A new approximation for the generalized fractional derivative and its application to generalized fractional diffusion equation

In this paper, we derive a fourth order approximation for the generalized fractional derivative that is characterized by a scale function z(t) and a weight function w(t) . Combining the new approximation with compact finite difference method, we develop a numerical scheme for a generalized fractional diffusion problem. The stability and convergence of the numerical scheme are proved by the energy method, and it is shown that the temporal and spatial convergence orders are both 4. Several numerical experiments are provided to illustrate the efficiency of our scheme.     

NMR Studies of Drugs. Applications of Achiral and Chiral Lanthanide Shift Reagents to the Analgesic,Famprofazone: “Anomalous Shifts”

The 200 MHz ¹H NMR spectra of the analgesic, famprofazone, 1, have been studied in CDCl₃ solution at ambient temperatures with the achiral lanthanide shift reagent (LSR) tris (6, 6, 7, 7, 8, 8, 8-heptaf luoro-2, 2-dimethyl-3, 5-octanedionato) europium (III), Eu(FOD)₃, 2, for spectral simplification, and with the chiral LSR, tris [3-(heptafluoropropylhydroxymethylene) - (+) camphorato] europium (III), Eu (HFC)₃, 3. Lanthanide induced shift (LIS) magnitudes suggested predominant LSR binding at the carbonyl oxygen. Substantial enantiomeric shift differences were observed for several nuclei of 1 with added 3 which could permit direct determinations of enantiomeric excess.     

Synthesis of Fluorinated Graphene Oxide and its Amphiphobic Properties

The richly functionalized basal plane bonded to polar organic moieties makes graphene oxide (GO) innately hydrophilic. Here, a methodology to synthesize fluorinated graphene oxide by oxidizing the basal plane of fluorinated graphite, allowing for tunable hydrophobicity of GO, is reported. Fluorine exists as tertiary alkyl fluorides covalently bonded to graphitic carbons, and using magic‐angle spinning (MAS) ¹³C NMR as a primary tool chemical structures for the two types of synthesized fluorinated graphene oxides (FGOs) with significantly different fluorine contents are proposed. The low surface energy of the C–F bond drastically affects GO's wetting behavior, leading to amphiphobicity in its highly fluorinated form. Ease of solution processing enables the fabrication of inks that are spray‐painted on various porous/non‐porous substrates. These coatings maintain amphiphobicity for solvents with surface tensions down to 59 dyn/cm, thus bypassing existing lithographic means to create similar surfaces. The approach towards fluorinating GO and fabricating graphene‐based surfaces with tunable wettability opens the path towards unique, accessible, carbon‐based amphiphobic coatings.     

What happens during vocal warm-up?

Most singers prefer to warm up their voices before performing. Although the subjective effect is often considerable, the underlying physiological effects are largely unknown. Because warm-up tends to increase blood flow in muscles, it seems likely that vocal warm-up might induce decreased viscosity in the vocal folds. According to the theory of vocal-fold vibration, such a decrease should lead to a lower phonation threshold pressure. In this investigation the effect of vocal warm-up on the phonation threshold pressure was examined in a group of male and female singers. The effect varied considerably between subjects, presumably because the vocal-fold viscosity was not a dominating factor for the phonation-threshold pressure.     

Urban rapid transit network capacity expansion

This paper examines a multi-period capacity expansion problem for rapid transit network design. The capacity expansion is realized through the location of train alignments and stations in an urban traffic context by selecting the time periods. The model maximizes the public transportation demand using a limited budget and designing lines for each period. The location problem incorporates the user decisions about mode and route. The network capacity expansion is a long-term planning problem because the network is built over several periods, in which the data (demand, resource price, etc.) are changing like the real problem changes. This complex problem cannot be solved by branch and bound, and for this reason, a heuristic approach has been defined in order to solve it. Both methods have been experimented in test networks.     

Anchimeric assistance in the gas phase dehydrohalogenation of 5-chloro-2-methylpent-2-ene

5-Chloro-2-methylpent-2-ene decomposes at temperatures of 370–420°C with initial pressures from 61to 158 torr to yield hydrogen chloride and a mixture of methylpentadiene isomers. In a static system, with seasoned vessel and propene inhibitor, the reaction is homogeneous, unimolecular, and of the first order. The rate coefficient is expressed by the following Arrhenius equation: log k (sec^?1) = (13.43 ± 0.30) ? (215.0 ± 3.7) kJ/mol/2.303RT. The result ofthe present work additionally supports the participation of the neighboringaliphatic olefinic double bond in the rate of HCl elimination of alkenyl chlorides in the gas phase. Moreover, it also confirms the three-membered conformation as the most favored structure for anchimeric assistance.     

Reactive properties of trans-dichlorooxirane in relation to the contrasting carcinogenicities of vinyl chloride and trans-dichloroethylen

Our objective in this work is to gain insight into the contrasting carcinogenic activities of vinyl chloride (definitely carcinogenic) and trans-dichloroethylene (apparently inactive). The initial metabolic step for each molecule is believed to be epoxidation of the double bond, and there is evidence indicating that for vinyl chloride, this epoxide (chlorooxirane) is its ultimate (direct-acting) carcinogenic form. This article presents the findings of a computational study of the reactive properties of trans-dichlorooxirane (the epoxide of trans-dichloroethylene). An ab initio SCF -MO procedure was used to determine the energy requirements for stretching the C? O and C? Cl bonds (S_N1 reactivity) and to study the epoxide's S_N2 interactions with ammonia, taken as a model nucleophile. The starting points were the oxygen- and chlorine-protonated forms of the epoxide. The structure of the system was reoptimized at each step along the various reaction pathways. The results of this work are compared to an analogous earlier study of the reactive properties of chlorooxirane. The chlorineprotonated C? Cl bonds are found to have much lower energy barriers to stretching than do the oxygen-protonated C? O bonds. In the S_N2 processes, intermediate complexes are formed with ammonia by both the oxygen- and the chlorine-protonated epoxides; the latter complexes are the more stable. Based on our results, we propose two mechanisms (one S_N1 and the other S_N2) whereby trans-dichlorooxirane can interact with N₇ of guanine to produce an adduct analogous to one formed by chlorooxirane, which has been found to be the primary in vivo DNA alkylation product of vinyl chloride and to which has been attributed the carcinogenicity of the latter. Overall, trans-dichlorooxirane is found to be chemically more reactive than chlorooxirane; this may help to account for the much lesser carcinogenic and mutagenic activities of trans-dichloroethylene, since the epoxide may be reacting with other cellular nucleophiles before it reaches the key site(s) at which the carcinogenic or mutagenic interaction would occur. We also offer some speculations concerning other possible factors related to the differing carcinogenicities of vinyl chloride and trans-dichloroethylene, such as ease of epoxide formation and the likelihood of oxygen protonation.