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Kinds of Compounds Terms modified by Compounds Selected AbstractsEFFECTS OF FIVE NEW COMPOUNDS ON THE LARVAL GROWTH AND DIGESTIVE PHYSIOLOGY OF THE ASIATIC CORN BORER, OSTRINIA FURNACALIS LARVAEINSECT SCIENCE, Issue 3 2003Jia He Abstract Five new compounds were tested on the growth and antifeeding activity compared with toosendanin against fifth instar larvae Ostrinia furnacalis. The activities of two proteases, a weak alkaline trypsine-like enzyme and a chymotrypsin-like enzyme, in the midgut of Ostrinia furnacalis larvae were also measured. Experimental results suggest that when incorporated into an artificial diet at the concentration of 500mg/kg, the antifeeding activities of toosendanin, C19, C23, C24, C26, C28 were 51.16%, 57.61%, 4.28%, 51.08%, 36.73% and 51.67%, respectively, C19, C24, C28 had no significant difference with toosendanin. At 20mg/kg, the larval growth were remarkably suppressed by C19, C26, C28, the inhibition of C28 was close to toosendanin in 48 h. The two proteases were activated by toosendanin and C28 while they were inhibited in 48 h but activated in 24 h by C19, C24 and C26. In this paper, the related functions and mechanisms were discussed. [source] CHANGES IN MAJOR ANTIOXIDANT COMPOUNDS DURING AGING OF TRADITIONAL BALSAMIC VINEGARJOURNAL OF FOOD BIOCHEMISTRY, Issue 1 2010ELENA VERZELLONI ABSTRACT Traditional balsamic vinegar (TBV) shows antioxidant capacity that increases passing from cask 5, containing the youngest vinegar, to cask 1 containing the oldest vinegar. This increase in antioxidant capacity is a consequence of both the concentration of compounds already present and of new antioxidants formation and is positively related to the increase in the polyphenolic content and in the Maillard reaction/caramellization products. During TBV aging, some reactions involving flavonoids and tannins take place. Tannins can undergo acid-catalyzed cleavage of their interflavonoid bonds with subsequent condensation of other flavonoid molecules. In addition, the low pH, the decrease of the water content and the presence of aldehydes, may promote flavonoids polycondensation. These reactions explain the observed increase in polymeric phenolic compounds and the decrease in monomeric flavonoids. During TBV aging an increase in the browning index is observed as a consequence of the polycondensation reactions of flavonoids and of brown melanoidins accumulation. PRACTICAL APPLICATIONS Traditional balsamic vinegar is a potentially healthy seasoning with high antioxidant capacity that increases during the aging resulting in a product with a strong antioxidant capacity and rich in phenolic compounds such as phenolic acids, monomeric catechins, flavonols and tannins. It also contains other antioxidants such as melanoidins derived from the Maillard and caramelization reaction that occur during must boiling and traditional balsamic vinegar aging. Independently of their bioavailability, traditional balsamic vinegar can contribute to supply antioxidant molecules that play an important role in protecting the gastrointestinal tract itself against peroxidation, thereby limiting the formation of detrimental lipid degradation products. [source] PHENOLIC COMPOUNDS, TOCOPHEROLS AND OTHER MINOR COMPONENTS IN VIRGIN OLIVE OILS OF SOME TUNISIAN VARIETIESJOURNAL OF FOOD BIOCHEMISTRY, Issue 2 2007D. KRICHENE ABSTRACT The phenols, ,-tocopherols, fatty acids and oxidative stability of six monovarietal virgin olive oils (VOOs) were determined. Fourteen phenolic compounds were detected and quantified by solid phase extraction and reversed phase-high performance liquid chromatography. Dialdehydic form of elenolic acid linked to tyrosol and hydroxytyrosol, oleuropein and ligstroside aglycones were the main components in all samples. Pinoresinol was the most abundant component in lignan fraction. The total phenol content of these monovarietal oils varied from 66.82 mg/kg in "Neb Jmel" oil to 662.74 mg/kg in "El Hor" oil. A wide range of ,-tocopherol contents was also noticed; it varied from 141.94 mg/kg in "Semni" variety to 364.23 mg/kg in "Jdallou" variety. With regard to pigments, chlorophylls and carotenoids were found at variable concentrations: with median values of 11.33 and 3.10 mg/kg, respectively. Among the studied varieties, "Oueslati" and El Hor were characterized by the lowest levels of palmitic and linoleic acids and the highest values of oleic acid. [source] PHENOLIC COMPOUNDS IN THE FLESH OF KOREAN APPLE CULTIVAR, BUSAJOURNAL OF FOOD BIOCHEMISTRY, Issue 6 2002HEA-JEUNG WHANG ABSTRACT Phenolic compounds were purified from Busa, the most widely cultivated apple cultivar in Korea, by a sequential separation employing PVPP, Ambertite XAD-2 and Sephadex LH-20 column chromatography. Phenolic compounds in some fractions were farther identified by directly comparing with corresponding phenolic standards after separation on HPLC and GC-MS. The phenolic compounds identified were p-hydoxybenzoic, protocatechuic, 4-hydroxymetyl-benzonic, caffeic, p-coumaric, o-coumaric, ferulic, sinapic and chlorogenic acids and (±)-catechin. Among them, 4-hydroxymethylbenzoic, protocatechuic, o-coumaric and sinapic acids were ascertained as new members of a family of phenolic acids present-in apples. Also the presence of rutin, quercetin and phlorizin in apples were demonstrated using HPLC. [source] SUPERCRITICAL CARBON DIOXIDE SELECTIVITY TO FRACTIONATE PHENOLIC COMPOUNDS FROM THE DRY ETHANOLIC EXTRACT OF PROPOLISJOURNAL OF FOOD PROCESS ENGINEERING, Issue 1 2010LOSIANE C. PAVIANI ABSTRACT The global yield and composition of extracts obtained by supercritical carbon dioxide (SC-CO2) extraction from a dry ethanolic extract of propolis were measured in order to determine the possibility of using SC-CO2 to fractionate components of interest present in these extracts. The global yield extraction was measured, and also the concentrations of the following phenolic compounds in the resulting supercritical fluid extracts (SFEs): 3,5-diprenyl-4-hydroxycinnamic acid (known as artepillin C), 3-prenyl-4-hydroxycinnamic acid, 4-hydroxycinnamic acid (p- coumaric acid) and 4-methoxy-3,5,7-trihydroxyflavone (kaempferide), of which artepillin C was the target component of greatest interest. The results showed extraction yields between 3.82 (at 150 bar) and 13.07% (at 350 bar), which could be highly correlated with the density of the SC-CO2 at a constant temperature of 60C. The resulting concentrations in the SFE indicated that the selectivity of the carbon dioxide could be manipulated, and it was more selective at lower pressures, although with lower extraction yields. PRACTICAL APPLICATIONS Supercritical fluid extraction is an interesting process for the production of natural extracts because it is a clean process, and extractions using carbon dioxide (CO2) as the solvent have been gaining attention in recent years. This study presented important aspects with respect to the fractionation of a dry ethanolic extract of propolis using supercritical carbon dioxide, and it is important to explore the potential applications of propolis extracts and the biological properties of its fractions in the food, pharmaceutical and cosmetic industries, such as in dental hygiene products, wound healing creams and antibacterial soaps. [source] COMPARISON OF VOLATILE COMPOUNDS AND CHEMICAL AND PHYSICAL PROPERTIES IN ORANGE JUICE FROM DIFFERENT PARTS OF JINCHEN FRUITJOURNAL OF FOOD QUALITY, Issue 2 2010YU QIAO ABSTRACT Jinchen is a native sweet cultivar of Citrus sinensis and one of the most important varieties used in orange juice processing in China. The study of flavor components of Jinchen orange juice has not been carried out before. In this paper, the color characteristics, pH value, total soluble solids, total acids, as well as organic acids and sugars were determined in Jinchen orange juice from different parts of fruit (peeled juice, pulp juice, whole fruit juice). The color characteristics were significantly different among three types of Jinchen orange juice. The level of vitamin C and total soluble solids/total acids ratio (TSS/TA) is higher in whole fruit juice. The organic acids and sugars also changed. Pulp juice is rich in the highest amounts of organic acids and sugars. Volatiles from three juices were studied using the solid phase microextraction (SPME) combined with gas chromatography/mass spectrometry. The whole fruit juice has the highest amount of volatile compounds (53.07 mg/L) followed by peeled juice (51.044 mg/L) and pulp juice (27.107 mg/L). Some differences in the constituents of the volatile compounds of three type juices were observed. These results indicated that volatile compounds and quality properties differed in Jinchen orange juice from different parts of fruit. PRACTICAL APPLICATIONS The peeled orange fruits are usually used for juice processing. Great amounts of aroma components with intensive odor are located in the peel of orange. The aroma of pulp possessing weak fresh citrus odor is different from peel. The different parts of the orange utilized in processing have direct impact on juice quality. It is very essential to obtain the data of chemical and physical properties in juice from different parts of orange fruit. The quality information could be used to modify the orange aroma. [source] COMPARISON OF HEADSPACE SOLID PHASE MICROEXTRACTION AND XAD-2 METHODS TO EXTRACT VOLATILE COMPOUNDS PRODUCED BY SACCHAROMYCES DURING WINE FERMENTATIONSJOURNAL OF FOOD QUALITY, Issue 1 2006JEFFRI C. BOHLSCHEID ABSTRACT A modified headspace solid phase microextraction (HS-SPME) method was compared with Amberlite® XAD-2 resin for the extraction of volatile compounds. In the HS-SPME method, volatiles were extracted using an 85 ,m polyacrylate fiber from wines that contained a standardized amount of ethanol (10% v/v), NaCl (0.325 g/mL) and internal standards (dodecanol and nonanoic acid). Both extraction procedures yielded high relative recoveries (>92%) and reproducibilities (coefficient of variations , 11%) for the different higher alcohols, esters and medium-chain fatty acids. Overall, limits of detection for the HS-SPME and XAD-2 methods were below sensory threshold concentrations. HS-SPME and XAD-2 performed similarly in the analysis of a Riesling wine; however, the HS-SPME method did not require organic solvents and was generally quicker to perform. In applying the HS-SPME method, differences in concentrations of volatile compounds produced in Riesling and Chenin blanc wines by 11 different yeast strains were noted. [source] IMPACTS OF SOLAR UV RADIATION ON THE PHOTOSYNTHESIS, GROWTH, AND UV-ABSORBING COMPOUNDS IN GRACILARIA LEMANEIFORMIS (RHODOPHYTA) GROWN AT DIFFERENT NITRATE CONCENTRATIONS,JOURNAL OF PHYCOLOGY, Issue 2 2009Yangqiao Zheng Solar ultraviolet radiation (UVR, 280,400 nm) is known to affect macroalgal physiology negatively, while nutrient availability may affect UV-absorbing compounds (UVACs) and sensitivity to UVR. However, little is known about the interactive effects of UVR and nitrate availability on macroalgal growth and photosynthesis. We investigated the growth and photosynthesis of the red alga Gracilaria lemaneiformis (Bory) Grev. at different levels of nitrate (natural or enriched nitrate levels of 41 or 300 and 600 ,M) under different solar radiation treatments with or without UVR. Nitrate-enrichment enhanced the growth, resulted in higher concentrations of UVACs, and led to negligible photoinhibition of photosynthesis even at noon in the presence of UVR. Net photosynthesis during the noon period was severely inhibited by both ultraviolet-A radiation (UVA) and ultraviolet-B radiation (UVB) in the thalli grown in seawater without enriched nitrate. The absorptivity of UVACs changed in response to changes in the PAR dose when the thalli were shifted back and forth from solar radiation to indoor low light, and exposure to UVR significantly induced the synthesis of UVACs. The thalli exposed to PAR alone exhibited higher growth rates than those that received PAR + UVA or PAR + UVA + UVB at the ambient or enriched nitrate concentrations. UVR inhibited growth approximately five times as much as it inhibited photosynthesis within a range of 60,120 ,g UVACs · g,1 (fwt) when the thalli were grown under nitrate-enriched conditions. Such differential inhibition implies that other metabolic processes are more sensitive to solar UVR than photosynthesis. [source] SENSORY CHARACTERISTICS OF CHEMICAL COMPOUNDS POTENTIALLY ASSOCIATED WITH BEANY AROMA IN FOODS,JOURNAL OF SENSORY STUDIES, Issue 1 2004SUNTAREE VARA-UBOL ABSTRACT The sensory characteristic "beany" is a limiting factor in introducing soy products to many consumers in western cultures. This research described sensory properties of beany flavor and described sensory odor characteristics of 19 chemicals that have been associated with beany aroma and flavor in previous literature. Seven concentrations varying from 1 to 100,000 ppm of each chemical (if soluble in propylene glycol) were examined by a five member trained descriptive panel. The panel described beany as having multiple attributes. Musty/earthy, musty/dusty, sour aromatics, and characterizing attributes such as green/pea pod, nutty, or brown collectively imparted beany aroma and flavor of most beans. Starchy flavor and powdery texture also were intrinsically associated with beany in bean product samples. Some chemicals tested were not beany at any level tested. Three alcohols, two ketones, one aldehyde, and one pyrazine exhibited beany characteristics (green/peapod or brown) only at low concentrations, generally 1-10 ppm. [source] ODOR PERCEPTION OVER LIQUID EMULSIONS CONTAINING SINGLE AROMA COMPOUNDS: EFFECTS OF AROMA CONCENTRATION AND OIL VOLUME FRACTIONJOURNAL OF SENSORY STUDIES, Issue 6 2002CHANTAL BROSSARD ABSTRACT This study aimed to check the hypothesis that aroma concentration in the aqueous phase of an oil-in-water emulsion controlled the odor intensity of single aroma compounds. A set of flavored oil-in-water emulsions, prepared according to a 22 experimental design (aroma concentration, oil volume fraction) with two central points, was assessed for odor intensity by a 24-member panel during four sessions. In each session, three of the four-studied aroma molecules (benzaldehyde, ethyl butyrate, linalool and acetophenone) were investigated. Whatever the aroma, the experimental data showed that the oil volume fraction of the emulsion (from 0.12 to 0.48) did not influence the odor intensity. For each emulsion composition, aroma concentrations at equilibrium in both phases were calculated using the oil-water partition coefficient of the compound. Odor intensities, estimated from aroma concentration in the aqueous phase using previously reported modeling of odor intensity above water solutions, were then compared to experimental data. It is confirmed that the perceived odor intensity is governed by the aroma concentration in the aqueous phase at the time of the trial and not by the averaged apparent concentration in the emulsion. [source] INFLUENCE OF AROMA COMPOUNDS ON LARGE DEFORMATION PROPERTIES OF STARCH-BASED SYSTEMS DURING AGINGJOURNAL OF TEXTURE STUDIES, Issue 3 2001G. ARVISENET The effect of aroma compounds on the texture of gelled aqueous corn starch systems was studied by uniaxial compression during aging for 18 days. Three different types of behavior were observed, depending on the nature of the added aroma compound. Isoamyl acetate did not modify the measured parameters, compared with nonflavored products. Linalool, known for its ability to form inclusion complexes with amylose, modified the parameters which are usually considered to be governed by the rearrangement of amylose chains. Ethyl hexanoate modified the parameters depending mostly on amylopectin. These results suggest that the nature of the aroma compound may play a major role in interactions with starch. These interactions can be different from inclusion complexes involving amylose chains only, the latter being widely described by different authors. [source] VOLATILE ORGANIC COMPOUNDS IN GROUND WATER FROM RURAL PRIVATE WELLS, 1986 TO 1999,JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION, Issue 5 2004Michael J. Moran ABSTRACT: The U.S. Geological Survey (USGS) collected or compiled data on volatile organic compounds (VOCs) in samples of untreated ground water from 1,926 rural private wells during 1986 to 1999. At least one VOC was detected in 12 percent of samples from rural private wells. Individual VOCs were not commonly detected with the seven most frequently detected compounds found in only 1 to 5 percent of samples at or above a concentration of 0.2 microgram per liter (,g/l). An assessment level of 0.2 ,g/l was selected so that comparisons of detection frequencies between VOCs could be made. The seven most frequently detected VOCs were: trichloromethane, methyl tert -butyl ether, tetrachloroethene, dichlorodifluoromethane, methylbenzene, 1,1,1-trichloroethane, and 1,2-dibromo-3-chloropropane. Solvents and trihalomethanes were the most frequently detected VOC groups in private wells. The distributions of detections of gasoline oxygenates and fumigants seemed to be related to the use patterns of compounds in these groups. Mixtures were a common mode of occurrence of VOCs with one-quarter of all samples with detections including two or more VOCs. The concentrations of most detected VOCs were relatively small and only 1.4 percent of samples had one or more VOC concentrations that exceeded a federally established drinking water standard or health criterion. [source] Rh(I) and Pd(II) complexes of methoxy functionalized heterocyclic carbene: Synthesis and characterizationCRYSTAL RESEARCH AND TECHNOLOGY, Issue 6 2006M. E. Günay Abstract A new methoxy functionalized 2-(trichloromethyl)-1,3-diarylimidazolidin (6) was synthesized as the precursor for N-heterocyclic carbene complexes of Pd(II) and Rh(I) by the condensation of N,N'-bis(2,4-dimethoxyphenyl)-1,2-diaminoethane with chloral. The structures of all compounds have been elucidated by a combination of multinuclear NMR spectroscopy, elemental analysis and in one instance, by single crystal X-ray diffraction. Compound 8, C27H34N2O4ClRh, crystallizes in the triclinic space group P-1 with cell dimensions a = 9.7642(12)Å, b = 11.1914(11)Å, c = 13.0102(14)Å, , = 104.034(9)°, , = 106.658(9)°, , = 99.658(9)° with Z = 2. The molecular structure of 8 shows the geometry around the Rh metal to be a slightly distorted square planar. The crystal structure shows the formation of centrosymmetric dimers via intermolecular C-H...Cl hydrogen bonds. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Behavioural observations of Pieris brassicae larvae indicate multiple mechanisms of action of analogous drimane antifeedantsENTOMOLOGIA EXPERIMENTALIS ET APPLICATA, Issue 3 2000L. Messchendorp Abstract We tested 11 analogous synthetic drimane antifeedant compounds for their feeding inhibiting effects on larvae of the large white butterfly Pieris brassicae L. (Lepidoptera: Pieridae) in no-choice tests on the host plant Brassica oleracea L. Furthermore, we observed larval feeding behaviour in no-choice tests to analyze temporal effects of five drimanes. The results show that the five analogous antifeedants differentially influence feeding behaviour and locomotion activity. Warburganal and polygodial are most likely sensory mediated antifeedants. Habituation to these compounds occurs soon after the onset of the tests (i.e., within 0.5,1.5 h). Compound 5 and confertifolin are probably not direct, sensory mediated antifeedants. After 0.5,1.5 h of exposure, these compounds inhibit not only feeding, but also locomotion behaviour, indicating postingestive, toxic effects. Isodrimenin inhibits feeding from the onset of the test and is probably a sensory mediated antifeedant. No habituation occurs to this compound, indicating that isodrimenin is either a very strong antifeedant or that it additionally has postingestive, toxic effects. Topical application of the drimanes on the larval cuticle revealed feeding inhibiting effects, but these could not be related to the occurrence of postingestive feeding inhibiting effects, indicating that this method is inappropriate to show possible postingestive effects of drimanes in P. brassicae. In conclusion, the behavioural observations performed in this research indicate that analogous drimanes inhibit feeding by P. brassicae larvae through multiple mechanisms of action. The results show that, when developing a structure activity relationship (SAR) for a series of antifeedants, it is important to distinguish the mode of action which underlies inhibition of feeding. [source] A Single-Source Co/Li/O Organometallic Precursor for Nanocrystalline LiCoO2 , Synthesis, Formation Pathway, and Electrochemical Performance,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2010Jayaprakash Khanderi Abstract A single-source precursor route to phase-pure LiCoO2 by employing the organometallic precursor [(COD)2CoLi(thf)2] (1) to introduce a Co/Li/O 1:1:2 stoichiometry is described for the first time. Compound 1 undergoes decomposition in the presence of oxygen, forming nanoscaled, electrochemically active LiCoO2 starting at a temperature as low as 200 °C. Its temperature-dependent formation pathway was studied by various spectroscopic and microscopic techniques. The transition temperature for the evolution of layered LiCoO2 is above 400 °C. Electrochemical studies indicate that the low-temperature modification of LiCoO2 can be obtained at 500 °C, showing moderate electrochemical battery performance. [source] A Dynamically Entangled Coordination Polymer: Synthesis, Structure, Luminescence, Single-Crystal-to-Single-Crystal Reversible Guest Inclusion and Structural TransformationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2010Arshad Aijaz Abstract A ZnII coordination polymer {[Zn2(cpa)2(bpy)]·3H2O}n (1) (cpa2, = 4-(methoxycarbonyl)benzoate and bpy = 4,4,-bipyridine) has been synthesized under solvothermal condition and structurally characterized. This coordination polymer has nanotubular threefold entangled (2D,3D) structure with embedded water molecules; the water molecules can be partially exchanged in reversible single-crystal-to-single-crystal (SC-SC) fashion by different solvent molecules like methanol, ethanol and acetone giving rise to {[Zn2(cpa)2(bpy)]·(0.5MeOH)·(2.5H2O)}n (2), {[Zn2(cpa)2(bpy)]·(0.5EtOH)·(0.5H2O)}n (3) and {[Zn2(cpa)2(bpy)]·(0.5Me2CO)·(H2O)}n (4). Inclusion of EtOH or MeOH leaves the size of the voids in the framework unaltered. Inclusion of acetone, however, is accompanied by shrinking of the voids in the framework. Heating of 1 at 100 °C under vacuum for 4 h affords the de-solvated compound, {Zn2(cpa)2(bpy)}n (1,). Single-crystal X-ray structure of 1, shows sliding of the individual nanotubular components expanding the overall framework. Thus, the coordination polymer exhibits dynamic motion of the molecular components in SC-SC fashion. All compounds were further characterized via IR spectroscopy, PXRD, elemental and TGA analysis. When 1 is placed in benzene at 100 °C for 2 days, compound {[Zn2(cpa)2(bpy)]·(2.5H2O)}n (5) is formed in a SC-SC fashion where coordination number of ZnII ion increases from four to five. Compound 1 also exhibits reversible guest-dependent photoluminescence properties. [source] Dehydrogenation of Hydridoirida-,-diketones in Methanol: The Selective Formation of Mono- and Dinuclear Acyl ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2010Roberto Ciganda Abstract The hydridoirida-,-diketone [IrH{(PPh2(o -C6H4CO))2H}Cl] (1) reacts with diimines (NN) or with pyridine (py) in refluxing methanol to undergo dehydrogenation. The reactions afford selectively the cis -acyl, trans -phosphane isomers of the cationic [Ir(PPh2(o -C6H4CO))2(NN)]+ {NN = 2,2,-bipyridine (2); R,N=C(CH3),C(CH3)=N,R, [R = R, = NH2 (3); R = R, = OH (4); R = OH, R, = NH2 (5)]} or neutral [IrCl(PPh2(o -C6H4CO))2(py)] (6) derivatives. The reactions are faster for ligands containing amino substituents. Refluxing 1 in MeOH affords the formation of an equimolar mixture of dimercationic species [Ir2(,-Cl)(,-PPh2(o -C6H4CO))2(PPh2(o -C6H4CO))2]+ (7a and 7b) containing two acyls and a chloride as bridging groups. The isomers could be separated by fractional precipitation. Compound [3]Cl, containing amino substituents in the imino functionalities, catalyses the hydrogen transfer from 2-propanol to cyclohexanone to afford cyclohexanol. All the complexes were fully characterised spectroscopically. Single crystal X-ray diffraction analysis was performed on complexes 6 and [7b]ClO4. [source] Magnetic and Electrochemical Properties of a Heterobridged ,-Phenoxido,,1,1 -Azide Dinickel(II) Compound: A Unique Example Demonstrating the Bridge Distance Dependency of Exchange IntegralEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 33 2009Rajesh Koner Abstract The synthesis, structure, magnetic and electrochemical properties of the heterobridged ,-phenoxido,,1,1 -azide dinickel(II) compound [NiII2(HL1)3(,1,1 -N3)]·3H2O (1) derived from the tetradentate Schiff base ligand N -(2-hydroxyethyl)-3-methoxysalicylaldimine (H2L1) are described. The title compound crystallizes in the triclinic system (space group P). Electrochemical analyses reveal that compound 1 exhibits two-step quasireversible couples in the reduction window with E1/2 values of ,1412 and ,1762 mV. The variable-temperature (2,300 K) magnetic susceptibilities at 1 T of the title compound were measured. The interaction between the metal centres is weak ferromagnetic (J = 5.0 cm,1, g = 2.23, D1 = 29.2 cm,1 and D2 = 10.7 cm,1). Comparison of the exchange integral of 1 with that of the only reported ,-phenoxido,,1,1 -azide dinickel(II) compound results in the emergence of a unique example of the dependence of strength of magnetic exchange interaction on the metal,ligand bridge distance. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Reactions of [Et4N][Tp*W(,3 -S)(,-S)2(CuSCN)2] with Nitrogen Donor Ligands: Syntheses, Structures, and Third-Order Nonlinear Optical PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2009Zhen-Hong Wei Abstract Reactions of the preformed cluster [Et4N][Tp*W(,3 -S)(,-S)2(CuSCN)2] (1) with pyridine (py), 4,4,-bipyridine (4,4,-bipy), or 1,3-bis(4-pyridyl)propane (bpp) led to the formation of three neutral [Tp*W(,3 -S)(,-S)2Cu2]-based compounds [Tp*W(,3 -S)(,-S)2Cu2(SCN)(py)2] (2), [{Tp*W(,3 -S)(,-S)2Cu2(SCN)}2(4,4,-bipy)]·3.5H2O (3·3.5H2O), and [Tp*W(,3 -S)(,-S)2Cu2(SCN)(bpp)]2 (4), respectively. Compounds 2,4 were characterized by elemental analysis, IR spectra, UV/Vis spectra, 1H NMR, and X-ray analysis. There are two linkage isomers [Tp*W(,3 -S)(,-S)2Cu2(SCN)(py)2] and [Tp*W(,3 -S)(,-S)2Cu2(NCS)(py)2], each of which has its own enantiomeric pair in the crystal of 2. Compound 3 has a double butterfly-shaped structure in which two [Tp*W(,3 -S)(,-S)2Cu2(SCN)] fragments are linked with a single 4,4,-bipy bridge. For 4, the two butterfly-shaped [Tp*W(,3 -S)(,-S)2Cu2(SCN)] fragments are interconnected by a pair of bpp bridges. The third-order nonlinear optical (NLO) performances of 2,4 in DMF were also investigated by Z -scan techniques.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Molecular Iodine Stabilization in an Extended N···I,I···N AssemblyEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2009Francesco Isaia Abstract The adduct [bis(quinoxaline)-2,2,,3,3,-disulfide·I2], (Q2S2·I2), (1) can be easily synthesised from the reaction of Q2S2 and I2 in CH2Cl2 or, in the absence of any solvent, through diffusion of I2 vapours at 60 °C. X-ray diffraction analysis shows the presence of an extended N···I,I···N assembly in which each I2 molecule links a Q2S2 molecule at both ends through a nitrogen atom to form a polymeric species; the d(I,I) and d(N,I) bond lengths confirm a very weak nitrogen,iodine interaction at the base of the N···I,I···N assembly. DFT calculations provide optimised distances for the N···I and I,I bonds and explanation for the zigzag chain formation: the mPW1PW functional and the B3LYP hybrid functional with a variety of basis sets for the I atomic species [CRENBL, LANL2DZ, LANL2DZ(d,p), LANL08(d), SBKJC, SBKJC polarised-LFK and Stuttgart RLC] have been tested. Compound 1 proved stable up to nearly 100 °C, and the stability is to be mainly attributed to the lattice energy of its polymeric structure then to donor,acceptor stabilisation. The facile insertion of molecular iodine into the Q2S2 network makes this compound an interesting iodine sponge, suitable for I2 storage; moreover, Q2S2 can easily collect and release I2(g) by a temperature-controlled process (60 and 97 °C, respectively). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] The Inorganic,Organic Hybrid Compound {[Mn(trien)]2SnS4}·4H2O: Exhibiting a Hitherto Unknown Binding Mode of the [SnS4]4, TetrahedronEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2009Nicole Pienack Abstract The compound {[Mn(C6H18N4)]2SnS4}·4H2O (C6H18N4 = triethylenetetramine) was obtained under solvothermal conditions. In the structure of the {[Mn(C6H18N4)]2SnS4}, chain, two S atoms of the [SnS4]4, anion act in a hitherto never observed ,3 bridging mode that connects the Mn2S2N8 di-octahedra. The Mn2+ ions are octahedrally coordinated by four N and two S atoms, and two symmetry-related octahedra share a common S,S edge. Three of the H2O molecules are joined into chains through H-bonding interactions.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2-(Me2NCH2)C6H4]2Sb FragmentEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2009Laura M. Opris Abstract Compounds containing the [2-(Me2NCH2)C6H4]2Sb moiety were prepared by using R2SbX [X = Cl (1), Br (2)] as starting materials. The reaction of 1 with Me3SiCH2MgCl gave the mixed alkyl,aryl stibine R2SbCH2SiMe3 (3). Reduction of 2 with Mg in thf followed by in situ air oxidation or treatment with S8 resulted in the isolation of (R2Sb)2E [E = O (4), S (5)]. Compound 5 is also formed from R2SbCl and Na2S. The reaction of 4 with [W(CO)5(thf)] gives the unexpected complex [(R2SbOH)W(CO)5] (6). The new compounds were investigated by IR, 1H, and 13C NMR spectroscopy, as well as by mass spectrometry. The structures of 3,6 were determined by single-crystal X-ray diffraction. For compounds 3,5, both nitrogen atoms from the pendant arms are involved in intramolecular N,Sb coordination, which results in distorted square-pyramidal (C,N)2SbC or (C,N)2SbE (E = O, S) cores. By contrast, in 6 only one nitrogen atom is strongly coordinated to the antimony center, whereas the second nitrogen atom is involved in N···H,O bonding. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Two Hexanickel-Substituted Keggin-Type Germanotungstates,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2008Jun-Wei Zhao Abstract Two new inorganic,organic hybrid germanotungstates built from trivacant Keggin fragments and in situ generated hexanickel clusters [Ni(en)2]0.5[{Ni6(,3 -OH)3(en)3(H2O)6}(B-,-GeW9O34)]·3H2O (1) and [{Ni6(,3 -OH)3(dap)3(H2O)6}(B-,-GeW9O34)]·H3O·4H2O (2) (en = ethylenediamine and dap = 1,2-diaminopropane) were hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, single-crystal X-ray diffraction and magnetic analysis. Compound 1 crystallizes in the monoclinic space group P21/n; whereas compound 2 crystallizes in the monoclinic space group P21/c. Single-crystal X-ray diffraction indicates that both contain a hexa-NiII -substituted trivacant Keggin unit [{Ni6(,3 -OH)3(L)3(H2O)6}(B-,-GeW9O34)], (L = en or dap). Magnetic susceptibility measurements show the presence of ferromagnetic coupling interactions within the hexa-NiII clusters for 1 and 2. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Self-Assembled Two-Dimensional Water-Soluble Dipicolinate Cu/Na Coordination Polymer: Structural Features and Catalytic Activity for the Mild Peroxidative Oxidation of Cycloalkanes in Acid-Free MediumEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2008Marina V. Kirillova Abstract The new water-soluble 2D Cu/Na coordination polymer [Cu(,-dipic)2{Na2(,-H2O)4}]n·2nH2O (1) has been synthesized by self-assembly in aqueous medium from copper(II) nitrate, dipicolinic acid (H2dipic) and sodium hydroxide in the presence of triethanolamine. It has been characterized by IR spectroscopy, FAB+ -MS, elemental and single-crystal X-ray diffraction analyses, the latter featuring a layered 2D metal,organic structure that is extended to a 3D supramolecular assembly by extensive hydrogen bonding between adjacent layers and involving crystallization water molecules. Compound 1 has been shown to act as a catalyst precursor for the peroxidative oxidation of cyclohexane and cyclopentane to the corresponding cyclic ketones and alcohols by aqueous H2O2 in MeCN solution and in the absence of acid additives.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Dual Supermesityl Stabilization: A Room-Temperature-Stable 1,2,4-Triphosphole Radical, Sigmatropic Hydrogen Rearrangements, and Tetraphospholide Anion,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2008Alex S. Ionkin Abstract Cesium 3,5-bis(2,4,6-tri- tert -butylphenyl)-1,2,4-triphospholide (12) and cesium 5-(2,4,6-tri- tert -butylphenyl)tetraphospholide (13) were synthesized and isolated with flat five-membered rings, which are an indication of the aromaticity in these anions. Compound 13 is the first example of a stable tetraphospholide anion, which is structurally characterized. Kinetic stabilization of the 1,2,4-triphospholide system by two supermesityl groups resulted in the detection of the room-temperature-stable radical 17 and the observation of a series of successive sigmatropic hydrogen shifts in the first stable 1H -1,2,4-triphosphole 14 with a P,H bond.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] P-Chirogenic Benzo-Fused Phenoxaphosphane: Synthesis, Resolution and Study of the Stereochemical Properties of the Corresponding Palladium ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2008Franco Doro Abstract The synthesis and resolution of chiral phenoxaphosphane 3, with the stereogenic center at the phosphorus atom, is described. Compound 3 has been synthesized following a well-known procedure for trapping a phosphorus atom within a six-membered ring. The resolution of the racemic mixture of 3 was achieved through separation of its diastereomeric palladacycle derivatives 7a,b and 9a,b. The absolute configuration of enantiopure phosphanes 3a,b was assigned unequivocally by means of X-ray crystal structure determination for complex 9a and by combination of NOE(1H,1H)/COSY(1H,1H) spectroscopy and DFT calculations for complexes 7a,b, which in both cases led to identical results. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis and Characterization of the New Tetrameric Magnesium Imide Compound [(thf)MgNSiPh3]4EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2008Alexander Fuchs Abstract Reaction between di- n -butylmagnesium and the primary amine H2NSiPh3 affords the tetrameric magnesium imide [(thf)MgNSiPh3]4, representing the first example of a structurally characterized magnesium imide in which the group attached to the nitrogen is not aryl. The four Mg and N atoms are arranged in the form of a distorted heterocubane unit. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Novel (3,4)- and (4,5)-Connected Lanthanide Metal,Organic FrameworksEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2008Xian-Wen Wang Abstract The three-dimensional lanthanide noninterpenetrating metal,organic frameworks formulated as [Ln(3,5-pdc)(C2O4)0.5(H2O)2]·H2O (Ln = LuIII, GdIII, TmIII and YbIII for complex 1,4, respectively; 3,5-pdc = 3,5-pyridinedicarboxylate) were synthesized by hydrothermal reactions of 3,5-H2pdc with lanthanide oxide and perchloric acid. Compound 1 shows (3,4)-connected (4.82)(4.85) dmc-type topological network, and complexes 2,4 display the novel (4,5)-connected (44.6.8)(44.62.84) xww-type topology. The lanthanide-mediated transformation of CO2 to oxalate under hydrothermal conditions was observed. The fluorescence properties of complexes 1,4 were investigated. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] First Example of a Gold(I) N -Heterocyclic-Carbene-Based Initiator for the Bulk Ring-Opening Polymerization of L -LactideEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2006Lipika Ray Abstract Synthesis, structure, and catalysis studies of two Au- and Ag-based initiators, namely, [3-(N - tert -butylacetamido)-1-(2-hydroxycyclohexyl)imidazol-2-ylidene]AuCl (1c) and [3-(N - tert -butylacetamido)-1-(2-hydroxycyclohexyl)imidazol-2-ylidene]AgCl (1b), for the bulk ring-opening polymerization of L -lactide are reported. Specifically, gold complex 1c was obtained from silver complex 1b by the transmetalation reaction with (SMe2)AuCl. Silver complex 1b was synthesized by the treatment of 3-(N - tert -butylacetamido)-1-(2-hydroxycyclohexyl)imidazolium chloride (1a) with Ag2O. Compound 1a was synthesized directly from the reaction of N - tert -butyl-2-chloroacetamide, cyclohexene oxide, and imidazole. The molecular structures of 1a, 1b, and 1c have been determined by X-ray diffraction studies. The formation of neutral monomeric complexes with linear geometries at the metal centers was observed for both 1b and 1c. The Au and Ag complexes 1c and 1b successfully catalyzed the bulk ring-opening polymerization of L -lactide at elevated temperatures under solvent-free melt conditions to produce moderate to low molecular weight polylactide polymers with narrow molecular weight distributions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Solvothermal Synthesis, Crystal Structures, and Properties of New Selenidoantimonates [Ln(en)4(SbSe4)] (Ln = La, Nd) and [Sm(en)4]SbSe4·0.5en: The First Example of an SbSe43, Anion Acting as a Ligand to a Lanthanide ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2006Ding-Xian Jia Abstract Three new lanthanide selenidoantimonates [Ln(en)4(SbSe4)] [Ln = La (1), Nd (2)] and [Sm(en)4]SbSe4·0.5en (3) (en = ethylenediamine) were first synthesized by treating LnCl3, Sb, and Se in a stoichiometric ratio with en under mild solvothermal conditions. Compounds 1 and 2 are isostructural. The Ln3+ ion has a nine-coordinate environment involving eight N atoms from four en ligands and one Se atom from the SbSe43, anion forming a distorted bicapped pentagonal bipyramid. [La(en)4(SbSe4)] and [Nd(en)4(SbSe4)] are the first examples of solvothermally synthesized selenidoantimonates with an SbSe43, anion acting as a ligand in a lanthanide complex. The crystal structure of 3 contains an isolated bicapped trigonal-prismatic coordinated [Sm(en)4]3+ cation, a tetrahedral SbSe43, anion, and half a free en molecule in its asymmetric unit. The bandgaps of 2.22 eV for 1, 2.33 eV for 2, and 2.54 eV for 3 have been derived from optical absorption spectra. Compound 1 loses the en ligands in one step, whereas compound 2 loses them in two steps. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] |