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41.
Investigating sorption-driven dissolved organic matter fractionation by multidimensional fluorescence spectroscopy and PARAFAC 总被引:1,自引:0,他引:1
Banaitis MR Waldrip-Dail H Diehl MS Holmes BC Hunt JF Lynch RP Ohno T 《Journal of colloid and interface science》2006,304(1):271-276
Soil organic matter is involved in many ecosystem processes, such as nutrient supply, metal solubilization, and carbon sequestration. This study examined the ability of multidimensional fluorescence spectroscopy and parallel factor analysis (PARAFAC) to provide detailed chemical information on the preferential sorption of higher-molecular-weight components of natural organic matter onto mineral surfaces. Dissolved organic matter (DOM) from soil organic horizons and tree leaf tissues was obtained using water extracts. The suite of fluorescence spectra was modeled with PARAFAC and it was revealed that the DOM extracts contained five fluorescing components: tryptophan-like (peak location at excitation <255 nm:emission 342 nm), tyrosine-like (276 nm:312 nm), and three humic-substance-like components (<255 nm:456 nm, 309 nm:426 nm, <255 nm:401 nm). In general, adsorption onto goethite and gibbsite increased with increasing DOM molecular weight and humification. PARAFAC analysis of the pre- and post-sorption DOM indicated that the ordering of sorption extent was humic-like components (average 91% sorption) > tryptophan-like components (52% sorption) > tyrosine-like components (29% sorption). This differential sorption of the modeled DOM components in both the soil organic horizon and leaf tissue extracts led to the fractionation of DOM. The results of this study demonstrate that multidimensional fluorescence spectroscopy combined with PARAFAC can quantitatively describe the chemical fractionation process due to the interaction of DOM with mineral surfaces. 相似文献
42.
A convenient and efficient four step synthesis of 2-methyl-5-(methylthio)benzothiazole is presented. 相似文献
43.
Harfmann RG Deshmukh BK Conklin J Turowski M Lynch S 《Journal of AOAC International》2007,90(3):786-793
A collaborative study was performed to determine the reproducibility of a method for the determination of methylcellulose (MC) and hydroxypropyl methylcellulose (HPMC) in food. These widely used food gums possess unusual solubility characteristics and cannot accurately be determined by existing dietary fiber methods. The new method uses the enzyme-digestion procedure of AOAC Official Method 991.43. Digestate solutions must be refrigerated to fully hydrate MC or HPMC. The chilled solutions are filtered and analyzed by size-exclusion liquid chromatography. Collaborating laboratories received 28 samples containing MC or HPMC in the range of 0-100%. The sample set included blind duplicates of 5 food matrixes (bread, milk, fish, potato, and powdered juice drink). Cochran and Grubbs tests were used to eliminate outliers. For food samples containing MC, values for within-laboratory precision, repeatability relative standard deviation (RSDr), ranged from 4.2 to 16%, and values for among-laboratories precision, reproducibility relative standard deviation (RSDR), ranged from 11 to 20%. For HPMC samples, RSDr values ranged from 6.4 to 27%, and RSDR values ranged from 17 to 39%. Recoveries of MC and HPMC from the food matrixes ranged from 78 to 101%. These results show acceptable precision and reproducibility for the determination of MC and HPMC, for which no Official AOAC Methods exist. It is recommended that this method be adopted as AOAC Official First Action. 相似文献
44.
Sessler JL Roznyatovskiy V Pantos GD Borisova NE Reshetova MD Lynch VM Khrustalev VN Ustynyuk YA 《Organic letters》2005,7(23):5277-5280
[reaction: see text] Two easy-to-synthesize polypyrrolic 2,5-diamidothiophene Schiff base macrocycles are reported, along with their anion binding properties as determined via UV-vis spectroscopic titrations carried out in dichloroethane. There is a striking difference between the interactions with anions of the two macrocycles, a finding ascribed to differences in their rigidity. For example, the more flexible dipyrromethane-derived macrocycle displays a 1.2:1 hydrogen sulfate versus nitrate selectivity, while its more rigid bipyrrole-derived congener shows a 7.4:1 selectivity in favor to hydrogen sulfate. 相似文献
45.
Park IW Yoo J Kim B Adhikari S Kim SK Yeon Y Haynes CJ Sutton JL Tong CC Lynch VM Sessler JL Gale PA Lee CH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(9):2514-2523
A ditopic ion-pair receptor (1), which has tunable cation- and anion-binding sites, has been synthesized and characterized. Spectroscopic analyses provide support for the conclusion that receptor 1 binds fluoride and chloride anions strongly and forms stable 1:1 complexes ([1·F](-) and [1·Cl](-)) with appropriately chosen salts of these anions in acetonitrile. When the anion complexes of 1 were treated with alkali metal ions (Li(+), Na(+), K(+), Cs(+), as their perchlorate salts), ion-dependent interactions were observed that were found to depend on both the choice of added cation and the initially complexed anion. In the case of [1·F](-), no appreciable interaction with the K(+) ion was seen. On the other hand, when this complex was treated with Li(+) or Na(+) ions, decomplexation of the bound fluoride anion was observed. In contrast to what was seen with Li(+), Na(+), K(+), treating [1·F](-) with Cs(+) ions gave rise to a stable, host-separated ion-pair complex, [F·1·Cs], which contains the Cs(+) ion bound in the cup-like portion of the calix[4]pyrrole. Different complexation behavior was seen in the case of the chloride complex, [1·Cl](-). Here, no appreciable interaction was observed with Na(+) or K(+). In contrast, treating with Li(+) produces a tight ion-pair complex, [1·Li·Cl], in which the cation is bound to the crown moiety. In analogy to what was seen for [1·F](-), treatment of [1·Cl](-) with Cs(+) ions gives rise to a host-separated ion-pair complex, [Cl·1·Cs], in which the cation is bound to the cup of the calix[4]pyrrole. As inferred from liposomal model membrane transport studies, system 1 can act as an effective carrier for several chloride anion salts of Group 1 cations, operating through both symport (chloride+cation co-transport) and antiport (nitrate-for-chloride exchange) mechanisms. This transport behavior stands in contrast to what is seen for simple octamethylcalix[4]pyrrole, which acts as an effective carrier for cesium chloride but does not operates through a nitrate-for-chloride anion exchange mechanism. 相似文献
46.
Kasthuri Balasubramani Packianathan Thomas Muthiah Daniel E Lynch 《Chemistry Central journal》2007,1(1):1-10
Background
The characterization of three types of Marche (Italy) honeys (Acacia, Multifloral, Honeydew) was carried out on the basis of the their quality parameters (pH, sugar content, humidity) and mineral content (Na, K, Ca, Mg, Cu, Fe, and Mn). Pattern recognition methods such as principal components analysis (PCA) and linear discriminant analysis (LDA) were performed in order to classify honey samples whose botanical origins were different, and identify the most discriminant parameters. Lastly, using ANOVA and correlations for all parameters, significant differences between diverse types of honey were examined.Results
Most of the samples' water content showed good maturity (98%) whilst pH values were in the range 3.50 – 4.21 confirming the good quality of the honeys analysed. Potassium was quantitatively the most relevant mineral (mean = 643 ppm), accounting for 79% of the total mineral content. The Ca, Na and Mg contents account for 14, 3 and 3% of the total mineral content respectively, while other minerals (Cu, Mn, Fe) were present at very low levels. PCA explained 75% or more of the variance with the first two PC variables. The variables with higher discrimination power according to the multivariate statistical procedure were Mg and pH. On the other hand, all samples of acacia and honeydew, and more than 90% of samples of multifloral type have been correctly classified using the LDA. ANOVA shows significant differences between diverse floral origins for all variables except sugar, moisture and Fe.Conclusion
In general, the analytical results obtained for the Marche honeys indicate the products' high quality. The determination of physicochemical parameters and mineral content in combination with modern statistical techniques can be a useful tool for honey classification. 相似文献47.
Lynch M Hehir S Kavanagh P Leech D O'Shaughnessy J Carty MP Aldabbagh F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(11):3218-3226
The key step in the synthesis of new five, six and seven-membered alicyclic ring [1,2-a]-fused bioreductive benzimidazolequinones was radical cyclisation. Six and seven-membered tributyltin hydride-mediated homolytic aromatic substitutions of nucleophilic N-alkyl radicals onto the benzimidazole-2-position occurred in high yields (63-70 %) when quaternising the pyridine-like 3-N of imidazole with camphorsulfonic acid and using large excesses of the azo-initiator, 1,1'-azobis(cyclohexanecarbonitrile), to supplement the non-chain reaction. Elaboration of benzimidazoles to the benzimidazolequinones occurred in excellent yields. The IC50 values for the cytotoxicity of benzimidazolequinones towards the human skin fibroblast cell line GM00637 were in the nanomolar range, as determined by using the MTT assay. The benzimidazolequinones were much more cytotoxic than indolequinone analogues. 1,2,3,4-Tetrahydropyrido[1,2-a]benzimidazole-6,9-dione was the most potent compound prepared being more than 300 times more cytotoxic than the clinically used bioreductive drug, mitomycin C. The latter benzimidazolequinone was more potent under hypoxic conditions (associated with solid tumors), being 4.4 times more cytotoxic than under aerobic conditions, while mitomycin C was 1.8 times more selective towards hypoxia. The cyclopropane fused pyrido[1,2-a]benzimidazolequinone, 1a,2,3,9b-tetrahydro-1H-cyclopropa[3,4]pyrido[1,2-a]benzimidazole-5,8-dione was less cytotoxic and selective than the five-membered ring analogue, 1,1a,8,8a-tetrahydrocyclopropa[3,4]pyrrolo[1,2-a]benzimidazole-3,6-dione. Modifying the structure of the most potent pyrido[1,2-a]benzimidazolequinone by attaching methyl substituents onto the quinone moiety increased reductive potentials and decreased cytotoxicity and selectivity towards hypoxia. 相似文献
48.
Dr. Kuppuswamy Arumugam C. Daniel Varnado Jr. Dr. Stephen Sproules Dr. Vincent M. Lynch Prof. Dr. Christopher W. Bielawski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):10866-10875
High yielding syntheses of 1‐(ferrocenylmethyl)‐3‐mesitylimidazolium iodide ( 1 ) and 1‐(ferrocenylmethyl)‐3‐mesitylimidazol‐2‐ylidene ( 2 ) were developed. Complexation of 2 to [{Ir(cod)Cl}2] (cod=cis,cis‐1,5‐cyclooctadiene) or [Ru(PCy3)Cl2(?CH‐o‐O‐iPrC6H4)] (Cy=cyclohexyl) afforded 3 ([Ir( 2 )(cod)Cl]) and 5 ([Ru( 2 )Cl2(?CH‐o‐O‐iPrC6H4)]), respectively. Complex 4 ([Ir( 2 )(CO)2Cl]) was obtained by bubbling carbon monoxide through a solution of 3 in CH2Cl2. Spectroelectrochemical IR analysis of 4 revealed that the oxidation of the ferrocene moiety in 2 significantly reduced the electron‐donating ability of the N‐heterocyclic carbene ligand (ΔTEP=9 cm?1; TEP=Tolman electronic parameter). The oxidation of 5 with [Fe(η5‐C5H4COMe)Cp][BF4] as well as the subsequent reduction of the corresponding product [ 5 ][BF4] with decamethylferrocene (Fc*) each proceeded in greater than 95 % yield. Mössbauer, UV/Vis and EPR spectroscopy analysis confirmed that [ 5 ][BF4] contained a ferrocenium species, indicating that the iron center was selectively oxidized over the ruthenium center. Complexes 5 and [ 5 ][BF4] were found to catalyze the ring‐closing metathesis (RCM) of diethyl diallylmalonate with observed pseudo‐first‐order rate constants (kobs) of 3.1×10?4 and 1.2×10?5 s?1, respectively. By adding suitable oxidants or reductants over the course of a RCM reaction, complex 5 was switched between different states of catalytic activity. A second‐generation N‐heterocyclic carbene that featured a 1′,2′,3′,4′,5′‐ pentamethylferrocenyl moiety ( 10 ) was also prepared and metal complexes containing this ligand were found to undergo iron‐centered oxidations at lower potentials than analogous complexes supported by 2 (0.30–0.36 V vs. 0.56–0.62 V, respectively). Redox switching experiments using [Ru( 10 )Cl2(?CH‐o‐O‐iPrC6H4)] revealed that greater than 94 % of the initial catalytic activity was restored after an oxidation–reduction cycle. 相似文献
49.
Naphthocrown‐Strapped Calix[4]pyrroles: Formation of Self‐Assembled Structures by Ion‐Pair Recognition 下载免费PDF全文
Dr. Sung Kuk Kim Hong Gyu Lee Dr. Gabriela I. Vargas‐Zúñiga Dr. Vincent M. Lynch Prof. Dr. Cheal Kim Prof. Dr. Jonathan L. Sessler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(37):11750-11759
A new approach to the construction of self‐assembled structures is reported that is based on ion‐pair recognition. Towards this end, the calix[4]pyrrole naphthocrown‐4 hybrid structures 2 and 3 were prepared. These multitopic receptors contain recognition sites for both anions and cations. On the basis of solution‐phase 1H NMR spectroscopic analysis and solid‐state single‐crystal X‐ray diffraction structural studies, it was established that receptors 2 and 3 are able to bind specific ion pairs with high selectivity via different binding modes. In the case of CsF and CsCl, the ion‐pair complexes formed from receptors 2 and 3 were found to self‐assemble to produce either linear supramolecular polymeric crystalline solids or nanotube‐like cyclic hexamers depending on the specific choice of ion pairs and crystallization solvents. Proton NMR studies provided evidence for solution‐phase self‐association in organic media. 相似文献
50.
A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State 下载免费PDF全文
Junpeng He Nolan W. Waggoner Samuel G. Dunning Dr. Alexander Steiner Dr. Vincent M. Lynch Prof. Simon M. Humphrey 《Angewandte Chemie (International ed. in English)》2016,55(40):12351-12355
A tetra(carboxylated) PCP pincer ligand has been synthesized as a building block for porous coordination polymers (PCPs). The air‐ and moisture‐stable PCP metalloligands are rigid tetratopic linkers that are geometrically akin to ligands used in the synthesis of robust metal–organic frameworks (MOFs). Here, the design principle is demonstrated by cyclometalation with PdIICl and subsequent use of the metalloligand to prepare a crystalline 3D MOF by direct reaction with CoII ions and structural resolution by single crystal X‐ray diffraction. The Pd?Cl groups inside the pores are accessible to post‐synthetic modifications that facilitate chemical reactions previously unobserved in MOFs: a Pd?CH3 activated material undergoes rapid insertion of CO2 gas to give Pd?OC(O)CH3 at 1 atm and 298 K. However, since the material is highly selective for the adsorption of CO2 over CO, a Pd?N3 modified version resists CO insertion under the same conditions. 相似文献