Thermodynamics of action and organization in a system

Complexity in nature is astounding yet the explanation lies in the fundamental laws of physics. The Second Law of Thermodynamics and the Principle of Least Action are the two theories of science that have always stood the test of time. In this article, we use these fundamental principles as tools to understand how and why things happen. In order to achieve that, it is of absolute necessity to define things precisely yet preserving their applicability in a broader sense. We try to develop precise, mathematically rigorous definitions of the commonly used terms in this context, such as action, organization, system, process, etc., and in parallel argue the behavior of the system from the first principles. This article, thus, acts as a mathematical framework for more discipline‐specific theories. © 2015 Wiley Periodicals, Inc. Complexity 21: 307–317, 2016     

Effect of nitrogen on mechanical,oxidation and structural behaviour of Ti–Si–B–C–N nanocomposite hard coatings deposited by DC sputtering

Ti–Si–B–C–N film was deposited by DC magnetron sputtering at different argon and nitrogen ratios such as N₂/Ar = 1 : 5, 2 : 4, 3 : 3, 4 : 1 and 5 : 0. The formation of TiN and TiB phases was observed because of incorporation of nitrogen. The hardness, modulus, microstructure, structure and bond formation with different nitrogen contents during the deposition were studied by nanoindentation, scanning electron microscope, X‐ray diffraction and X‐ray photoelectron spectroscopy, respectively. The oxidation kinetics of Ti–Si–B–C–N was investigated. The nitrogen incorporation during deposition influences different properties of the coating. Hardness and modulus decreased, and microstructure showed very fine grain presence, and film changes to fully amorphous because of incorporation of nitrogen in the film. Copyright © 2016 John Wiley & Sons, Ltd.     

Application of principal component analysis in protein unfolding: an all-atom molecular dynamics simulation study

We have performed molecular dynamics (MD) simulation of the thermal denaturation of one protein and one peptide-ubiquitin and melittin. To identify the correlation in dynamics among various secondary structural fragments and also the individual contribution of different residues towards thermal unfolding, principal component analysis method was applied in order to give a new insight to protein dynamics by analyzing the contribution of coefficients of principal components. The cross-correlation matrix obtained from MD simulation trajectory provided important information regarding the anisotropy of backbone dynamics that leads to unfolding. Unfolding of ubiquitin was found to be a three-state process, while that of melittin, though smaller and mostly helical, is more complicated.     

Diastereoselective C-C bond formation at C-5 of vinyl sulfone-modified hex-5-enofuranosyl carbohydrates: diversity-oriented synthesis of branched-chain sugars and beyond

This is the first report on the diastereoselective addition of carbon nucleophiles to vinyl sulfone-modified hex-5-enofuranosides. The stereoelectronic properties of the substituents at the C-3 position and their interactions with the incoming carbon nucleophiles control the diastereoselectivity of addition at the C-5 position, favoring the formation of l-ido derivatives as major products in most of the cases studied. This new concept of stereocontrolled carbon-carbon bond formation in vinyl sulfone-modified carbohydrates is general in nature. The novel chirons generated by this diversity-oriented synthetic method have been implemented in the preparation of a wide range of hexofuranosyl C-5 branched-chain sugars, bicyclic derivatives, chirally pure enals, and densely functionalized carbocycles.     

K-Carrageenan Stimulates Pre-Osteoblast Proliferation and Osteogenic Differentiation: A Potential Factor for the Promotion of Bone Regeneration?

Current cell-based bone tissue regeneration strategies cannot cover large bone defects. K-carrageenan is a highly hydrophilic and biocompatible seaweed-derived sulfated polysaccharide, that has been proposed as a promising candidate for tissue engineering applications. Whether κ-carrageenan can be used to enhance bone regeneration is still unclear. In this study, we aimed to investigate whether κ-carrageenan has osteogenic potential by testing its effect on pre-osteoblast proliferation and osteogenic differentiation in vitro. Treatment with κ-carrageenan (0.5 and 2 mg/mL) increased both MC3T3-E1 pre-osteoblast adhesion and spreading at 1 h. K-carrageenan (0.125–2 mg/mL) dose-dependently increased pre-osteoblast proliferation and metabolic activity, with a maximum effect at 2 mg/mL at day three. K-carrageenan (0.5 and 2 mg/mL) increased osteogenic differentiation, as shown by enhanced alkaline phosphatase activity (1.8-fold increase at 2 mg/mL) at day four, and matrix mineralization (6.2-fold increase at 2 mg/mL) at day 21. K-carrageenan enhanced osteogenic gene expression (Opn, Dmp1, and Mepe) at day 14 and 21. In conclusion, κ-carrageenan promoted MC3T3-E1 pre-osteoblast adhesion and spreading, metabolic activity, proliferation, and osteogenic differentiation, suggesting that κ-carrageenan is a potential osteogenic inductive factor for clinical application to enhance bone regeneration.     

Gastroprotective Effects of Biological Macromolecule: Polysaccharides

The large molecular weight of the macromolecules sets them apart from all other components. This may range from 10 000 to over a million. While the molecular weight of other plant metabolites is seldom beyond 1000. Chemically, macromolecules are made up of long chains and little “building pieces,” which are joined covalently in a variety of ways. Biological macromolecules are large, naturally occurring cellular building blocks that play a range of crucial roles in the development and existence of living organisms. Biomacromolecules are essential in the biomedical field and other related professions. They feature a variety of beneficial properties, including excellent biodegradability, suitable mechanical strength, enhanced bioavailability, etc. They also have significant biocompatibility. They display a variety of biological characteristics, such as antimalignant, antidiabetic, antibacterial, antioxidant, and immunomodulatory. The use of essential carbohydrates including alginate, chitosan, pectin, starches, carrageenan, fucoidan, etc. is common in commercial applications. Natural substance-based pharmacotherapy is now considered to be a highly promising future alternative to conventional medicine. Along with proteins and polynucleotides, polysaccharide is a vital biomacromolecule that has a crucial function in the growth and expansion of living things. A crucial element of higher plants, cell membranes of animal, and cell walls of microbes is polysaccharide. It is intimately tied to physiological processes as well. The importance of polysaccharides as a significant class of bioactive natural compounds has received more attention recently. Numerous studies have shown that natural polysaccharides contain bioactivities, which have led to the use of polysaccharides in the treatment of illness. The many parts of the research findings on the bioactivities of polysaccharides in gastro-protection are included in this paper.     

Esterification of butyric acid with n-butanol: Kinetic study using experimental data and modeling

Present study involves the investigation of the esterification kinetics between butyric acid and n-butanol. This reaction was conducted in a batch reactor, utilizing homogeneous methanesulfonic acid (MSA) catalyst. Response surface methodology (RSM) was conducted prior to the kinetic study using “Design Expert; version-11.0” for finding the causal factors influencing the conversion of butyric acid. Most important factors identified with their limits against conversions (during optimization of the process using RSM) were taken up to critically analyze the effect of them on butyric acid conversion. Concentration and activity-based model of the process were proposed assuming second order reversible reaction scheme using homogeneous MSA catalyst. During the study of non-ideal behavior of the system, UNIFAC model was adapted for assessing the activity coefficients of species present in equilibrated liquid phase. Experimental data were used to evaluate kinetic and thermodynamic parameters such as rate constants, activation energy, enthalpy, and entropy of the system. The endothermic nature of esterification was confirmed by positive value of enthalpy obtained. The effect of various levels of causal variables like temperature (60–90°C), catalyst concentration (0.5–1.5 wt.%), and molar ratio of n-butanol to butyric acid (1–3) on conversion kinetics of butyric acid was investigated during transient and equilibrium phase of the reaction. It has been observed that molar ratio of butanol to butyric acid has the highest influence on the conversion. The rate equation derived offered a kinetic and thermodynamic framework to the generated data. It also exhibits a notable degree of conformity of predicted data to the experimental ones and effectively characterizes the system across different reaction temperatures, reactant molar ratio, and catalyst concentration.     

Degeneracy in one dimension: Role of singular potentials

That the bound energy eigenstates of one-dimensional quantum systems can be degenerate in the presence of specific singular or supersingular potentials is demonstrated by choosing a family of bistable and other oscillators. Relevance of our study to spectroscopic observations is noted. Quasi-degeneracy is found even in the absence of any singularity in the potential and the importance of tunneling is highlighted in this context to analyze the general nature of such potentials leading to double degeneracy. Additionally, the case of spiked oscillators is discussed with particular reference to the “Klauder phenomenon,” revealing clearly that the mere presence of singularity in the potential is not a sufficient criterion for the occurrence of degeneracy. © 1996 John Wiley & Sons, Inc.     

Chemical Degradation of Mercury Alkyls Mediated by Copper Selenide Nanosheets

Methylation and demethylation of mercury compounds are two important competing processes that control the net production of highly toxic mercury alkyls, methylmercury (MeHg⁺) and dimethylmercury (Me₂Hg), in environment. Although the microbial and the photochemical methylation and demethylation processes are well studied in recent years but the chemical methylation and demethylation processes have not been studied well. Herein, we report for the first time that the CuSe nanosheet has remarkable ability to activate the highly inert Hg?C bonds of various MeHg⁺ and Me₂Hg compounds at room temperature (21 °C). It facilitates the conversion of MeHg⁺ into Me₂Hg in the absence of any proton donors. Whereas, in the presence of any proton source, it has unique ability to degrade MeHg⁺ into CH₄ and inorganic mercury (Hg²⁺). Detailed studies revealed that the relatively fast Hg?C bond cleavage was observed in case of MeHgSPh or MeHgI in comparison to MeHgCl, indicating that the Hg?C bond in MeHgCl is relatively inert in nature. On the other hand, the Hg?C bond in Me₂Hg is considered to be exceedingly inert and, thus, difficult to cleave at room temperature. However, CuSe nanosheets showed unique ability to degrade Me₂Hg into CH₄ and Hg²⁺, via the formation of MeHg⁺, under acidic conditions at room temperature. DFT calculations revealed that the Hg?C bond activation occurs through adsorption on the surface of (100)‐faceted CuSe nanosheets.     

Quantum Phase Properties of Photon Added and Subtracted Displaced Fock States

Quantum phase properties of photon added and subtracted displaced Fock states (and their limiting cases) are investigated from a number of perspectives, and it is shown that the quantum phase properties are dependent on the quantum state engineering operations performed. Specifically, the analytic expressions for quantum phase distributions and angular Q distribution as well as measures of quantum phase fluctuation and phase dispersion are obtained. The uniform phase distribution of the initial Fock states is observed to be transformed by the unitary operation (i.e., displacement operator) into non‐Gaussian shape, except for the initial vacuum state. It is observed that the phase distribution is symmetric with respect to the phase of the displacement parameter and becomes progressively narrower as its amplitude increases. The non‐unitary (photon addition/subtraction) operations make it even narrower in contrast to the Fock parameter, which leads to broadness. The photon subtraction is observed to be a more powerful quantum state engineering tool in comparison to the photon addition. Further, one of the quantum phase fluctuation parameters is found to reveal the existence of antibunching in both the engineered quantum states under consideration. Finally, the relevance of the engineered quantum states in the quantum phase estimation is also discussed.