded joint specimen for various de-bond lengths measured from the lap end along the mid-bond line of the adhesive. The finite element results were post processed to estimate the SERR components G (I) and G (II) using the Modified Virtual Crack Closure Integral (MVCCI) procedure. In experimental work, specimens were fabricated and fatigue de-bond growth tests were conducted at a stress ratio R = -1. The results obtained from both numerical analyses and testing have been used to generate de-bond growth curve and establish de-bond growth law in the Paris regime for such joints. The de-bond growth rate is primarily function of mode-I SERR component G (I) since the rate of growth in shear mode is relatively small. The value of Paris exponent m is found to be 6.55. The high value of de-bond growth exponent in Paris regime is expected, since the adhesive is less ductile than conventional metallic materials. This study is important for estimating the life of adhesively bonded joints under both constant and variable amplitude fatigue loads.

Pricing Defaultable Bonds in a Markov Modulated Market

We address the problem of pricing defaultable bonds in a Markov modulated market. Using Merton's structural approach we show that various types of defaultable bonds are combination of European type contingent claims. Thus pricing a defaultable bond is tantamount to pricing a contingent claim in a Markov modulated market. Since the market is incomplete, we use the method of quadratic hedging and minimal martingale measure to derive locally risk minimizing derivative prices, hedging strategies and the corresponding residual risks. The price of defaultable bonds are obtained as solutions to a system of PDEs with weak coupling subject to appropriate terminal and boundary conditions. We solve the system of PDEs numerically and carry out a numerical investigation for the defaultable bond prices. We compare their credit spreads with some of the existing models. We observe higher spreads in the Markov modulated market. We show how business cycles can be easily incorporated in the proposed framework. We demonstrate the impact on spreads of the inclusion of rare states that attempt to capture a tight liquidity situation. These states are characterized by low risk-free interest rate, high payout rate and high volatility.

Non-monotonic, distance-dependent relaxation of water in reverse micelles: Propagation of surface induced frustration along hydrogen bond networks

Layer-wise, distance-dependent orientational relaxation of water confined in reverse micelles (RM) is studied using theoretical and computational tools. We use both a newly constructed ``spins on a ring'' (SOR) Ising-type model (with Shore-Zwanzig rotational dynamics) and atomistic simulations with explicit water. Our study explores the effect of reverse micelle size and role of intermolecular correlations, compromised by the presence of a highly polar surface, on the distance (from the interface) dependence of water relaxation. The ``spins on a ring'' model can capture some aspects of distance dependence of relaxation, such as acceleration of orientational relaxation at intermediate layers. In atomistic simulations, layer-wise decomposition of hydrogen bond formation pattern clearly reveals that hydrogen bond arrangement of water at a certain distance away from the surface can remain frustrated due to the interaction with the polar surface head groups. This layer-wise analysis also reveals the presence of a non-monotonic slow relaxation component which can be attributed to this frustration effect and which is accentuated in small to intermediate size RMs. For large size RMs, the long time component decreases monotonically from the interface to the interior of the RMs with slowest relaxation observed at the interface. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4732095]

A method for stabilizing the cis prolyl peptide bond: influence of an unusual n -> pi* interaction in 1,3-oxazine and 1,3-thiazine containing peptidomimetics

The cis/trans isomer ratios of the Xaa-Pyr (Pyr = pyrrolidine) 3 degrees amide bonds are significantly high (similar to 90% cis) in the novel peptidomimetics where Pyr contains 1,3-oxazine (Oxa) or 1,3-thiazine (Thi) at its 2 position. We find that an unusual n -> pi(i-1)* interaction, selectively stabilizes the cis conformer and the n X n repulsion destabilizes the trans conformer of these molecules. Both these electronic effects oppose the steric effects in the 3 degrees amide bond. The structural requirements for manifestation of these electronic effects are determined. (c) 2012 Elsevier Ltd. All rights reserved.

Bond Graph Modeling for Energy-Harvesting Wireless Sensor Networks

Researchers can use bond graph modeling, a tool that takes into account the energy conservation principle, to accurately assess the dynamic behavior of wireless sensor networks on a continuous basis.

A new method for fracture toughness determination of graded (Pt,Ni)Al bond coats by microbeam bend tests

A novel method is proposed for fracture toughness determination of graded microstructurally complex (Pt,Ni)Al bond coats using edge-notched doubly clamped beams subjected to bending. Micron-scale beams are machined using the focused ion beam and loaded in bending under a nanoindenter. Failure loads gathered from the pop-ins in the load-displacement curves combined with XFEM analysis are used to calculate K-c at individual zones, free from substrate effects. The testing technique and sources of errors in measurement are described and possible micromechanisms of fracture in such heterogeneous coatings discussed.

Anticancer Activity of Hydrogen-Bond-Stabilized Half-Sandwich RuII Complexes with Heterocycles

Neutral half-sandwich organometallic ruthenium(II) complexes of the type (?6-cymene)RuCl2(L)] (H1H10), where L represents a heterocyclic ligand, have been synthesized and characterized spectroscopically. The structures of five complexes were also established by single-crystal X-ray diffraction confirming a piano-stool geometry with ?6 coordination of the arene ligand. Hydrogen bonding between the N?H group of the heterocycle and a chlorine atom attached to Ru stabilizes the metalligand interaction. Complexes coordinated to a mercaptobenzothiazole framework (H1) or mercaptobenzoxazole (H6) showed high cytotoxicity against several cancer cells but not against normal cells. In vitro studies have shown that the inhibition of cancer cell growth involves primarily G1-phase arrest as well as the generation of reactive oxygen species (ROS). The complexes are found to bind DNA in a non-intercalative fashion and cause unwinding of plasmid DNA in a cell-free medium. Surprisingly, the cytotoxic complexes H1 and H6 differ in their interaction with DNA, as observed by biophysical studies, they either cause a biphasic melting of the DNA or the inhibition of topoisomerase IIa activity, respectively. Substitution of the aromatic ring of the heterocycle or adding a second hydrogen-bond donor on the heterocycle reduces the cytotoxicity.

Origin of grand minima in Sunspot cycles

One of the most striking aspects of the 11-year sunspot cycle is that there have been times in the past when some cycles went missing, a most well-known example of this being the Maunder minimum during 1645-1715. Analyses of cosmogenic isotopes (C-14 and Be-10) indicated that there were about 27 grand minima in the last 11 000 yrs, implying that about 2.7% of the solar cycles had conditions appropriate for forcing the Sun into grand minima. We address the question of how grand minima are produced and specifically calculate the frequency of occurrence of grand minima from a theoretical dynamo model. We assume that fluctuations in the poloidal field generation mechanism and in the meridional circulation produce irregularities of sunspot cycles. Taking these fluctuations to be Gaussian and estimating the values of important parameters from the data of the last 28 solar cycles, we show from our flux transport dynamo model that about 1-4% of the sunspot cycles may have conditions suitable for inducing grand minima.

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.

B-H Bond Activation Using an Electrophilic Metal Complex: Insights into the Reaction Pathway

A highly electrophilic ruthenium center in the RuCl(dppe)(2)]OTf] complex brings about the activation of the B H bond in ammonia borane (H3N center dot BH3, AB) and dimethylamine borane (Me2HN center dot BH3, DMAB). At room temperature, the reaction between RuCl(dppe)(2)]OTf] and AB or DMAB results in trans-RuH(eta(2)-H-2)(dppe)(2)]OTf] trans-RuCl(eta(2)-H-2)(dppe)(2)]OTf], and trans-RuH(Cl)(dppe)(2)], as noted in the NMR spectra. Mixing the ruthenium complex and AB or DMAB at low temperature (198/193 K) followed by NMR spectral measurements as the reaction mixture was warmed up to room temperature allowed the observation of various species formed enroute to the final products that were obtained at room temperature. On the basis of the variable-temperature multinuclear NMR spectroscopic studies of these two reactions, the mechanistic insights for B-H bond activation were obtained. In both cases, the reaction proceeds via an eta(1)-B-H moiety bound to the metal center. The detailed mechanistic pathways of these two reactions as studied by NMR spectroscopy are described.

Charge Density Analysis of Ferulic Acid: Robustness of a Trifurcated C-H center dot center dot center dot O Hydrogen Bond

The toplogical features of a sporadic trifurcated C-H center dot center dot center dot O interaction region, where an oxygen atom acts as an acceptor of three weak hydrogen bonds, has been investigated by experimental and theoretical charge density analysis of ferulic acid. The interaction energy of the asymmetric molecular dimer formed by the trifurcated C-H center dot center dot center dot O motif, based on the multipolar model, is shown to be greater than the corresponding asymmetric O-H center dot center dot center dot O dimer in this crystal structure. Further, the hydrogen bond energies associated with these interaction motifs have been estimated from the local kinetic and potential energy densities at the bond critical points. The trends suggest that the interaction energy of the trifurcated C-H center dot center dot center dot O region is comparable to that of a single O-H center dot center dot center dot O hydrogen bond.

Electrophile-Induced C-C Bond Activation of Vinylcyclopropanes for the Synthesis of Z-Alkylidenetetrahydrofurans

We present a detailed study on the behavior of vinylcyclopropanes as masked donor acceptor system toward the stereoselective synthesis of Z-alkylidenetetrahydrofurans. Results of bromenium catalyzed indirect activation of C-C bond of vinylcyclopropanes and concomitant cyclization to alkylidenetetrahydrofuran and other heterocycles have been discussed. The stereoselective formation of the Z-isomer is strongly controlled by the extent of destabilization of one of the gauche conformers of the vinylcyclopropane. The ring-opening/cyclization step was found to be stereospecific as in the case of DA cyclopropanes. The activation of the C-C bond leads to a tight-carbocation intermediate, which is evident from the complete retention of the stereochemistry. The retention of configuration has been established by a necessary control experiment that rules out the possibility of a double inversion pathway. The present results serve as direct stereochemical evidence in support of a tight ion-pair intermediate versus the controversial S(N)2 pathway. A 2D potential energy scan has been carried out at B3LYP/6-31G(d) level theory to obtain the relative energies of the conformers. The Z-selectivity observed has been explained on the basis of the relative population of the conformers and modeling the intermediate and transition state involved in the reaction at M06-2x/6-31+G(d) level. Energy profile for the cyclization step was modeled considering various possible pathways through which cyclization can happen. The methodology has been successfully demonstrated on vinylcyclobutanes as well.

Relative roles of instruction count and cycles per instruction in WCET estimation

Most of the existing WCET estimation methods directly estimate execution time, ET, in cycles. We propose to study ET as a product of two factors, ET = IC * CPI, where IC is instruction count and CPI is cycles per instruction. Considering directly the estimation of ET may lead to a highly pessimistic estimate since implicitly these methods may be using worst case IC and worst case CPI. We hypothesize that there exists a functional relationship between CPI and IC such that CPI=f(IC). This is ascertained by computing the covariance matrix and studying the scatter plots of CPI versus IC. IC and CPI values are obtained by running benchmarks with a large number of inputs using the cycle accurate architectural simulator, Simplescalar on two different architectures. It is shown that the benchmarks can be grouped into different classes based on the CPI versus IC relationship. For some benchmarks like FFT, FIR etc., both IC and CPI are almost a constant irrespective of the input. There are other benchmarks that exhibit a direct or an inverse relationship between CPI and IC. In such a case, one can predict CPI for a given IC as CPI=f(IC). We derive the theoretical worst case IC for a program, denoted as SWIC, using integer linear programming(ILP) and estimate WCET as SWIC*f(SWIC). However, if CPI decreases sharply with IC then measured maximum cycles is observed to be a better estimate. For certain other benchmarks, it is observed that the CPI versus IC relationship is either random or CPI remains constant with varying IC. In such cases, WCET is estimated as the product of SWIC and measured maximum CPI. It is observed that use of the proposed method results in tighter WCET estimates than Chronos, a static WCET analyzer, for most benchmarks for the two architectures considered in this paper.

Engagement of CF3 Group in N-H center dot center dot center dot F-C Hydrogen Bond in the Solution State: NMR Spectroscopy and MD Simulation Studies

Unambiguous evidence for the engagement of CF3 group in N-H center dot center dot center dot F-C hydrogen bond in a low polarity solvent, the first observation of its kind, is reported. The presence of such weak molecular interactions in the solution state is convincingly established by one and two-dimensional H-1, F-19, and natural abundant N-15 NMR spectroscopic studies. The strong and direct evidence is derived by the observation of through-space couplings, such as, (1h)J(FH), (1h)J(FN), and (2h)J(FF), where the spin polarization is transmitted through hydrogen bond. In an interesting example of a molecule containing two CF3 groups getting simultaneously involved in hydrogen bond, where hydrogen bond mediated couplings are not reflected in the NMR spectrum, F-19-F-19 NOESY experiment yielded confirmatory evidence. Significant deviations in the strengths of (1)J(NH), variable temperature, and the solvent induced perturbations yielded additional support. The NMR results are corroborated by both DFT calculations and MD simulations, where the quantitative information on different ways of involvement of fluorine in two and three centered hydrogen bonds, their percentage of occurrences, and geometries have been obtained. The hydrogen bond interaction energies have also been calculated.