bluuebunny/crossref_metadata_2025_split huggingface dataset:
Novel Luminescent Mixed‐Metal PtTl‐Alkynyl‐Based Complexes: The Role of the Alkynyl Substituent in Metallophilic and η2(π⋅⋅⋅Tl)‐Bonding Interactions
Authors: Berenguer Jesús R. , Forniés Juan , Gil Belén , Lalinde Elena 
Published: September 2005

AbstractA novel series of [PtTl2(CCR)4]n (n=2, R=4‐CH3C6H4 (Tol) 1, 1‐naphthyl (Np) 2; n=∞, R=4‐CF3C6H4 (TolF) 3) complexes has been synthesized by neutralization reactions between the previously reported [Pt(CCR)4]2− (R=Tol, TolF) or novel (NBu4)2[Pt(CCNp)4] platinum precursors and TlI (TlNO3 or TlPF6). The crystal structures of [Pt2Tl4(CCTol)8]⋅4 acetone, 1⋅4 acetone, [Pt2Tl4(CCNp)8]⋅3 acetone⋅1/3 H2O, 2⋅3 acetone ⋅1/3 H2O and [{PtTl2(CCTolF)4}(acetone)S]∞ (S=acetone 3 a; dioxane 3 b) have been solved by X‐ray diffraction studies. Interestingly, whereas in the tolyl (1) and naphthyl (2) derivatives, the thallium centers exhibit a bonding preference for the electron‐rich alkyne entities to yield crystal lattices based on sandwich hexanuclear [Pt2Tl4(CCR)8] clusters (with additional Tl⋅⋅⋅acetone (1) or Tl⋅⋅⋅naphthyl (2) secondary interactions), in the C6H4CF3 (TolF) derivatives 3 a and 3 b the basic PtII center forms two unsupported PtTl bonds. As a consequence 3 a and 3 b form an extended columnar structure based on trimetallic slipped PtTl2(CCTolF)4 units that are connected through secondary Tl⋅⋅⋅(η2‐acetylenic) interactions. The luminescent properties of these complexes, which in solution (blue; CH2Cl2 1,2; acetone 3) are very different to those in solid state (orange), have been studied. Curiously, solid‐state emission from 1 is dependent on the presence of acetone (green) and its crystallinity. On the other hand, while a powder sample of 3 is pale yellow and displays blue (457 nm) and orange (611 nm) emissions, the corresponding pellets (KBr, solid) of 3, or the fine powder obtained by grinding, are orange and only exhibit a very intense orange emission (590 nm).
Tunable N‐substitution in Zwitterionic Benzoquinonemonoimine Derivatives: Metal Coordination, Tandemlike Synthesis of Zwitterionic Metal Complexes, and Supramolecular Structures
Authors: Yang Qing‐Zheng , Siri Olivier , Braunstein Pierre 
Published: September 2005

AbstractFull details on a very efficient transamination reaction for the synthesis of zwitterionic N,N′‐dialkyl‐2‐amino‐5‐alcoholate‐1,4‐benzoquinonemonoiminium derivatives [C6H2(${^{\underline{.....}}}$NHR)2(${^{\underline{.....}}}$O)2] 5–16 are reported. The molecular structures of zwitterions 5 (R=CH3) in 5⋅H2O, 13 (R=CH2CH2OMe), 15 (R=CH2CH2NMe2), and of the parent, unsubstituted system [C6H2(${^{\underline{.....}}}$NH2)2(${^{\underline{.....}}}$O)2] 4 in 4⋅H2O have been established by single‐crystal X‐ray diffraction. This one‐pot preparation can be carried out in water, MeOH, or EtOH and allows access to new zwitterions with N‐substituents bearing functionalities such as OMe (13), OH (9–12), NR1R2 with R1= or ≠R2 (14–16) or an alkene (8), leading to a rich coordination chemistry and allowing fine‐tuning of the supramolecular arrangements in the solid state. As previously described for 15, which reacted with Zn(acac)2 to afford the octahedral ZnII complex [Zn{C6H2(NCH2CH2NMe2)O(O)(NHCH2CH2NMe2)}2] (20), ligands 13 and 16 with coordinating “arms” afforded with Zn(acac)2 the 2:1 adducts [Zn{C6H2(NCH2CH2X)O(O)(NHCH2CH2NX)}2] 19 (X=OMe) and 21 (X=NHEt), with N2O4 and N4O2 donor sets around the octahedral ZnII center, respectively. Furthermore, zwitterions 15 and 16 reacted with ZnCl2 to give the stable, crystallographically characterized ZnII zwitterionic complexes [ZnCl2{C6H2(NCH2CH2NR1R2)O(O)(NHCH2CH2NHR1R2)}] 22 (R1=R2=Me) and 23 (R1=Et, R2=H) by means of an unprecedented, tandemlike synthesis in which 1) the two pendant amino groups of the organic benzoquinonemonoimine zwitterionic precursor favor metal coordination and proton transfer and 2) the saturated linker prevents π‐conjugation between the charges. The nature of the structural arrangements in the solid state for both inorganic (20, 22, 23) and organic (5, 9, 13, and 15) molecules is determined by subtle variations in the nature of the N‐substituent on the zwitterion precursor.
Improved catalytic activity of homochiral dimeric cobalt–salen complex in hydrolytic kinetic resolution of terminal racemic epoxides
Authors: Kureshy Rukhsana I. , Singh Surendra , Khan Noor‐Ul H. , Abdi Sayed H.R. , Ahmad Irshad , Bhatt Achyut , Jasra Raksh V. 
Published: September 2005

AbstractEnantiomerically pure epoxides (99%, ee) and diols (98%, ee) from racemic epichlorohydrin, 1,2‐epoxypropane, 1,2‐epoxyhexane, 1,2‐epoxyoctane, and 1,2‐epoxydodecane were obtained in 2–12 h by hydrolytic kinetic resolution (HKR) using the recyclable dimeric homochiral Co(III)–salen complex 1′ (0.2 mol %) derived from 5,5‐(2′,2′‐dimethylpropane)‐di‐[(R,R)‐{N‐(3‐tert‐butylsalicylidine)‐N′‐(3′,5′‐di‐tert‐butylsalicylidine)}‐1,2‐cyclohexanediamine] with cobalt(II) acetate. Unlike its monomeric version, the catalyst could be recycled several times without loss in performance. The use of BF4 as counter ion in HKR reactions was also investigated. © 2005 Wiley‐Liss, Inc. Chirality 17:590–594, 2005.
Detailed studies on the enantioselective synthesis and HPLC enantioseparation of N‐protected 3‐hydroxyglutarimides
Authors: Ruan Yuan‐Ping , Wei Bang‐Guo , Xu Xiu‐Qing , Liu Gang , Yu De‐Sheng , Liu Liang‐Xian , Huang Pei‐Qiang 
Published: September 2005

AbstractAn analytical HPLC method using CHIREX (S)‐LEU/(S)‐α‐NEA column was developed for the determination of the enantiomeric excesses of N‐protected (S)‐3‐hydroxyglutarimides. Using this method, detailed studies on the base‐promoted ring‐expansion reaction of the amidolactones, derived from l‐glutamic acid, were undertaken. © 2005 Wiley‐Liss, Inc. Chirality 17:595–599, 2005.
Activity and expression of the vanilloid receptor 1 (TRPV1) is altered by long‐term diabetes in epineurial arterioles of the rat sciatic nerve
Authors: Davidson Eric P. , Coppey Lawrence J. , Yorek Mark A. 
Published: September 2005

AbstractBackgroundEpineurial arterioles of the sciatic nerve are innervated by sensory nerves containing calcitonin gene‐related peptide (CGRP). We postulated that treating these resistance vessels with capsaicin would cause the release of endogenous CGRP and vascular relaxation.MethodsVideomicroscopy was used to examine the effect of capsaicin and neuropeptides on vascular reactivity of epineurial arterioles from control and streptozotocin‐induced diabetic rats. Using immunohistochemistry, we examined expression of neuropeptide Y (NPY) and vanilloid receptor 1 in epineurial arterioles.ResultsInstead of relaxation, capsaicin was found to cause a concentration‐dependent vasoconstriction in epineurial arterioles. The effect of capsaicin was transient, refractory, blocked by capsazepine and duplicated by resiniferatoxin. When examining potential candidates for the mediation of capsaicin‐induced constriction, we found that vasopressin (VP), NPY, serotonin (5HT) and endothelin (ET), but not neurokinin A or substance P, caused a concentration‐dependent vasoconstriction of epineurial arterioles. Epineurial arterioles express NPY and receptor antagonists to NPY significantly decreased capsaicin‐induced vasoconstriction. In long‐term diabetic rats, vasoconstriction to capsaicin was significantly attenuated. However, long‐term diabetes did not impair vasoconstriction of epineurial arterioles to exogenous VP, NPY, 5HT or ET. Examining the expression of vanilloid receptor 1 in epineurial arterioles from control and long‐term diabetic rats, we found that immunoreactivity for vanilloid receptor 1 was decreased by diabetes.ConclusionsThese studies suggest that long‐term diabetes causes vascular dysfunction in epineurial arterioles of the sciatic nerve that includes a decrease in capsaicin‐induced vasoconstriction that is likely due to a decrease in the expression of vanilloid receptor 1. Copyright © 2005 John Wiley & Sons, Ltd.
Systematic investigation of lard polymorphism using combined DSC and time‐resolved synchrotron X‐ray diffraction
Authors: Kalnin Daniel , Lesieur Pierre , Artzner Franck , Keller Gerard , Ollivon Michel 
Published: September 2005

AbstractThe polymorphic behavior of lard was systematically investigated by differential scanning calorimetry (DSC) while simultaneously monitoring the formation of the different crystal forms with X‐ray diffraction (XRDT). To interpret the complex polymorphic evolution of the sample analyzed by regular DSC, both XRD patterns and DSC curves were recorded at the same time from the same sample (20 mg) using a laboratory‐made calorimeter (http://www.umr‐cnrs8612.u‐psud.fr/Francais/pdf/MICROCALIX.pdf) installed at a synchrotron radiation bench capable of both small‐ and wide‐angle X‐ray diffraction and time‐resolved experiments. Lard exhibits a large melting range (−30 °C ≤ T ≤ 50 °C) with three main crystallization peaks. In this range, lard polymorphism was investigated by varying the cooling and heating rates between 10 and 0.15 K/min, and by isothermal recrystallization at −10 and 15 °C. XRD lines observed by SAXS at about 35, 43.8 and 48.2 Å are identified to subcells α, β'1, β'2 and β, and attributed to the main DSC peaks. The crystalline forms appearing during the cooling depend on the cooling rate and on the final temperature. Higher cooling rates lead to unstable α forms that transform subsequently upon heating and/or storage into β' forms. The persistence of a monotropic transformation at −10 °C that was monitored during isothermal storage is explained by the presence of a liquid phase at this temperature.
The influence of pretreatment on pork fat crystallization
Authors: Svenstrup Gitte , Brüggemann Dagmar , Kristensen Lars , Risbo Jens , Skibsted Leif H. 
Published: September 2005

AbstractMelting points of two types of pork fat, lard and leaf fat, were studied in three different products: extracted fat, raw fat, and fat as an ingredient in liver pâté. The number of melting points and the temperature of melting were found, by differential scanning calorimetry, to correlate with the cooling rate for all of the products: Rapid cooling led to lowering of the melting point, assigned to the presence of unstable β crystals. The melting points varied also with the treatment of the fat, as the melting point of lard made by slow cooling and assigned to mainly β' crystals was different in the three products and found to be 39, 45, and 48 °C for extracted fat, raw fat, and fat as an ingredient in liver pâté, respectively, while slowly cooled leaf fat was found to have melting points at 48, 50, and 51 °C for the same three products, respectively. The fraction of unsaturated fatty acids present in the fat was important for both crystallization rate and melting points of α and β' crystals in extracted lard, an effect which was found less pronounced in liver pâté because of the presence of diverse components such as proteins.
Insight in model parameters by studying temperature influence on isothermal cocoa butter crystallization
Authors: Foubert Imogen , Vanrolleghem Peter A. , Dewettinck Koen 
Published: September 2005

AbstractThe aim of this research was to get more insight into the crystallization parameters of the model of Foubert et al.. (2002) by examining the isothermal crystallization of two cocoa butters at different temperatures. The nucleation in the α polymorph was studied by scanning diffusive light scattering and was shown to agree with the Turnbull–Fisher equation. In accordance with the solubility principle, the amount of α crystals decreases as a function of temperature. The four parameters of the crystallization model were used to describe the influence of temperature on the β' crystallization. The parameter aF decreases from temperatures of 20.5 °C onwards. The induction time increases with temperature while the rate constant K decreases as the temperature increases, especially at higher temperatures. Three hypotheses on the nature of the reverse reaction as described in the model were formulated and tested based on the temperature and cocoa butter dependency of the reverse reaction order n. The temperature dependence itself does not allow us to rule out one of the hypotheses, but the clear temperature dependence of the influence of the chemical composition is in favor of the hypothesis that the reverse reaction is dominantly either a re‐melting or a redissolving reaction, depending on the crystallization temperature.
Crystallisation and rheological properties of hydrogenated palm oil and palm oil blends in relation to crystal networking
Authors: Omar Zaliha , Let Chong Chiew , Seng Cheow Chong , Rashid Norizzah Abd. 
Published: September 2005

AbstractRefined bleached deodorised palm oil (RBDPO) was blended with 4–25 wt‐% hydrogenated palm oil (HPO). The physical, chemical and rheological properties of these samples were studied during 4 wk of storage at 15 °C. During storage, it was observed that there was an increase in solid fat content, compression force, hardness index (HI), melting temperatures, and storage modulus (G') with increasing concentration of HPO in the blends and with storage time. X‐ray diffraction results showed that the crystal networks of the blends were stabilised in the β' polymorphic form. However, in pure RBDPO, a very weak β form was observed. An increase in storage modulus (G'), compression force and HI indicated that the crystal networks of the blends became more highly structured with increasing storage time and concentration of HPO, which implies that post‐hardening had occurred without transformation of the polymorphic form from β’ to β.
Microstructure of fat crystallizing on a collagenous surface
Authors: Rogers Michael A. , Wright Amanda J. , Marangoni Alejandro G. 
Published: September 2005

AbstractThe effect of surface quality on fat crystallization was examined for glass and gelatin surfaces using three‐dimensional polarized light microscopy in an attempt to develop a model system for how fat may crystallize in arteries. A mixture of the high‐melting fraction of milk fat and triolein was crystallized from 60 °C to 30 °C at a rate of 0.5 °C/min on both glass and gelatin surfaces. Crystallization of fat on the gelatin surface led to an increase in the amount of nucleation and resulted in a more even distribution of crystal mass than crystallization on the glass surface. No evidence of crystal precipitation or glass surface crystallization was evident. We postulate that the gelatin acted as a template for nucleation. Similar trends were identified using fractal analysis. Fat crystallized on gelatin had a higher fractal dimension than fat crystallized on glass.
The influence of emulsifiers on the crystallisation behaviour of a palm oil‐based blend
Authors: Garbolino Chiara , Bartoccini Marta , Flöter Eckhard 
Published: September 2005

AbstractIn margarine manufacture, blends containing palm oil show a slow rate of crystallisation and, occasionally, a tendency to recrystallise. This phenomenon is caused by the segregation of the triacylglycerol 1,3‐dipalmitoyl 2‐oleoyl glycerol that undergoes the polymorphic transition from the β’ to the β form. Emulsifiers can be used to control fat crystallisation properties. Although some studies have been performed on crystallisation properties of emulsifiers, there are no conclusive results. The purpose of the present work was to investigate the effects of some selected emulsifiers on a fat blend containing palm oil. A fixed amount (2%) of sucrose esters or sorbitan esters was added. After melting, the samples were crystallised in bulk and submitted to temperature cycling. At regular intervals during crystallisation and after cycling, the hardness and the solid fat content of the samples were evaluated and the crystal morphology investigated with a polarised‐light microscope. In addition, samples at the end of storage time were evaluated with X‐ray diffraction in order to investigate the polymorphic behaviour. The addition of the emulsifiers showed an effect on the crystal morphology as well as the textural properties of the samples. The differences observed in the micro‐ and macrostructure are explained in terms of the acyl‐acyl interactions between the fatty acid residues of the emulsifiers and the triacylglycerols.
Molecular modeling of organic and biomolecular systems using BOSS and MCPRO
Authors: Jorgensen William L. , Tirado–Rives Julian 
Published: September 2005

AbstractAn overview is provided of the capabilities for the current versions of the BOSS and MCPRO programs for molecular modeling of organic and biomolecular systems. Recent applications are noted, particularly for QM/MM studies of organic and enzymatic reactions and for protein‐ligand binding. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1689–1700, 2005
The lotto numbers L(n,3,p,2)
Authors: Bougard Nicolas 
Published: September 2005

AbstractAn (n,k,p,t)‐lotto design is an n‐set N and a set ${\cal B}$ of k‐subsets of N (called blocks) such that for each p‐subset P of N, there is a block $B \in {\cal B}$ for which $\left | P \cap B \right | \geq t$. The lotto number L(n,k,p,t) is the smallest number of blocks in an (n,k,p,t)‐lotto design. The numbers C(n,k,t) = L(n,k,t,t) are called covering numbers. It is easy to show that, for n ≥ k(p − 1),

For k = 3, we prove that equality holds if one of the following holds:

n is large, in particular $ n\geq \big \{ {\matrix{(p - 1)(2p - 3)\quad {\rm if }n \not \equiv p(\bmod \;2),\cr (p - 1)(4p - 8)\quad {\rm if }n \equiv p(\bmod \;2),}}$
$n \equiv p - 4,p - 3, \ldots ,3p - 1(\bmod 6(p - 1)),$
2 ≤ p ≤ 6.

© 2006 Wiley Periodicals, Inc. J Combin Designs 14: 333–350, 2006
Comparison of contrast agents with high molarity and with weak protein binding in cerebral perfusion imaging at 3 T
Authors: Thilmann Oliver , Larsson Elna‐Marie , Björkman‐Burtscher Isabella M. , Ståhlberg Freddy , Wirestam Ronnie 
Published: September 2005

AbstractPurposeTo examine and compare properties of high‐molarity contrast agent gadobutrol (Gadovist) and weakly protein‐binding agent gadobenate‐dimeglumine (MultiHance®) in dynamic susceptibility contrast (DSC) perfusion imaging at 3 T.Materials and MethodsSixteen healthy volunteers underwent three separate examinations with contrast agent doses of 0.1 and 0.2 mmol/kg body weight (bw) gadobutrol and 0.1 mmol/kg bw gadobenate‐dimeglumine. Maps of relative regional cerebral blood volume (rCBV) and blood flow (rCBF) were calculated using deconvolution based on singular value decomposition. Signal and concentration time curves, the concentration‐to‐noise ratio (SNRc), and gray matter (GM)‐to‐white matter (WM) rCBV and rCBF contrast and ratios were evaluated in a region of interest (ROI)‐based analysis. Image quality of calculated parametric maps was assessed in direct visual comparison and with respect to suitability for diagnostic purposes.ResultsThe contrast agents displayed very similar results in the 0.1 mmol/kg examinations, both with respect to the quantitative evaluation parameters and in the qualitative assessment of the calculated parametric maps. Maps from 0.2 mmol/kg examinations were rated as being superior in quality, but with respect to diagnostic suitability all contrast agents and doses yielded images of sufficient quality.ConclusionAt 3 T, a gadobutrol or gadobenate‐dimeglumine dose of 0.1 mmol/kg is sufficient for DSC magnetic resonance imaging (MRI) perfusion assessment. At the used small injection volumes, the tissue concentration curve was determined only by the gadolinium (Gd) dosage in mmol/kg, and the T2* relaxation effects of the two agents can be considered to be nearly identical in the applied gradient‐echo (GRE) sequence. J. Magn. Reson. Imaging 2005. © 2005 Wiley‐Liss, Inc.
Wash‐in rate on the basis of dynamic contrast‐enhanced MRI: Usefulness for prostate cancer detection and localization
Authors: Kim Jeong Kon , Hong Seong Sook , Choi Young Jun , Park Seong Ho , Ahn Hanjong , Kim Choung‐Soo , Cho Kyoung‐Sik 
Published: September 2005

AbstractPurposeTo evaluate the usefulness of the wash‐in rate based on dynamic contrast‐enhanced (DCE) MRI for the detection and localization of prostate cancer.Materials and MethodsIn 53 patients, the wash‐in rate was measured in the cancer area and in three normal areas (the peripheral zone, inner portion of the transitional zone, and outer portion of the transitional zone). On the basis of these data, parametric imaging was generated and then its accuracy for cancer detection and location was evaluated compared to that of T2‐weighted imaging without the use of an endorectal coil. For that purpose the entire prostate was divided into 18 segments.ResultsThe wash‐in rate value was greater in cancer tissue (9.2/second) than in three normal tissues (3.3/second, 6.7/second, and 3.2/second, respectively; P < 0.001). The sensitivity and specificity were greater on parametric imaging of the wash‐in rate compared to T2‐weighted imaging in the entire prostate (96% and 82% vs. 65% and 60%, respectively) and the peripheral zone (96% and 97% vs. 75% and 53%; P < 0.05). In the transitional zone, the sensitivity was greater on parametric imaging (96%) than on T2‐weighted imaging (45%; P = 0.016), but the specificity was similar (51% vs. 73%; P = 0.102).ConclusionThe wash‐in rate based on DCE‐MRI is a useful parameter for prostate cancer detection and localization. J. Magn. Reson. Imaging 2005. © 2005 Wiley‐Liss, Inc.
Polysomnographic and pharmacokinetic findings in levodopa‐induced augmentation of restless legs syndrome
Authors: Vetrugno Roberto , Contin Manuela , Baruzzi Agostino , Provini Federica , Plazzi Giuseppe , Montagna Pasquale 
Published: September 2005

AbstractAugmentation, defined as a loss of circadian recurrence with progressively earlier daily onset and increase in the duration, intensity, and anatomy of symptoms, not compatible with the half‐life of the drug, is associated with dopaminergic treatment in restless legs syndrome (RLS) patients. The pathogenesis of augmentation is unclear. We describe a patient with idiopathic RLS who developed augmentation after 8 months of levodopa treatment. Videopolysomnographic and pharmacokinetic studies with monitoring of plasma levodopa levels demonstrated marked motor hyperactivity during augmentation, with anarchic discharges of motor unit potentials, tonic grouped discharges and flexor spasms, associated with painful dysesthesia. Symptoms and signs of augmentation were related to low plasma levodopa levels, abating 75 minutes after oral levodopa administration and reappearing after 3 hours, closely mirroring the rapid rise and fall of plasma levodopa concentration. This case is the first report in which RLS augmentation is shown to be characterized by motor hyperkinesias paralleling levodopa plasma pharmacokinetic profile. © 2005 Movement Disorder Society