Insight into chain dimensions in PEO/water solutions

Small‐Angle Neutron Scattering has been performed from poly(ethylene oxide) in deuterated water at temperature ranging from 10 to 80 °C. A simple fitting model was used to obtain a correlation length and a Porod exponent. The correlation length L characterizes the average distance between entanglements in the semidilute region and is proportional to the individual coil sizes in the dilute region. L was found to increase with temperature in the semidilute region but it decreases with temperature in the dilute region. This decrease is the precursor to the single‐chain collapse which applies to very dilute polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2196–2200, 2007     

Synthesis of Important New Pyrrolo[3,4‐c]Pyrazoles and Pyrazolyl‐Pyrrolines from Heterocyclic β‐Ketonitriles

Treatment of heterocyclic β‐ketonitriles 1a,b with hydrazine hydrate and phenylhydrazine afforded the hydrazine derivatives 2a‐d which cyclized in PPA into pyrrolo[3,4‐c]pyrazoles 3a‐d. Reaction of 1a,b with cyanoacetohydrazide furnished the cyanoacetyl pyrrolo[3,4‐c]pyrazoles 4a,b. The hydrazine 2c reacted with β‐diketone and β‐ketoesters to afford pyrazolyl‐pyrrolines 5‐7. Also the later hydrazine reacted with some D‐aldoses and aceteophenone to give the corresponding hydrazones 10‐12 and hydrazine carboxamide derivatives 15a,b respectively.     

Synthesis of new pyrrolo-[3,4-c]isoxazole, pyrrolo[2,3-d]-[1,2,3]triazole, triazolo[4,5-c]-pyridazine, and dipyrrolo-[3,2-b:3′,4′-d]pyran derivatives

New pyrrolo[3,4-c]isoxazole derivatives were synthesized from the key intermediates 4-cyanopyrrolidin-3-ones in two steps. Pyrrolo[2,3-d][1,2,3]triazoles and triazolo[4,5-c]pyridazine were obtained from 2-arylhydrazono-4-cyano-1-(4′-methoxyphenyl)-3-oxopyrrolidines by refluxing with phenylhydrazine in either ethanol or glacial acetic acid. Aldol self-condensation of 1-aryl-4-cyanopyrrolidin-3-ones afforded dipyrrolo-[3,2-b:3′, 4′-d]pyran derivatives. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1841–1848, December, 2007.     

Simulation of convectively coupled waves using WRF: a framework for assessing the effects of mesoscales on synoptic scales

The atmospheric variability in the tropics is primarily driven by convective heating. Observations revealed that convection in the tropics is organized into a hierarchy of multiscale convective systems ranging from the individual cloud cells to planetary scale disturbances that are nested within each other like Russian dolls. Current global climate models simulate very poorly these convectively coupled waves due in part to inadequate treatment of organized convection by the underlying cumulus parameterizations. Here, we present idealized simulations of convectively coupled equatorial waves (CCWs) using the weather research and forecast model in a horizontally limited domain consisting of a 4,500 km-wide square centered at the equator at moderate horizontal resolution of 10 km. We attempted and compared various configuration options, including switching on and off the cumulus parameterization (CP) and nesting a fine resolution 3.33 km domain, a 2,000 km-wide square, in the middle of the domain. It turns out that the results without a CP are much superior than those using a CP. While the cases without a CP resulted in a coherent eastward propagating CCW, which has many common features with observed convectively coupled Kelvin waves, the cumulus parameterization tends to destroy both the coherence of the propagating waves, even in the case with a nested domain, and reduces dramatically the variability. A primary demonstration on how such results could be used to show evidence of energy exchange, through momentum transport, between small-scale circulation due to mesoscale convection and the propagating synoptic scale wave will be reported is also presented.     

Simple models for the diurnal cycle and convectively coupled waves

This paper presents a study of the diurnal cycle of tropical precipitation and its interaction with convectively coupled waves in the context of simple models with crude vertical resolution. One and two baroclinic mode models are tested in both the context of a one-column model and the context of a full spatial dependency that permits waves to propagate and interact with the diurnal cycle. It is found that a one baroclinic mode model is capable of reproducing a realistic diurnal cycle of tropical precipitation both over land and over the ocean provided an adequate switch function is used to mimic the congestus preconditioning mechanism that operates in the multicloud model of Khouider and Majda. However, a full two baroclinic mode multicloud model is needed to capture the interaction of convectively coupled tropical waves with the diurnal cycle. In a more conventional mass flux parameterization framework, both one and two baroclinic mode models fail to capture the diurnal cycle of tropical precipitation.     

Further on Set-Valued Equilibrium Problems and Applications to Browder Variational Inclusions

In this paper, we introduce some concepts of convexity and semicontinuity for real set-valued mappings similar to those of real single-valued mappings. Then, we obtain different results on the existence of solutions of set-valued equilibrium problems generalizing in a common way several old ones for both single-valued and set-valued equilibrium problems. Applications to Browder variational inclusions, with weakened conditions on the involved set-valued operator, are given.     

Les Sels de Bismuth (III) Comme Catalyseurs Dans la Reaction D'ouverture Des Epoxydes Par Les Amines

BiCl 3 and Bi (OTf) 3 catalyze the opening of epoxides ( 1-7 ) by amines ( 8-12 ). High regioselectivities are observed. BiCl 3 et Bi (OTf) 3 catalysent la réaction d'ouverture des époxydes ( 1-7 ) par les amines ( 8-12 ). La réaction est fortement régiosélective.     

Amorphous carbon nitride as an alternative electrode material in electroanalysis: Simultaneous determination of dopamine and ascorbic acid

Boron-doped diamond (BDD) films are excellent electrode materials, whose electrochemical activity for some analytes can be tuned by controlling their surface termination, most commonly either to predominantly hydrogen or oxygen. This tuning can be accomplished by e.g. suitable cathodic or anodic electrochemical pretreatments. Recently, it has been shown that amorphous carbon nitride (a-CN_x) films may present electrochemical characteristics similar to those of BDD, including the influence of surface termination on their electrochemical activity toward some analytes. In this work, we report for the first time a complete electroanalytical method using an a-CN_x electrode. Thus, an a-CN_x film deposited on a stainless steel foil by DC magnetron sputtering is proposed as an alternative electrode for the simultaneous determination of dopamine (DA) and ascorbic acid (AA) in synthetic biological samples by square-wave voltammetry. The obtained results are compared with those attained using a BDD electrode. For both electrodes, a same anodic pretreatment in 0.1 mol L⁻¹ KOH was necessary to attain an adequate and equivalent separation of the DA and AA oxidation potential peaks of about 330 mV. The detection limits obtained for the simultaneous determination of these analytes using the a-CN_x electrode were 0.0656 μmol L⁻¹ for DA and 1.05 μmol L⁻¹ for AA, whereas with the BDD electrode these values were 0.283 μmol L⁻¹ and 0.968 μmol L⁻¹, respectively. Furthermore, the results obtained in the analysis of the analytes in synthetic biological samples were satisfactory, attesting the potential application of the a-CN_x electrode in electroanalysis.     

Concentration dependence of the first cumulant for partially labeled chains in dilute solutions

We use Zimm's single-contact approximation to investigate the concentration dependence of the first cumulant for partially labeled chains in dilute solutions. This approximation allows us to express interchain properties (such as the interference part of the generalized mobility) in terms of static structure factors, which are then modeled using a Gaussian chain model. We present numerical results for three specific labeling sequences.