Negative hyperconjugation and red-, blue- or zero-shift in X-Z center dot center dot center dot Y complexes

A generalized explanation is provided for the existence of the red-and blue-shifting nature of X-Z bonds (Z = H, halogens, chalcogens, pnicogens, etc.) in X-Z center dot center dot center dot Y complexes based on computational studies on a selected set of weakly bonded complexes and analysis of existing literature data. The additional electrons and orbitals available on Z in comparison to H make for dramatic differences between the H-bond and the rest of the Z-bonds. The nature of the X-group and its influence on the X-Z bond length in the parent X-Z molecule largely controls the change in the X-Z bond length on X-Z center dot center dot center dot Y bond formation; the Y-group usually influences only the magnitude of the effects controlled by X. The major factors which control the X-Z bond length change are: (a) negative hyperconjugative donation of electron density from X-group to X-Z sigma* antibonding molecular orbital (ABMO) in the parent X-Z, (b) induced negative hyperconjugation from the lone pair of electrons on Z to the antibonding orbitals of the X-group, and (c) charge transfer (CT) from the Y-group to the X-Z sigma* orbital. The exchange repulsion from the Y-group that shifts partial electron density at the X-Z sigma* ABMO back to X leads to blue-shifting and the CT from the Y-group to the sigma* ABMO of X-Z leads to red-shifting. The balance between these two opposing forces decides red-, zero- or blue-shifting. A continuum of behaviour of X-Z bond length variation is inevitable in X-Z center dot center dot center dot Y complexes.

Dynamics of the chemical bond: inter- and intra-molecular hydrogen bond

In this discussion, we show that a static definition of a `bond' is not viable by looking at a few examples for both inter-and intra-molecular hydrogen bonding. This follows from our earlier work (Goswami and Arunan, Phys. Chem. Chem. Phys. 2009, 11, 8974) which showed a practical way to differentiate `hydrogen bonding' from `van der Waals interaction'. We report results from ab initio and atoms in molecules theoretical calculations for a series of Rg center dot center dot center dot HX complexes (Rg = He/Ne/Ar and X = F/Cl/Br) and ethane-1,2-diol. Results for the Rg center dot center dot center dot HX/DX complexes show that Rg center dot center dot center dot DX could have a `deuterium bond' even when Rg center dot center dot center dot HX is not `hydrogen bonded', according to the practical criterion given by Goswami and Arunan. Results for ethane-1,2-diol show that an `intra-molecular hydrogen bond' can appear during a normal mode vibration which is dominated by the O center dot center dot center dot O stretching, though a `bond' is not found in the equilibrium structure. This dynamical `bond' formation may nevertheless be important in ensuring the continuity of electron density across a molecule. In the former case, a vibration `breaks' an existing bond and in the later case, a vibration leads to `bond' formation. In both cases, the molecule/complex stays bound irrespective of what happens to this `hydrogen bond'. Both these cases push the borders on the recent IUPAC recommendation on hydrogen bonding (Arunan et al. Pure. Appl. Chem. 2011, 83 1637) and justify the inclusive nature of the definition.

Pluronic copolymer encapsulated SCR7 as a potential anticancer agent

Nonhomologous end joining (NHEJ) of DNA double strand breaks (DSBs) inside cells can be selectively inhibited by 5,6-bis-(benzylideneamino)-2-mercaptopyrimidin-4-ol (SCR7) which possesses anticancer properties. The hydrophobicity of SCR7 decreases its bioavailability which is a major setback in the utilization of this compound as a therapeutic agent. In order to circumvent the drawback of SCR7, we prepared a polymer encapsulated form of SCR7. The physical interaction of SCR7 and Pluronic (R) copolymer is evident from different analytical techniques. The in vitro cytotoxicity of the drug formulations is established using the MTT assay.

Spatio-temporal correlations in aqueous systems: computational studies of static and dynamic heterogeneity by 2D-IR spectroscopy

Local heterogeneity is ubiquitous in natural aqueous systems. It can be caused locally by external biomolecular subsystems like proteins, DNA, micelles and reverse micelles, nanoscopic materials etc., but can also be intrinsic to the thermodynamic nature of the aqueous solution itself (like binary mixtures or at the gas-liquid interface). The altered dynamics of water in the presence of such diverse surfaces has attracted considerable attention in recent years. As these interfaces are quite narrow, only a few molecular layers thick, they are hard to study by conventional methods. The recent development of two dimensional infra-red (2D-IR) spectroscopy allows us to estimate length and time scales of such dynamics fairly accurately. In this work, we present a series of interesting studies employing two dimensional infra-red spectroscopy (2D-IR) to investigate (i) the heterogeneous dynamics of water inside reverse micelles of varying sizes, (ii) supercritical water near the Widom line that is known to exhibit pronounced density fluctuations and also study (iii) the collective and local polarization fluctuation of water molecules in the presence of several different proteins. The spatio-temporal correlation of confined water molecules inside reverse micelles of varying sizes is well captured through the spectral diffusion of corresponding 2D-IR spectra. In the case of supercritical water also, we observe a strong signature of dynamic heterogeneity from the elongated nature of the 2D-IR spectra. In this case the relaxation is ultrafast. We find remarkable agreement between the different tools employed to study the relaxation of density heterogeneity. For aqueous protein solutions, we find that the calculated dielectric constant of the respective systems unanimously shows a noticeable increment compared to that of neat water. However, the `effective' dielectric constant for successive layers shows significant variation, with the layer adjacent to the protein having a much lower value. Relaxation is also slowest at the surface. We find that the dielectric constant achieves the bulk value at distances more than 3 nm from the surface of the protein.

Ultrasonic Guided Wave Sensor Network Optimization for Monitoring Rivet Line

Guided waves using piezo-electric wafer active sensors (PWAS) is one of the useful techniques of damage detection. Sensor network optimization with minimal network hardware footprint and maximal area of coverage remains a challenging problem. PWAS sensors are placed at discrete locations in order to inspect damages in plates and the idea has the potential to be extended to assembled structures. Various actuator-sensor configurations are possible within the network in order to identify and locate damages. In this paper we present a correlation based approach to monitor cracks emanating from rivet line using a simulated guided wave signal whose sensor is operating in pulse echo mode. Discussions regarding the identification of phase change due to reflections from the crack are also discussed in this paper.

薄膜非线性撕裂三种弯曲模型的解答及讨论

针对薄膜非线性撕裂的弯曲模型,引入了3种表征薄膜撕裂过程的双参数准则.这3种表征分别为:(1)界面断裂韧度和分离应力;(2)界面断裂韧度和薄膜的裂尖转角;(3)界面断裂韧度和薄膜在裂尖的临界Mises等效应变.从3种双参数准则入手,分析并给出了针对上述各准则的薄膜非线性撕裂问题的解答.通过分析和比较,建立弯曲模型解答与严格平面应变弹塑性分析解答之间的关联.

The effect of nucleation time on the growth of a microvoid in a viscoelastic material

In this paper, discussions are focused on the growth of a nucleated void in a viscoelastic material. The in situ tensile tests of specimens made of high-density polyethylene, filled with spherical glass beads (HDPE/GB) are carried out under SEM. The experimental result indicates that the microvoid nucleation is induced by the partially interfacial debonding of particles. By means of the Laplace transform and the Eshelby's equivalent inclusion method, a new analytical expression of the void strain at different nucleation times is derived. It can be seen that the strain of the nucleated void depends not only on the remote strain history, but also on the nucleation time. This expression is also illustrated by numerical examples, and is found to be of great usefulness in the study of damage evolution in viscoelastic materials.

Escritura y tradición : Karl Rahner en el “primer conflicto doctrinal” del Vaticano II

Resumen: En 2012 se cumplen 50 años del inicio del Concilio Vaticano II, inaugurado por el Papa Juan XXIII el 11 de octubre de 1962. Es un dato reconocido el importante papel que desarrollaron muchos teólogos a lo largo de los diversos debates conciliares. Entre ellos destaca la figura de K. Rahner. Su principal contribución se dirigió a los asuntos eclesiológicos. Menos conocido es su aporte a los debates que, iniciados en octubre de 1962, conducirían, recién en 1965, a la aprobación de la Constitución Dei Verbum. Luego de una breve introducción, me detengo, en primer lugar, en el informe que Rahner preparó en noviembre de 1962 en contra del Esquema preparatorio, De fontibus revelationis. En un segundo momento, describo otro texto, el llamado “Esquema Rahner – Ratzinger”, elaborado en la misma época, pensado como un texto alternativo al oficial. En tercer lugar, destaco algunas ideas centrales de una conferencia de Rahner de 1963, titulada “Escritura y Tradición”. Finalmente, analizo el número noveno de Dei Verbum que, como se advertirá, muestra que las posiciones bíblico-sistemáticas de Rahner se direccionaban en el sentido de la llamada mayoría conciliar.

La percepción de los valores morales

Resumen: El autor aborda un tema que a veces pasa inadvertido aun para muchos adherentes al iusnaturalismo: el conocimiento de la ley natural. Mientras abundan estudios que centran sus argumentos en la existencia de esta normativa supra positiva o que ahondan su ontología y extensión, sin embargo a veces no se repara en una cuestión liminar que resulta necesario dilucidar: ¿cómo se conocen los principios y las conclusiones de la ley natural?, ¿es naturalmente conocida?, ¿qué se entiende por “naturalmente”? Sobre el contenido de la ley natural el documento afirma que “no es un conjunto cerrado y completo de normas morales, sino la fuente de inspiración constante, presente y operativa de las diversas etapas de la economía de la salvación”. El término “percepción” hace referencia a una “experiencia” y que por tanto es exterior. Se concluye entonces que consiste en un conocimiento objetivo (no innato) de los preceptos morales, más allá de la presencia natural de un hábito que permite su captación (sindéresis).