The presentation of an approach for estimating the intramolecular hydrogen bond strength in conformational study of β-Aminoacrolein

All the plausible conformations of β-aminoacrolein (AMAC) have been investigated by the Bekes-Lee-Yang-Parr (B3LYP) nonlocal density functional with extended 6-311++G** basis set for studying the stability order of conformers and the various possibilities of intramolecular hydrogen bonding formation. In general the ketoamine (KA) conformers of AMAC, by mean average, are more stable than the corresponding enolimine (EI) and ketoimine (KI) analogues and this stability is mainly due to the π-electron resonance in these conformers that established by NH2 functional group. The contribution of resonance to the stability of chelated KA conformers is about 75.6 kJ/mol, which is greater than that of the hydrogen bond energy (E_HB=35.0 kJ/mol). The relative decreasing order of the various hydrogen bond energies was found to be: O–HN_imine(strong)>N_amine-HO_keto (normal)>N_imine-HO_hydroxyl (weak) > N_imine-HO_keto (weak). Hydrogen bond energies for all systems were obtained from the method that we called related rotamers method (RRM). The topological properties of the electron density contributions for various type of intramolecular hydrogen bond have been analyzed in term of the Bader theory of atoms in molecules (AIM). The results of these calculations support the previous calculations, which obtained by the related rotamer methods.     

Effect of Silica Particle Size on Polymer Adsorption. Morphological,Energetic and Conformational Relationships

A series of six chemically treated and untreated fumed silicas with increasing particle size (ranging from the nano- to the micrometer size) was prepared. Surface areas (and morphologies) and surface energies were determined by nitrogen adsorption and inverse gas chromatography, respectively. The adsorption of a series of PDMS with different and well-defined molecular weights was studied at different polymer concentrations. Amounts of adsorbed polymer were determined by gravimetry and the energies of adsorption were assessed by flow-microcalorimetry. Results are discussed in terms of particle surface energy and morphology effects on the conformation and the inter-connectivity of adsorbed polymer molecules.     

Measuring the size of polymers with negative radii using MALS/QELS: an exploration of the thermodynamic radius

The concept of 'size' in polymer science can have several interpretations, including definitions that rely on either statistical or equivalent-hard-sphere measures of the spatial extent of macromolecules in solution. A definition such as that of the equivalent thermodynamic radius (R(T)), which relies on the second virial coefficient of the polymer solution, offers the possibility of a zero or even a negative size parameter for macromolecules, depending on whether the polymer solution is in a theta or poor thermodynamic state, respectively. Here, we present the results of multi-angle light scattering measurements of R(T) for polystyrene and poly(methyl methacrylate), showing positive, negative, and zero values for this radius, depending on dilute solution thermodynamics. These results are augmented with measurements of the hydrodynamic radius, using quasi-elastic light scattering, and with random-walk-based calculations of the root-mean-square and viscometric radii. Re-examination of the literature provides additional examples of negative radii of polymers and oligomers.     

Van Hove singularities in intersubband transitions in multiquantum well photodetectors

High dynamics measurements of spectral response were carried out on quantum well infrared photodetectors (QWIP). Photocurrent spectra were studied over more than three orders of magnitude, revealing the presence of spectral structures which were never observed hitherto. Electric field assisted tunneling and, more surprisingly, Van Hove singularities at the miniband edges, are shown to play an important role in the low and high energy parts of the QWIP photocurrent spectra, respectively. These experimental features motivated us to initiate a theoretical study of the absorption in a multiquantum well structure. Our work is based on the study of the electronic wave function in a periodic structure.     

Effect of Different Heat Treatments on the Quality and Flavor Compounds of Black Tibetan Sheep Meat by HS-GC-IMS Coupled with Multivariate Analysis

There are limited reports about the effect of different heat treatments on the quality and flavor of Black Tibetan sheep meat. The current study examined the effect of pan-frying, deep-frying, baking, and boiling treatment on the quality of Black Tibetan sheep meat; the amino acid, fatty acid, and volatile flavor compounds (VFCs) were investigated by a texture analyzer, ultra-high-performance liquid chromatography (UHPLC), gas chromatography (GC), and headspace-gas chromatography-ion mobility (HS-GC-IMS). The key VFCs were identified through orthogonal partial least squares discrimination analysis (OPLS-DA), and variable importance projection (VIP) values. In addition, Pearson’s correlations between meat quality parameters and key VFCs were examined. The sensory scores, including texture, color, and appearance, of baked and pan-fried meat were higher than those of deep-fried and boiled meat. The protein (40.47%) and amino acid (62.93 µmol/g) contents were the highest in pan-fried meat (p < 0.05). Additionally, it contained the highest amounts of monounsaturated and polyunsaturated fatty acids, such as oleic, linoleic, and α-linolenic acids (p < 0.05). Meanwhile, pan-fried and deep-fried meat had higher amounts of VFCs than baked meat. The OPLS-DA similarity and fingerprinting analyses revealed significant differences between the three heat treatment methods. Aldehydes were the key aroma compounds in pan-fried meat. Importantly, 3-methylbutyraldehyde and 2-heptanone contents were positively correlated with eicosenoic, oleic, isooleic, linoleic, α-Linolenic, and eicosadiene acids (p < 0.05). To sum up, pan-fried Black Tibetan sheep meat had the best edible, nutritional, and flavor quality.     

A Rational Triplic Form for the Exponential

The theory of the power series solution is applied to the Hamburger DE to derive an improper fraction triplic form, E₂ ^N(x), for e^x on the real line. E₂ ^N turns out to be a simpler equivalent to the vertical sequence P₂ ^N of the related Padé table P_M ^N and with comparable summation features.     

Composite Surface Integral Transforms in Neutron Therapy of Cancer

Composite surface finite integral transforms are applied to formulate the optimal ballistic property for a temporally tuned multibeam neutron cancer 3D therapy as a single-valued dynamical system. By invoking Pontryagin's maximum principle, with the operation functions of the beams constituting the control vector, it is proved, in an inverse problem formulation, that for every spatial configuration of the neutron beams, there exists an optimal temporal control vector satisfying an a priori system of linear homogeneous Volterra integral equations of the first kind and convolution type. A version of this newly advanced, temporally optimalized, multibeam 3D irradiation therapy, with a linearized ballistic property, is shown to result from a shooting-type solution to a related, semihomogeneous dual system of linear integral equations of the first kind. A criterion for the controllability of this optimization problem has also been established.     

Two-Dimensional Liquid Chromatography (2D-LC) in Pharmaceutical Analysis: Applications Beyond Increasing Peak Capacity

One-dimensional liquid chromatography (1D-LC) is not always capable of efficiently separating complex samples. This drawback is not solely due to the lack of column efficiency, but is mainly due to insufficient selectivity and the need to separate the analytes of interest with orthogonal retention mechanisms. In this regard, two-dimensional liquid chromatography (2D-LC) is currently attracting much interest for its markedly higher resolving power compared to one-dimensional separation. In this work, three applications of 2D-LC from the pharmaceutical industry are presented with the goal not only to increase peak capacity, but also to support investigations. In the first application, the retention times of peaks of interest are matched under different mobile phase conditions for the purpose of transferring the method from a mass spectrometry (MS) incompatible buffer to an MS compatible buffer. The second application includes developing a method for simultaneous detection and quantitation of degradants and aggregates in a biologics and small molecule combination product. The third application supports method development by confirming the purity of separated peaks using orthogonal separation conditions in the first and second dimensions and to investigate mass balance issues where some peaks are expected to elute in the solvent front.     

Oxadiazole‐2‐thiol Adsorption on Gold Nanorods: A Joint Theoretical and Experimental Study by Using SERS,XPS, and DFT

The chemisorption of 1,3,4‐oxadiazole‐2‐thiol (ODT) on gold nanorods has been investigated by using surface‐enhanced Raman spectroscopy (SERS) and density functional theory (DFT). Although most of the SERS spectra have remarkable similarity to the normal Raman spectra of the pure analyte, the adsorption of ODT on a gold surface leads to a drastic change in its Raman spectrum and distinct vibrational features are obtained with gold nanorods and spherical nanoparticles. Simulated Raman spectra for hybrid systems that consist of an oxadiazole moiety coordinated to a Au₂₀ gold cluster provided valuable information about the coordination mode and enabled us to assign vibration modes.