Retention Time of Unretained Compound Calculation and Determination of Retention Indices of Some Monosubstituted Benzenes Using a Multiparametric Method in Binary, Ternary and Quaternary Solvent RP-LC Systems

In reversed phase liquid chromatography (RP-LC), the validity of a multiparametric (MP) non-linear least-squares regression iterative method has been evaluated for 14 different aqueous mobile phases modified with one, two or three organic solvents [acetonitrile (ACN), methanol (MeOH), or tetrahydrofuran (THF)] for calculating the retention time of unretained compound t _M and the regression parameter (slope b), based on the use of alkan-2-ones and alkyl aryl ketones homologous series. The determination of t _M and b has been studied for eight binary (ACN?CH₂O or MeOH?CH₂O), 3 ternary (ACN?CMeOH?CH₂O) and 3 quaternary (ACN?CMeOH?CTHF?CH₂O) mobile phase systems on an Omnispher C₁₈ column. The multiparametric calculated t _M and b values were compared with those obtained by Guardino??s, and Grobler??s methods. The MP retention indices (RI) of ten monosubstituted benzenes with different functionality (hydroxyl, carbonyl, nitro, etc.) based on the alkan-2-ones retention index standards have been determined and compared for the different mobile phase compositions studied. The influence of organic modifier type, the nature of mobile phase system and water content on the variation of retention parameter studied in this work were discussed.     

The transducer vibratory profile effects on the detection of the transient ultrasonic field scattered by a rigid point reflector

In this study a generalized approach, based on the impulse response technique, is developed to evaluate the transient ultrasonic field scattered by a rigid point reflector and detected by a planar circular transducer characterized by a non-uniform vibratory profile. For this purpose, several analytical functions are used to represent the non-uniform vibration amplitude of the transducer. All these functions have maximum amplitude at the transducer’s center and decrease monotonically away from axis. The amplitude variation of these functions has a direct effect on the shape of the average pressure detected by the transducer. Some numerical results are presented to illustrate the effects of a non-uniformly vibrating source on the detected transient pressure. The results show the relative importance of the edge wave modifications in the case of source having non-uniform vibration amplitude distribution.     

On the minimal solution for some variational inequalities

Applying an asymptotic method, the existence of the minimal solution to some variational elliptic inequalities defined on bounded or unbounded domains is established. The minimal solution is obtained as limit of solutions to some classical variational inequalities defined on domains becoming unbounded when some parameter tends to infinity. The considered quasilinear operators are only monotone (not strictly) and noncoercive. Some related comparison principles are also investigated.     

Versatile and expeditious synthesis of aurones via Au I-catalyzed cyclization

Aurones are conveniently formed in a three-step procedure including a goldI-catalyzed cyclization of 2-(1-hydroxyprop-2-ynyl)phenols as a highly regio- and stereoselective key step. A wide diversity of derivatives can be obtained starting from substituted salicylaldehydes. Synthesis of natural 4,6,3',4'-tetramethoxyaurone and structure revision of two natural products (dalmaisione D and 4'-chloroaurone) were achieved.     

Effects of solvent, pH and β-cyclodextrin on the fluorescent behaviour of lomustine

Fluorescent behaviour of lomustine, a DNA cross-linking agent, was investigated in different solvents, pH and in the presence of β-cyclodextrin (β-CD). The solvents in which fluorescence spectra were observed play a major role in determining the spectral intensity of fluorophore, since it was found to exhibit new fluorescent properties essentially influenced by intermolecular interactions, particularly by intermolecular H-bonding formed with solvents. The pH-dependence profile was typically U-shape with a maximum at pH between 3.51 and 6.58. It was corroborated that the fluorescence emission band of lomustine is significantly intensified in the presence of β-CD. From the changes in the fluorescence spectra, it was concluded that β-CD forms a 1:1 inclusion complex with lomustine and its association constant was calculated.     

Comparison of Retention Indices of Some Monosubstituted Benzenes Calculated by Different Mathematical Methods in RP-LC

In reversed phase liquid chromatography, the retention indices of benzene and nine mono substituted benzenes with different functionality based on the alkan-2-ones and alkyl aryl ketones retention index standards have been determined by the application of two new mathematical adaptation methods, viz. a multiparametric least-squares regression iterative method based on the determination of the adjusted retention times and a local cubic interpolation method directly using the total retention times. The two methods were applied to two types of columns. The first group includes four octadecyl-C₁₈ columns with different packing materials obtained from different manufacturers, while the second comprises an octyl-C₈ column. The retention indices have been extensively studied using either methanol–water or acetonitrile–water mobile phase systems. The influences of the concentration of the organic modifier in the mobile phase (methanol or acetonitrile), the column temperature, and the column packing material on retention indices of the set of the ten monoaromatics studied were also investigated. The calculated multiparametric retention indices values, those obtained by the local cubic interpolation and Kováts’ methods are compared. Good agreement was observed between the retention indices calculated by the three methods.     

Quantum chemical investigations on hydrogen bonding interactions established in the inclusion complex β-cyclodextrin/benzocaine through the DFT,AIM and NBO approaches

Structure and stability of an inclusion complex formed by Benzocaine (BZC) and β-cyclodextrin (β-CD) were investigated computationally using different levels of theory. The conformational research based on PM6 method allowed reach two minimum-energy structures: model A and model B. The lowest conformers have been exposed to fully geometry optimization employing four DFT functionals: B3LYP, CAM-B3LYP, M05-2X and M06-2X. The performed DFT calculations have identified the model B, in which the amino group is located at the primary face of β-CD, as the most stable complex by an amount up to ?40 kcal/mol. Further, the greater stabilization of model B in respect to model A, has been ascertained through AIM and NBO analyses which clarified the main hydrogen bonds HBs interactions governing the reactivity of BZC inside the hydrophobic cavity of β-CD. Finally, the estimated isotropic ¹H nuclear magnetic shielding constants generated from the gauge-including-atomic-orbital calculation have been analyzed and then compared with the available experimental data.     

Cyclability of 3‐connected graphs

A subset S of vertices of a graph G is called cyclable in G if there is in G some cycle containing all the vertices of S. We denote by α(S, G) the number of vertices of a maximum independent set of G[S]. We prove that if G is a 3‐connected graph or order n and if S is a subset of vertices such that the degree sum of any four independent vertices of S is at least n + 2α(S, G) −2, then S is cyclable. This result implies several known results on cyclability or Hamiltonicity. © 2000 John Wiley & Sons, Inc. J Graph Theory 34: 191–203, 2000     

In situ monitoring of hydrogen loss during pyrolysis of wood by neutron imaging

Hydrogen is an element of fundamental importance for energy but hard to quantify in bulk materials. Neutron radiography was used to map in situ loss of elemental hydrogen from beech tree wood samples during pyrolysis. The samples consisted of three wood cylinders (finished dowel or cut branch) of approximately 1 cm in length. The samples were pyrolyzed under vacuum in a furnace vessel that was placed inside a cold neutron imaging beamline using a temperature ramp of 5 °C/min from ambient up to 400 °C. Neutron radiographs with exposures of 30 s were sequentially recorded with a charge-coupled device over the course of the experiment. Relative absorbance/scattering of the neutron beam by each sample was based on intensity (or brightness) values as a function of pixel position. The much larger neutron cross section for hydrogen compared to carbon and oxygen enables almost direct conversion of neutron attenuation into sample hydrogen content for each time step during the pyrolysis experiment. Target and vessel temperatures were recorded concurrently with collection of the radiographs so that changes could be directly correlated to different states of pyrolysis. The most visible change appeared at the initial phase of the 400 °C plateau as evidenced by strong hydrogen loss and primarily diametric shrinking of the samples. The loss of elemental hydrogen between initial and final states of pyrolysis was estimated to be about 70%.     

Copper(II) bromide as efficient catalyst for silyl- to bisarylmethyl ethers interconversion (transprotection)

Primary and secondary silylated alcohols are easily converted to bis(methoxyphenyl)methyl (BMPM) ethers in good yields using CuBr₂ as catalyst in acetonitrile at room temperature. Various other protecting groups are compatible with this mild and convenient process.