Theoretical scrutinization of nine benzoic acid dimers: Stability and energy decomposition analysis

Aromatic carboxylic acids are able to form diverse dimers and multimers due to their hydrogen bond donor and acceptor cites, as well as the aromatic rings. In this work, we examine nine benzoic acid dimers stabilized by hydrogen bonding and stacking interactions. Interacting quantum atoms methodology revealed that dominant attractive interactions in all of them, including hydrogen bonded systems, are due to exchange-correlation. Coulomb interactions are significant only in the most stable dimer with a double hydrogen bond, although the corresponding energy term is almost two times lower compared to the nonclassical one. Since interacting quantum atoms approach treats monomers binding by considering electronic energy only, in order to examine dissociation kinetics we performed density functional theory-based molecular dynamics simulations of selected stacked dimers: in 40% of the studied systems at 300 K thermal energy was sufficient to overpower barrier for dissociation within 1 ps, which resulted in the separation of the monomers, whereas 20% of them remained in the stacked position even after 5 ps. These results highlight the importance of noncovalent interactions, particularly weak stacking interactions, on the structure and dynamics of carboxylic acids and their derivatives.     

Thermodynamic model and Raman spectra of MgO–P2O5 glasses

Journal of Thermal Analysis and Calorimetry - The structure of binary glasses xMgO·(1?x)P2O5 (x?=?0.30, 0.35, 0.40, 0.45, 0.50, and 0.55) was studied by thermodynamic model...     

Capillary electrophoresis and ultra-high-performance liquid chromatography methods in clinical monitoring of creatinine in human urine: A comparative study

Creatinine is an important diagnostic marker and is also used as a standardization tool for the quantitative evaluation of exogenous/endogenous substances in urine. This study aimed at evaluating and comparing three analytical approaches, based on hyphenations of different separation [two-dimensional capillary isotachophoresis (CITP–CITP), capillary zone electrophoresis (CZE), ultra-high-performance liquid chromatography (UHPLC)] and detection [conductivity (CD), ultraviolet (UV), tandem mass spectrometry (MS/MS)] techniques, for their ability to provide reliable clinical data along with their suitability for the routine clinical use (cost, simplicity, sample throughput). The developed UHPLC–MS/MS, CITP–CITP–CD, and CZE–UV methods were characterized by favorable performance parameters, such as linearity (r ˃ 0.99), precision (relative standard deviation, 0.22–2.97% for the creatinine position in analytical profiles), and recovery (87.1–115.1%). Clinical data, obtained from the analysis of 24 human urine samples by a reference enzymatic method, were comparable with those obtained by the tested methods (Passing–Bablok regression and Bland–Altman analysis), approving their usefulness for the routine clinical use. In this context, the UHPLC–MS/MS method provides benefits of enhanced orthogonality/accuracy and high sample throughput (threefold shorter total analysis times than the CE methods), whereas advantages of the CE methods for routine labs are simplicity and low cost of both the instrumentation and measurements.     

Topological Properties of the Space of Convex Minimal Usco Maps

Set-Valued and Variational Analysis - We investigate the space of convex minimal usco maps from a Tychonoff space to the space of real numbers. Its elements are set-valued maps that are important...     

Smart,self-repair polymers based on acryloyl-6-aminocaproic acid and modified with magnetic nanoparticles—preparation and characterization

Capability of materials to self-repair is an innovative and unique property from a point of view both chemistry and physics. Moreover, such property could arouse special interests if such an ability could be caused by the selection of the environmental parameters. Such materials—polymers based on acryloyl-6-aminocaproic acid (A6ACA)—were synthesized in the present paper. In addition, mentioned polymers have been modified with different amount of magnetic nanoparticles solution. Subsequently, sorption capacity and behavior of synthesized polymers in simulated body fluids have been determined. What is also important, studies on cytotoxicity of prepared materials in relation to fibroblasts and cells of cancer origin have been conducted. Materials have also been analyzed by Fourier transform infrared spectroscopy and scanning electron microscopy method. Based on the research aiming at physicochemical characteristics of abovementioned materials it was proved that prepared hydrogels showed self-repair property in a low pH environment. Apart from this essential issue, these were characterized by high sorption capacity, high porosity which decreases with the introduced amount of nanoparticles and, what is important, cytotoxicity to cancer cells. Such combination is a very interesting from a point of view of many realms and due to its unique features may be widely applicable in the nearest future.     

Compactness of sequences of two-dimensional energies with a zero-order term. Application to three-dimensional nonlocal effects

In this paper we study the limit, in the sense of the Γ-convergence, of sequences of two-dimensional energies of the type , where A _n is a symmetric positive definite matrix-valued function and μ _n is a nonnegative Borel measure (which can take infinite values on compact sets). Under the sole equicoerciveness of A _n we prove that the limit energy belongs to the same class, i.e. its reads as , where is a diffusion independent of μ _n and μ is a nonnegative Borel measure which does depend on . This compactness result extends in dimension two the ones of [11,23] in which A _n is assumed to be uniformly bounded. It is also based on the compactness result of [7] obtained for sequences of two-dimensional diffusions (without zero-order term). Our result does not hold in dimension three or greater, since nonlocal effects may appear. However, restricting ourselves to three-dimensional diffusions with matrix-valued functions only depending on two coordinates, the previous two-dimensional result provides a new approach of the nonlocal effects. So, in the periodic case we obtain an explicit formula for the limit energy specifying the kernel of the nonlocal term.     

Linear-scaling symmetric square-root decomposition of the overlap matrix

We present a robust linear-scaling algorithm to compute the symmetric square-root or Lowdin decomposition of the atomic-orbital overlap matrix. The method is based on Newton-Schulz iterations with a new approach to starting matrices. Calculations on 12 chemically and structurally diverse molecules demonstrate the efficiency and reliability of the method. Furthermore, the calculations show that linear scaling is achieved.     

Electronic structure of copper phthalocyanine: an experimental and theoretical study of occupied and unoccupied levels

An experimental and theoretical study of the electronic structure of copper phthalocyanine (CuPc) molecule is presented. We performed x-ray photoemission spectroscopy (XPS) and photoabsorption [x-ray absorption near-edge structure (XANES)] gas phase experiments and we compared the results with self-consistent field, density functional theory (DFT), and static-exchange theoretical calculations. In addition, ultraviolet photoelectron spectra (UPS) allowed disentangling several outer molecular orbitals. A detailed study of the two highest occupied orbitals (having a(1u) and b(1g) symmetries) is presented: the high energy resolution available for UPS measurements allowed resolving an extra feature assigned to vibrational stretching in the pyrrole rings. This observation, together with the computed DFT electron density distributions of the outer valence orbitals, suggests that the a(1u) orbital (the highest occupied molecular orbital) is mainly localized on the carbon atoms of pyrrole rings and it is doubly occupied, while the b(1g) orbital, singly occupied, is mainly localized on the Cu atom. Ab initio calculations of XPS and XANES spectra at carbon K edge of CuPc are also presented. The comparison between experiment and theory revealed that, in spite of being formally not equivalent, carbon atoms of the benzene rings experience a similar electronic environment. Carbon K-edge absorption spectra were interpreted in terms of different contributions coming from chemically shifted C 1s orbitals of the nonequivalent carbon atoms on the inner ring of the molecule formed by the sequence of CN bonds and on the benzene rings, respectively, and also in terms of different electronic distributions of the excited lowest unoccupied molecular orbital (LUMO) and LUMO+1. In particular, the degenerate LUMO appears to be mostly localized on the inner pyrrole ring.