Stepwise syntheses of tri- and tetraphosphaporphyrinogens

A double ring-expansion methodology allows the stepwise synthesis of tri- and tetra-phosphaporhyrinogens. Structural and calculational methods reveal extended delocalisation about their phospholide centres.     

Preparation of Dry Extract of<em> Mikania glomerata</em> Sprengel (Guaco) and Determination of Its Coumarin Levels by Spectrophotometry and HPLC-UV

Guaco (Mikania glomerata Sprengel) syrup is one of the most popular herbal medicines used to treat the symptoms of asthmatic bronchitis, cough and hoarseness. The coumarin 2H-1-benzopyran-2-one, is one of the major constituents of Guaco and contributes to its pharmacological effects. The pharmaceutical capsule form of dry extract of Guaco is recommended by the Brazilian Program of Medicinal Plants and Herbal Medicines and used in primary health care. In order to identify a new protocol to obtain the raw material for Guaco capsule production we evaluated two methods, including a freeze-drying process (lyophilization) and the spray-dryer technique, as well as the use of two adjuvants, Maltodextrins and Aerosil^?, in different concentrations. The coumarin levels of the dried extracts were analyzed by UV-spectrophotometry and HPLC-UV/DAD. The adjuvant Aerosil^? 8% showed better dry powder physical appearance. Lyophilization was observed to be the best process to obtain the dry extract of Guaco based on the measured coumarin levels.     

Insight into the Dynamics of Lanthanide-DTPA Complexes As Revealed by Oxygen-17 NMR

DTPA chelates of various diamagnetic and paramagnetic lanthanide(III) metal ions, as well as the chemically similar DTPA chelate of Y(3+), were studied in aqueous solution by variable temperature (17)O NMR with the aim of characterizing their internal dynamics. As a consequence of poor chemical shift dispersion and fast quadrupole relaxation, no dynamic exchange process could be detected for the diamagnetic complexes nor for the Sm-DTPA complex. In contrast, the spectra recorded for the Eu-DTPA complex show chemical exchange due to the well-known racemization process and, at high temperature, feature signal broadening that reveals a fluxional process involving the interchange of the coordinated and noncoordinated oxygen atoms of the carboxylate groups. The spectra recorded for the Pr-DTPA complex feature coalescence events due to such a fluxional process, which is ascribable to the rotation of the carboxylate groups. The activation free energy barriers determined experimentally are remarkably lower than the calculated activation barriers recently reported for the rotation of the carboxylate groups of various Ln-DOTA complexes. Furthermore, the smallest activation free energy measured for the Pr-DTPA complex, about 45 kJ mol(-1), is significantly lower than the activation free energy characterizing the racemization process. The fluxional behavior of the carboxylate groups is, however, not expected to significantly affect the residence time of the water molecule coordinated to the metal ion.     

A hybrid adaptive large neighborhood search heuristic for lot-sizing with setup times

This paper presents a hybrid of a general heuristic framework and a general purpose mixed-integer programming (MIP) solver. The framework is based on local search and an adaptive procedure which chooses between a set of large neighborhoods to be searched. A mixed integer programming solver and its built-in feasibility heuristics is used to search a neighborhood for improving solutions. The general reoptimization approach used for repairing solutions is specifically suited for combinatorial problems where it may be hard to otherwise design suitable repair neighborhoods. The hybrid heuristic framework is applied to the multi-item capacitated lot sizing problem with setup times, where experiments have been conducted on a series of instances from the literature and a newly generated extension of these. On average the presented heuristic outperforms the best heuristics from the literature, and the upper bounds found by the commercial MIP solver ILOG CPLEX using state-of-the-art MIP formulations. Furthermore, we improve the best known solutions on 60 out of 100 and improve the lower bound on all 100 instances from the literature.     

Nanometer scale electronic reconstruction at the interface between LaVO3 and LaVO4

Electrons at interfaces, driven to minimize their free energy, are distributed differently than in bulk. This can be dramatic at interfaces involving heterovalent compounds. Here we profile an abrupt interface between V 3d2 LaVO3 and V 3d0 LaVO4 using electron energy loss spectroscopy. Although no bulk phase of LaVOx with a V 3d1 configuration exists, we find a nanometer-wide region of V 3d1 at the LaVO3/LaVO4 interface, rather than a mixture of V 3d0 and V 3d2. The two-dimensional sheet of 3d1 electrons is a prototypical electronic reconstruction at an interface between competing ground states.     

Alkylation of phenol: a mechanistic view

The current work utilizes the ab initio density functional theory (DFT) to develop a molecular level of the mechanistic understanding on the phenol alkylation in the presence of a cation-exchange resin catalyst, Amberlyst-15. The catalyst is modeled with the benzene sulfonic acid, and the effect of this acid on olefins such as isopropene (i-Pr) and tributene (t-Bu) in a phenol solution mimics the experimental condition. A neutral-pathway mechanism is established to account for early-stage high concentration of the phenolic ether observed in experiments. The mechanism involves an exothermic reaction between olefin and the benzene sulfonic acid to form ester followed by three reaction pathways leading to direct O-alkylation, o-C-alkylation, and p-C-alkylation. Our calculations conclude that O-alkylation to form the phenolic ether is the most energetically favorable in the neutral condition. An ionic rearrangement mechanism describes intramolecular migrations of the alkyl group from the phenolic ether to form C-alkylphenols, while the positively charged protonation significantly lowers transition barriers for these migrations. The ionic rearrangement mechanism accounts for high yields of o-C-alkylphenol and p-C-alkylphenol. Competition between the H atom and the alkyl R group at the substitutive site of the protonated ortho configuration is found to be the determining factor to the ortho/para ratio of C-alkylation products.     

Transmission‐mode diamond white‐beam position monitor at NSLS

Two transmission‐mode diamond X‐ray beam position monitors installed at National Synchrotron Light Source (NSLS) beamline X25 are described. Each diamond beam position monitor is constructed around two horizontally tiled electronic‐grade (p.p.b. nitrogen impurity) single‐crystal (001) CVD synthetic diamonds. The position, angle and flux of the white X‐ray beam can be monitored in real time with a position resolution of 500 nm in the horizontal direction and 100 nm in the vertical direction for a 3 mm × 1 mm beam. The first diamond beam position monitor has been in operation in the white beam for more than one year without any observable degradation in performance. The installation of a second, more compact, diamond beam position monitor followed about six months later, adding the ability to measure the angular trajectory of the photon beam.     

Mikrochemische Nachweise und Bestimmungen organischer Bestandteile des menschlichen oder tierischen Organismus

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