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31.
The general features of two series of sol-gel derived materials, designatedurethanesils (Ut), have been investigated by infrared and Raman spectroscopies with the goal of elucidating the chemical environment of
the Eu3+ cations.
The host frameworks of the two families of ormolytes studied have been represented by m-Ut(350) and d-Ut(300), where m stands
for mono, d stands for di, 350 and 300 are the average molecular weights of the organic precursors (poly(ethylene glycol)
methyl ether, PEGME, and poly(ethylene glycol), PEG, respectively).
The hybrid matrix of the mono-xerogels is composed by a siliceous backbone bonded by means of urethane linkages (-NHC (=O)O-)
to pendant methyl end capped oligopolymer chains with approximately 7 oxyethylene units, whereas that of the di-xerogels is
based on a siliceous network grafted through urethane groups to both ends of poly(oxyethylene) segments containing about 6
(OCH2CH2) repeat units.
Both classes of materials have been doped with europium triflate (Eu(CF3SO3)3). The doped samples have been identified by m-Ut(350)nEu(CF3SO3)3 and d-Ut(300)nEu(CF3SO3), where n is the molar ratio of (OCH2CH2) repeat units per Eu3+ ion. Materials with n ranging from ∞ to 5 have been analyzed. The spectral data obtained provide evidence that the cations
begin to coordinate to the ether oxygen atoms of the oligopolymer chains at n=40 in the mono-urethanesils and at n=10 in the
di-urethanesils. In mono-urethanesils samples with n>40 and in di-urethanesils materials with n>10, the Eu3+ coordinate exclusively to the carbonyl oxygen atoms of the urethane linkages.
Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001. 相似文献
32.
A paraxial ray-optics formalism proposed for designing radially symmetric variable-index lenses is extended to the case of lenses of elliptical symmetry of the index profile. 相似文献
33.
A series of molecular dynamics simulations have been performed to study the supramolecular structure of self‐assembled complexes formed by N‐dodecyltrimethylammonium cations and the synthetic polypeptide poly(α,L ‐glutamate). The influence of the type of solvent has been investigated, considering explicit environments of chloroform, water, and methanol on a stoichiometric complex containing 15 residues. In chloroform, the complex stabilizes in a regular structure: the polypeptide adopts an α‐helix conformation that is regularly surrounded by surfactant molecules to form electrostatic interactions through a multiple interaction pattern. However, this structure destabilizes in methanol and water: (a) the α‐helix unfolds in the two solvents and (b) the electrostatic links between the surfactant molecules and the polyanion are disrupted in aqueous solution, although these interactions are still preserved in methanol. The role of the solvent environment in stabilizing or destabilizing the polypeptide secondary structure, the organization of the surfactant molecules, and predominantly the surfactant–polypeptide supramolecular organization is discussed in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1122–1133, 2006 相似文献
34.
We report a rigorous theory to show the origin of the unexpected periodic behavior seen in the consecutive differences between prime numbers. We also check numerically our findings to ensure that they hold for finite sequences of primes, that would eventually appear in applications. Finally, our theory allows us to link with three different but important topics: the Hardy–Littlewood conjecture, the statistical mechanics of spin systems, and the celebrated Sierpinski fractal. 相似文献
35.
An automatic continuous-flow photometric method for the determination of ammonia is proposed. It is based on the Berthelot reaction, the product of which is temporarily immobilized on a suitable support (Sephadex QAE) located in the flow-cell. The retained product is eluted after measurement by a cationic surfactant contained in the carrier solution. The method allows the determination of the analyte between 0.4 and 20.0 gmg/ml, with an RSD of 0.8%, at a sampling frequency of 13/hr. The determination limit can be reduced by a factor of ten by using a flow-cell with a two-fold longer path length, but the sampling frequency is also reduced as a result. The method was applied to the determination of this analyte in agricultural samples (plants and soils) and compared with standard methods for these types of samples. 相似文献
36.
Two greener procedures for flow-injection spectrophotometric determination of nitrite in natural waters were developed and critically compared. Replacement of toxic reagents, waste minimization and treatment were exploited to attend the standards of clean chemistry. The flow system was designed with solenoid micro-pumps in order to minimize reagent consumption and waste generation. The first procedure is based on the Griess diazo-coupling reaction with sulfanilamide and N-(1-naphthyl)ethylenediamine (NED) yielding an azo dye, followed by photodegradation of the low amount of waste generated based on the photo-Fenton reaction. The second procedure is based on the formation of iodine from nitrite and iodide in acid medium in order to avoid the use of toxic reagents. For Griess method, linear response was achieved up to 1.0 mg L− 1, described by the equation A = − 0.007 + 0.460C (mg L− 1), r = 0.999. The detection limit was estimated as 8 μg L− 1 at the 99.7% confidence level and the coefficient of variation was 0.8% (n = 20). The sampling rate was estimated as 108 determinations per hour. The consumption of the most toxic reagent (NED) is reduced 55-fold and 20-fold in comparison to batch method and flow injection with continuous reagent addition, respectively. A colorless residue was obtained by in-line photodegradation with reduction of 87% of the total organic carbon content. The results obtained for natural water samples were in agreement with those achieved by the reference method at the 95% confidence level. For the nitrite–iodide method, linear response was observed up to 2.0 mg L− 1, described by the equation A = − 0.024 + 0.148C (mg L− 1), r = 0.999. The detection limit was estimated as 25 μg L− 1 at the 99.7% confidence level and the coefficient of variation was 0.6% (n = 20). The sampling rate was estimated as 44 determinations per hour. Despite avoiding the use of toxic reagents, the nitrite–iodide method presented worst performance in terms of selectivity and sensitivity. 相似文献
37.
The synthesis of a series of tetra‐ and pentadentate bispidine‐type ligands (bispidine=3,7‐diazabicyclo[3.3.1]nonane) – tetradentate ligands are donor‐substituted at C(2) and C(4), pentadentate ligands have an additional donor at N(3) or N(7), with pyridine, 2‐methylpyridine, or quinoline donor moieties – and of their CuII complexes are reported, together with single‐crystal structural analyses and solution studies (electrochemistry, electronic and EPR spectroscopy). Depending on the ligand geometry and on the co‐ligands (solvent or counter anion), there are various structural forms (pseudo‐Jahn–Teller elongation along all three molecular axes), and the structural data are correlated with the spectroscopic and electrochemical parameters. 相似文献
38.
Two vanadyl salen complexes having peripheral styryl substituents have been reacted with 1-methyl-3-(3-mercaptopropyl)-imidazolium chloride using azoisobutyronitrile as radical initiator. The resulting compounds contain at the same time a vanadyl salen complex and one imidazolium cation. In agreement with the expectations in view of their structure, these compounds were insoluble in conventional organic solvents, but completely miscible in imidazolium ionic liquids. These vanadyl salen complexes bonded to an imidazolium cation are highly active and reusable catalysts for the cyanosilylation of aldehydes. Moderate enantiomeric excesses were obtained using the chiral version of this complex. 相似文献
39.
A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results. 相似文献
40.
Alberto Avenoza Jesús H Busto Carlos Cativiela Francisco Corzana Jesús M Peregrina María M Zurbano 《The Journal of organic chemistry》2002,67(2):598-601
A short and efficient asymmetric synthesis of the (6R,7S)-7-tert-butoxycarbonylamino-2-ketocarbacepham is described. The key step involves the hetero Diels-Alder reaction of the benzylimine derived from the enantiomer of Garner's aldehyde with Danishefsky's diene. 相似文献