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Zinc Salts (zinc + salt)
Selected AbstractsN -Acetylation as a Means to Activate Polyfluoroarylamines for Selective ortho -Hydrodefluorination by Zinc in Aqueous Ammonia: A Concise Route to Polyfluorobenzo Azaheterocycles,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 2 2007Sergey S. Laev Abstract N -Acetylation of polyfluoroarylamines is proposed as a meansto remove the amino group blocking effect of their hydrodefluorination by zinc in aqueous ammonia. With pentafluoroacetanilide, the Zn ion specific effect has been demonstrated to be responsible for ortho hydrodefluorination. This regiochemistry is accompanied by the removal of a fluorine atom from the para position, which occurs predominantly in the initial phase of the process in the absence of deliberately added zinc salt. The CuCl2 additive has been found to accelerate the reaction and to propel it to double defluorination. Quantum chemical calculations suggest a diminished electron affinity of pentafluoroaniline, which is responsible for its inertness in relation to the hydrodefluorination reaction. The pentafluoroaniline radical anion, which essentially has a nonplanar structure, is prone to easy fragmentation to give an aminotetrafluorophenyl radical. For pentafluoroacetanilide, CVA experiments and quantum chemical calculations predict that the pentafluorophenyl moiety serves as the electron receptor and that the acetamido group is twisted out of coplanarity with the benzene ring; thus, together with the electron-withdrawing effect of the acetyl group, the amino group blocking effect is suppressed. On this ground, the selective ortho hydrodefluorination of polyfluoroacetanilides is developed as an important protocol for the expeditious and general synthesis of polyfluorobenzo azaheterocycles via readily accessible polyfluoroarylamines from base polyfluoroarenes. Its applicability has been illustrated by preparing quinolines that possess a polyfluorinated benzene moiety by the Skraup synthesis utilizing crude polyfluoroacetanilide hydrodefluorination products as starting materials. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] New Bis(mercaptoimidazolyl)(pyrazolyl)borate Ligands and Their Zinc Complex ChemistryEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2003Mouhai Shu Abstract Nine new tripodal NS2 ligands of the bis(mercaptoimidazolyl)(pyrazolyl)borate type with varying 3-R-mercaptoimidazolyl moieties were prepared as their potassium salts. Treatment with zinc salts yielded the complex types L·Zn,Cl, L·Zn,I, L·Zn,ONO2, L·Zn,OClO3 and [L·Zn(imidazole)]ClO4. Attempts at the formation of L·Zn,OH or cationic L·Zn complexes resulted in dismutation and formation of ZnL2 complexes. Hydrolytic destruction yielded one [OZn4(thiooimidazolate)6] complex. The ZnS2NO coordination which is present in the enzyme-substrate complex of alcohol dehydrogenase could be successfully modelled by an [L·Zn(C2H5OH)]+ complex. The L·Zn,X complexes showed very low catalytic activity in the dehydrogenation of 2-propanol or the hydrogenation of p -nitrobenzaldehyde. The new compounds were identified by a total of 12 structure determinations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Systematic study of interfacial interactions between clays and an ionomerJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010Yan Gao Abstract To study the interfacial interactions between an ionomer [poly(ethylene- co -acrylic acid) neutralized by zinc salts (PI)] and clays, PI,clay nanocomposites were prepared using a solution method. Two types of commercially available montmorillonite clays respectively K10 and KSF were used, and were modified with organic modifiers with chain lengths of 12,18 carbons. The interactions between the PI, clays, and modifiers were evaluated through study of the structure, morphology, and properties of the PI,clay nanocomposites. We found that the modifiers were successfully intercalated into the clay layers (Fourier transform infrared spectroscopy). The clay modified with a long-chain agent showed an exfoliated nature in the nanocomposite. The thermal stability and storage modulus of PI were improved greatly by the addition of the clays, especially when the long-chain modifier was used (thermogravimetric analysis and dynamic mechanical analysis). The differential scanning calorimetry results show that clay layers are inserted into the clusters because of solvent-directed morphological evolution, so the transition of the ionic domains and the crystallinity of PI are changed. The interaction between PI, the modifier, and the silicate layer played an important role in the determination of the properties of the nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Cause of death in Wilson diseaseMOVEMENT DISORDERS, Issue 15 2007John M. Walshe MD Abstract Before 1948, all patients with Wilson disease died shortly after diagnosis. In 1948, BAL (dimercaprol) was introduced as a possible effective treatment, to be followed by penicillamine (1955), zinc salts (1961), trientine (1969), liver transplantation (1982), and tetrathiomolybdate (1984). Despite this wide range of therapeutic options, patients still die. This article examines the cause of death in 67 patients (33 men, 34 women) out of a series of 300 seen between 1948 and 2000. Patients were classified according to their presentation as neurological, 32 patients, hepatic 11, mixed hepatic/neurological 10, hemolytic, 6, and "sibling biopsy " 8. Diagnostic failure was the principal cause of death but there were multiple other causes of which the principal was poor compliance and the development of malignant disease after 10 years of follow-up. The development of new symptoms should alert the physician to the possibility of a new pathology. © 2007 Movement Disorder Society [source] Flame retardancy mechanisms of metal phosphinates and metal phosphinates in combination with melamine cyanurate in glass-fiber reinforced poly(1,4-butylene terephthalate): the influence of metal cationPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 6 2008Ulrike Braun Abstract The pyrolysis and fire behavior of glass-fiber reinforced poly(butylene terephthalate) (PBT/GF) with two different metal phosphinates as flame retardants in combination with and without melamine cyanurate (MC) were analyzed by means of thermogravimetry, thermogravimetry coupled with infrared spectroscopy, flammability, and cone calorimeter tests as well as scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray fluorescence spectroscopy. In PBT/GF, dosages of 13,20% of the halogen-free flame retardant aluminum phosphinate or aluminum phosphinate in combination with MC fulfill the requirements for electrical engineering and electronics applications (UL 94,=,V-0; LOI,>,42%), whereas the use of the same amount of zinc phosphinate or zinc phosphinate in combination with MC does not improve the fire behavior satisfactorily (UL 94,=,HB; LOI,=,27,28%). The performance under forced flaming conditions (cone calorimeter) is quite similar for both of the metal phosphinates. The use of aluminum and zinc salts results in similar flame inhibition predominantly due to the release of the phosphinate compounds in the gas phase. Both metal phosphinates and MC interact with the polymer changing the decomposition characteristics. However, part of the zinc phosphinate vaporizes as a complete molecule. Because of the different decomposition behavior of the metal salts, only the aluminum phosphinate results in a small amount of thermally stable carbonaceous char. In particular, the aluminum phosphinate-terephthalate formed is more stable than the zinc phosphinate-terephthalate. The small amount of char has a crucial effect on the thermal properties and mechanical stability of the residue and thus the flammability. Copyright © 2008 John Wiley & Sons, Ltd. [source] Luminescent Excited-State Intramolecular Proton-Transfer (ESIPT) Dyes Based on 4-Alkyne-Functionalized [2,2,-Bipyridine]-3,3,-diol DyesCHEMISTRY - A EUROPEAN JOURNAL, Issue 14 2008Gilles Ulrich Dr. Abstract Functionalized 6,6,-dimethyl-3,3,-dihydroxy-2,2,-bipyridine dyes (BP(OH)2) exhibit relatively intense fluorescence from the relaxed excited state formed by excited-state intramolecular proton transfer (ESIPT). Bromo functionalization of (BP(OH)2) species followed by palladium(0)-catalyzed reactions allows the connection (via alkyne tethers) of functional groups, such as the singlet-emitter diazaboraindacene (bodipy) group or a chelating module (terpyridine; terpy). The X-ray structure of the terpy-based compound confirms the planarity of the 3,3,-dihydroxy-bipyridine unit. The new dyes exhibit relatively intense emission on the nanosecond timescale when in fluid solution, in the solid state at 298,K, and in rigid glasses at 77,K. In some cases, the excitation wavelength luminescence was observed and attributed to 1),inefficiency of the ESIPT process in particular compounds when not enough vibrational energy is introduced in the Franck,Condon state, which is populated by direct light excitation or 2),the presence of an additional excited state that deactivates to the ground state without undergoing the ESIPT process. For some selected species, the effect of the addition of zinc salts on the absorption and luminescence spectra was investigated. In particular, significant fluorescence changes were observed as a consequence of probable consecutive formation of a 1:1 and 1:2 molecular ratio of ligand/zinc adducts owing to coordination of ZnII ions by the bipyridyldiol moieties, except when an additional terpyridine subunit is present. In fact, this latter species preferentially coordinates to the ZnII ion in a 1:1 molecular ratio and further inhibits ZnII interaction. In the hybrid Bodipy/BP(OH)2 species, complete energy transfer from the BP(OH)2 to the bodipy fluorophore occurs, leading to exclusive emission from the lowest-lying bodipy subunit. Des composés colorés à base de 6,6,-dimethyl-3,3,-dihydroxy-2,2,-bipyridine (BP(OH)2) ont été synthétisés et présentent une fluorescence relativement intense issue de la relaxation d,un état excité provenant d,un transfert de proton dans l,état excité (ESIPT). La bromation de dérivés (BP(OH)2) suivie d,un couplage croisé catalysé par du Pd0sous-ligandé permet de connecter (par l,intermédiaire de pont alcyne) des groupes fonctionnels comme un groupe émetteur singulet de type boradiazaindacène (Bodipy) ou un module chélatant universel (une terpyridine). Une structure par diffraction aux rayons X a été obtenu avec le dérivé terpyridine, celle ci confirme la planéité de l,unité 3,3,-dihydroxy-bipyridine. Les nouveaux fluorophores possèdent une émission relativement intense avec une durée de vie de l,ordre de la nanoseconde, en solution et à l,état solide à 298,K ainsi que dans un verre à 77,K. Dans certain cas, la luminescence dépend de la longueur d,onde d,excitation, ce phénomène est attribué à (i) l,inefficacité du processus ESIPT, quand trop peu d,énergie vibrationnelle est introduite dans l,état Franck-Condon peuplé directement par la lumière d,excitation (ii) la présence d,un état excité supplémentaire qui désactive l,état fondamental sans passer par un processus ESIPT. Pour certains composés, l,effet de l,addition de sels de Zinc sur les spectres d,absorption et d,émission a été étudié : en particulier, des changements significatifs de fluorescence ont été observés, probablement due à la formation consécutive de complexes ligand/zinc de st,chiométrie 1:1 et 1:2, provenant de la coordination des cations ZnIIpar l,unité bipyridyl-diol, sauf quand une fonction terpyridine est présente. En fait, dans cette dernière espèce le zinc est préférentiellement coordiné par la terpyridine dans un ratio 1:1, et toute coordination supplémentaire de Zinc semble inhibée. Dans le composé hybride Bodipy/BP(OH)2,un transfert d,énergie quantitatif est observé du BP(OH)2vers le fluorophore Bodipy, entraînant une émission exclusive de la sous-unité Bodipy. Composti basati sulla subunità 6,6,-dimetil-3,3,-dididrossi-2,2,-bipiridina (BP(OH)2), variamente funzionalizzati, presentano fluorescenza relativamente intensa da stati eccitati formati attraverso trasferimento protonico nello stato eccitato (ESIPT). Bromo-funzionalizzazione dei composti di tipo BP(OH)2, seguita da reazioni catalizzate da Pd(0), permettono di connettere (con legame alchinico) gruppi funzionali quali il diazaboroindacene (Bodipy) o un modulo chelante (terpiridina) al frammento BP(OH)2. La struttura ai raggi X del composto contenente la terpiridina conferma la planarità dell,unità 3,3,-diidrossi-bipiridina. Le nuove specie presentano intensa emissione nella scala dei nanosecondi, in soluzione fluida ed allo stato solido a 298,K ed in matrice rigida a 77,K. In alcuni casi, la luminescenza dipende dalla lunghezza d,onda di eccitazione: questo fenomeno è attribuito a (i) inefficienza del processo ESIPT, quando non sufficiente energia vibrazionale è introdotta nello stato Franck-Condon a seguito di eccitazione luminosa o (ii) alla presenza di uno stato eccitato addizionale che si disattiva allo stato fondamentale senza passare dallo stato eccitato prodotto attraverso il meccanismo ESIPT. Per composti selezionati è stato anche studiato l,effetto della presenza di sali di zinco sulle proprietà di assorbimento elettronico e di luminescenza: significativi cambiamenti della fluorescenza sono stati osservati, come conseguenza della consecutiva formazione di addotti 1:1 e 1:2 (rapporto molare BP(OH)2/zinco), dovuta alla coordinazione di cationi di ZnIIda parte del bipiridil-diolo, che si verifica in tutti i casi studiati tranne in presenza di una subunità terpiridinica. In quest,ultimo caso, infatti, si forma soltanto l,addotto 1:1, e ulteriore coordinazione di cationi di ZnIIappare inibita. Nella specie ibrida Bodipy/BP(OH)2si verifica un completo trasferimento di energia elettronica dal BP(OH)2 al Bodipy, che porta ad emissione esclusivamente dalla subunità Bodipy, a piû bassa energia. [source] | |||||||||||||