On the Nature of the Positronic Bond

Recently it has been proposed that the positron, the anti-particle analog of the electron, is capable of forming an anti-matter bond in a composite system consists of two hydride anions and a positron [Angew. Chem. Int. Ed. 57 , 8859–8864 (2018)]. In order to dig into the nature of this novel bond the newly developed multi-component quantum theory of atoms in molecules (MC-QTAIM) is applied to this positronic system. The topological analysis reveals that this species is composed of two atoms in molecules, each containing a proton and half of the electronic and the positronic populations. Further analysis elucidates that the electron exchange phenomenon is virtually non-existent between the two atoms and no electronic covalent bond is conceivable in between. On the other hand, it is demonstrated that the positron density enclosed in each atom is capable of stabilizing interactions with the electron density of the neighboring atom. This electrostatic interaction suffices to make the whole system bonded against all dissociation channels. Thus, the positron indeed acts like an anti-matter glue between the two atoms.     

On the Nature of the Temperature-Induced Transition From the Molten Globule to the Unfolded State of Globular Proteins

In this paper we try to perform a thermodynamic analysis of the temperature-induced transition from the molten globule to the unfolded state of globular proteins. A series of calorimetric investigations showed that this process is not associated with an excess heat capacity absorption peak, and cannot be regarded as a first-order phase transition. This result contrasts with the well-established conclusion that the thermal unfolding of the native tertiary structure of globular proteins is a first-order phase transition. First, the theoretical approach developed by Ikegami is outlined to emphasize that a second-order or gradual transition induced by temperature is expected for globular proteins when the various secondary structure elements do not interact cooperatively. Secondly, a simple thermodynamic model is presented which, taking into account the independence of the secondary structure elements among each other, is able to rationalize the shape of the experimental DSC profiles.This revised version was published online in November 2005 with corrections to the Cover Date.     

"地小氢"和"月小氢"

Hydrogen is the most abundant chemical element in the Universe and is tightly related to human life. This article personifies hydrogen, bringing a close interaction between the hydrogen on the moon and the hydrogen on the Earth. Through lively and interesting dialogues, the history of hydrogen discovery and the properties are introduced, and the application of hydrogen in different aspects of the future is prospected.     

The computation of the representation matrices of the generators of the unitary group

A method is presented for the efficient computation of the representation matrices of the unitary group, U(n) in the Gelfand—Tsetlin basis (corresponding to the usual spin-symmetry adapted basis for an N electron CI). The present scheme is conceptually and computationally attractive in that it is formulated directly in terms of Weyl tableaux and also that it permits simultaneous basis vector generation and matrix element evaluation. In addition the basis vectors are ordered so that subsequent restriction to the three dimensional rotation group is facilitated. An illustrative example is also presented.Taken in part from a thesis submitted to the University of London in partial fulfilment of the requirements for the degree of PhD.     

On the scaling of the interface energy of the liquid clusters in the disordered nanoporous medium

Similarity of the extrusion curves of non-wetting liquid in a nanoporous medium with different initial fill volume fractions is observed experimentally. The similarity can be explained by the scaling of the interface energy and the self-similarity of the infinite percolation cluster of fluid-filled pores. Understanding the physical processes leading to the observed phenomena is a foundation for the development of high-performance devices for damping and energy storage on the basis of such heterogeneous systems.     

Concerning the deprotonation of the trimethylsulfonium ion by the dimethylsulfinyl anion

As shown by deuterium labelling experiments, the deprotonation of the trimethylsulfonium ion (1) by the dimsyl anion (8) is accompanied by extensive hydrogen exchange. This cannot be explained by an acid-base equilibrium between the trimethylsulfonium ion (1) and the dimsyl anion (8) on one side and dimethylsulfonium methylide (2) and DMSO on the other side, because for thermodynamic reasons this process is irreversible due to the limited life-time of 2. Therefore, the isotopic exchange that accompanies the deprotonation is an indicator of a more complex deprotonation process. It is suggested that in a kinetically controlled reaction, a proton of 1 is transferred to the O-atom of 8 rather than to the carbanionic centre. This means that instead of DMSO, its tautomer, hydroxy-methylsulfonium methylide (10), is obtained in the deprotonation process. Similarly, in the acid-base interaction between DMSO and its conjugate base 8, the formation of the DMSO tautomer 10 is kinetically favoured. The intermediate 10 produced in this way transfers a DMSO-derived proton to 1 when it intervenes in the back reaction 10 + 2→8 + 1. An alternative mechanism based on methyl group exchange between 1 and 8 could be excluded by a (13)C-labelling experiment. The hydrogen exchange according to the suggested scenario is taking place in competition with the reaction of dimethylsulfonium methylide (2) with electrophilic substrates. This explains the different degrees of isotopic exchange when compounds of different electrophilicities are used to scavenge 2 from the deprotonation-hydrogen distribution equilibria.     

Identification of the Enzymes Mediating the Maturation of the Seryl-tRNA Synthetase Inhibitor SB-217452 during the Biosynthesis of Albomycins

Albomycin δ₂ is a sulfur-containing sideromycin natural product that shows potent antibacterial activity against clinically important pathogens. The l -serine-thioheptose dipeptide partial structure, known as SB-217452, has been found to be the active seryl-tRNA synthetase inhibitor component of albomycin δ₂. Herein, it is demonstrated that AbmF catalyzes condensation between the 6′-amino-4′-thionucleoside with the d -ribo configuration and seryl-adenylate supplied by the serine adenylation activity of AbmK. Formation of the dipeptide is followed by C3′-epimerization to produce SB-217452 with the d -xylo configuration, which is catalyzed by the radical S-adenosyl-l -methionine enzyme AbmJ. Gene deletion suggests that AbmC is involved in peptide assembly linking SB-217452 with the siderophore moiety. This study establishes how the albomycin biosynthetic machinery generates its antimicrobial component SB-217452.     

A new terminology for the approaches to the quantification of the measurement uncertainty

A new terminology for the approaches to the quantification of the measurement uncertainty is presented, with a view to a better understanding of the available methodologies for the estimation of the measurement quality and differences among them. The knowledge of the merits, disadvantages and differences in the estimation process, of the available approaches, is essential for the production of metrologically correct and fit-to-purpose uncertainty estimations. The presented terminology is based on the level of the analytical information used to estimate the measurement uncertainty (e.g., supralaboratory or intralaboratory information), instead of the direction of information flow (“bottom-up” or “top-down”) towards the level of information where the test is performed, avoiding the use of the same designation for significantly different approaches. The proposed terminology is applied to the approaches considered on 19 examples of the quantification of the measurement uncertainty presented at the Eurachem/CITAC CG4 Guide, Eurolab Technical Report 1/2002 and Nordtest Technical Report 537. Additionally, differences of magnitude in the measurement uncertainty estimated by various approaches are discussed.     

On the validity of the BEBO method

The use of tha BEBO method proposed by Johnston and Parr is considered, taking into account the observations of Jordan and Kuafman. It is found that the original formulation is applicable even when the new values for noble gas pairs are employed,if an appropriate choice of the constant in Pauling's relation is made.     

Modeling the stability and the motion of DNA nucleobases on the gold surface

We simulate the structure and dynamics of the four DNA bases on the most stable gold surface. The experimental adsorption energies are reproduced to about 1 kcal mol(-1), and the existence of anchor points in the molecules is evidenced. The simulations also show that the bases drift on the gold surface with a degree of mobility that is not inversely proportional to the experimental (and calculated) desorption energies. When the same type of calculations is applied to pairs of bases it is seen that for at least two of them, namely GG and TT, there is a cooperative effect that increases their adsorption energy with respect to those of the single molecules. The molecular mobility on the surface is still present when a pair of interacting bases is considered.     

Where the rubber meets the hand: Unlocking the sensing potential of dielectric elastomers

Practice makes perfect to some extent. Research has shown that musicians who practice the piano for long periods of time can suffer a range of hand problems from loss of control to diminished speed. Now imagine a rubber keyboard that is springy, soft, and elastic. This is the new type of input device that dielectric elastomers (DE) can create. However their usage in large sensing systems is limited by a scalability challenge. Each DE sensor is married to a pair of connection cables and electronics, adding to the complexity of the background overheads. A new efficient multi‐frequency method is presented that is capable of detecting internal pressure changes from a difference in the DE's capacitance without the need for any additional wires or connections. This effectively segments the DE into smaller sections, achieving information from a single sensor equivalent to multiple sensors. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 465–472     

The energy pump and the origin of the non-equilibrium flux of the dynamical systems and the networks

The global stability of dynamical systems and networks is still challenging to study. We developed a landscape and flux framework to explore the global stability. The potential landscape is directly linked to the steady state probability distribution of the non-equilibrium dynamical systems which can be used to study the global stability. The steady state probability flux together with the landscape gradient determines the dynamics of the system. The non-zero probability flux implies the breaking down of the detailed balance which is a quantitative signature of the systems being in non-equilibrium states. We investigated the dynamics of several systems from monostability to limit cycle and explored the microscopic origin of the probability flux. We discovered that the origin of the probability flux is due to the non-equilibrium conditions on the concentrations resulting energy input acting like non-equilibrium pump or battery to the system. Another interesting behavior we uncovered is that the probabilistic flux is closely related to the steady state deterministic chemical flux. For the monostable model of the kinetic cycle, the analytical expression of the probabilistic flux is directly related to the deterministic flux, and the later is directly generated by the chemical potential difference from the adenosine triphosphate (ATP) hydrolysis. For the limit cycle of the reversible Schnakenberg model, we also show that the probabilistic flux is correlated to the chemical driving force, as well as the deterministic effective flux. Furthermore, we study the phase coherence of the stochastic oscillation against the energy pump, and argue that larger non-equilibrium pump results faster flux and higher coherence. This leads to higher robustness of the biological oscillations. We also uncovered how fluctuations influence the coherence of the oscillations in two steps: (1) The mild fluctuations influence the coherence of the system mainly through the probability flux while maintaining the regular landscape topography. (2) The larger fluctuations lead to flat landscape and the complete loss of the stability of the whole system.     

Synthesis of the Stereoisomers of the Sex Pheromones of the Southern Corn Rootworm

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On the generalized approach to the structure count

A generalized approach to the structure count of n-radical-m-cation systems based on the properties of the acyclic polynomial is presented. The mathematical proof for the expression relating the structure count to the coefficients of the acyclic polynomial is given. The connection between the structure count of biradical structures and the number of Dewar structures is discussed and tested on some examples.     

Measuring the interfacial tension of polymers in the presence of an interfacial modifier: Migrating the modifier to the interface

Compared to the dynamic mixing process used in melt blending operations, most techniques for measuring the interfacial tension can be considered as virtually static. For this reason, in order to measure the interfacial tension of an A-B immiscible system in the presence of an interfacial modifier, the problem of migrating the modifier to the interface is a central issue. In this study, the influence of the addition of an interfacial modifier, a polyethylene copolymer ionomer, on the interfacial tension between two high-density polyethylenes and a polyamide is investigated. The breaking thread method is used and the interfacial tension is measured as a function of ionomer content. In order to enhance the likelihood of placing the modifier in closer proximity to the interface, various sample preparations are compared. In all cases, the interfacial tension significantly drops with increasing ionomer content and tends to a limiting value. It is shown, however, that the preparation of the system for the breaking thread experiment via coextrusion using a conical die brings the modifier in closest proximity to the interface. With this approach an additional 1.45 times reduction of the interfacial tension at 10% compatibilizer concentration (based on the mass of HDPE) is observed compared to the classical technique of preparation. Confirmation of this effect is demonstrated using X-ray photoelectron spectroscopy where analysis of the thread surface of the system prepared by coextrusion indicates a more than fourfold enrichment of interfacial modifier. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1947–1958, 1998     

Effect of the Hydration Shell on the Carbonyl Vibration in the Ala-Leu-Ala-Leu Peptide

The vibrational spectrum of the Ala-Leu-Ala-Leu peptide in solution, computed from first-principles simulations, shows a prominent band in the amide I region that is assigned to stretching of carbonyl groups. Close inspection reveals combined but slightly different contributions by the three carbonyl groups of the peptide. The shift in their exact vibrational signature is in agreement with the different probabilities of these groups to form hydrogen bonds with the solvent. The central carbonyl group has a hydrogen bond probability intermediate to the other two groups due to interchanges between different hydrogen-bonded states. Analysis of the interaction energies of individual water molecules with that group shows that shifts in its frequency are directly related to the interactions with the water molecules in the first hydration shell. The interaction strength is well correlated with the hydrogen bond distance and hydrogen bond angle, though there is no perfect match, allowing geometrical criteria for hydrogen bonds to be used as long as the sampling is sufficient to consider averages. The hydrogen bond state of a carbonyl group can therefore serve as an indicator of the solvent’s effect on the vibrational frequency.     

Importance of the diamine reactant in the production of polyphosphonamides by the interfacial technique

The stirred interfacial polycondensation of phenylphosphonic dichloride and 1,6-hexanediamine has been studied as a function of several reaction variables. The reaction is rapid, being completed in less than 1 min. When organic solvent is varied and reactant molar ratio is varied with an excess of the acid chloride, yield is constant. When reactant molar ratio is varied polymer yield increases with increase in amine concentration. When reactant concentration is increased yield increases. With the addition of a soluble salt in the aqueous phase yield is increased. The above indicates that the diffusion of the amine to the reaction zone is of primary importance in determining polymerization rate and that the diffusion of the acid chloride is relatively unimportant. Polymer yield was found to be dependent on the pH of the amine in the aqueous phase. The observed trend is related to the apparent solubility of the amine in the aqueous phase such that the greater the apparent solubility of the amine, the less the polymer yield. Polymer molecular weight is found to be independent of reaction variables tested. Polymer was also formed from the condensation of phenylphosphonic dichloride with p-phenylenediamine, H₂N-D-NH₂ (where D is a 36-carbon hydrocarbon chain), 1,3-di-4-piperidylpropane, and 4-aminomethylpiperidine; phenyl phosphorodichloridate with 1,6-hexanediamine; chloromethyl phosphonic dichloride with 1,6-hexanediamine.     

On the validity of the elastic model for the nematic surface anchoring energy

The intrinsic uniform and non-uniform contributions to the anisotropic part of the surface energy are considered. Our analysis shows that the uniform part can be separated into an intrinsic and an extrinsic term. The first one is due to the nematic-nematic interaction only, whereas the second one is due to the nematic-substrate interaction. They are found to be of the same order of magnitude (≈1 erg cm²). The non-uniform part takes its origin from the spatial variation of the elastic constants. By means of a semi-microscopic model it is shown that, in the framework of perfect nematic order, the extrapolation length of the elastic origin is microscopic. On the contrary, if the spatial variation of the scalar order parameter is taken into account, simple calculations indicate that the extrapolation length is of the order of the coherence length in the nematic phase.     

On the Use of the Knox Equation. I. the Fit Problem

Abstract

To obtain significant A, B, and C parameters of the Knox equation, which corresponds to the plot of the reduced plate height, h, versus the reduced linear velocity, v, actual results must be fitted correctly. The Knox equation is analyzed, the rôle of each individual parameter is shown. The equation producing the coordinates of the minimum plate height (maximum efficiency) is fully derived from the derivative of the Knox equation. Two tables giving the minimum coordinates for usual A, B, and C ranges are listed. The classical fit method is derived and analyzed. A graphical fit method which uses the remarkable graphical capabilities of modern spreadsheet packages is described. A synthetical set of data was fitted. It is demonstrated that each Knox parameter, obtained through fit procedures, must be given with the fitting confidence interval which is often in the 20% range.     

Using of the Agglomeration-in-liquid for the Technology of the Fine Materials

The content of the fine and ultrafine particles in the raw material results in difficulty of the separation, the loss of the valuable components and ecological contamination. Secondary using of the fine particles is impossible without their granulation. This problem has been solved by the agglomeration-in-liquid method.An agglomeration-in-liquid method is a process to produce agglomerates in a liquid phase from solid particles suspended in the liquid. The surface of solid particles and the binding liquid must be of identical polarity, but the continuous phase must be of the opposite polarity. The water solutions of the surfactant are the binding liquids or the organic liquids.