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51.
Liu L John VT McPherson G Maskos K Bose A 《Langmuir : the ACS journal of surfaces and colloids》2005,21(9):3795-3801
A viscous reverse hexagonal surfactant mesophase containing bis(2-ethylhexyl) sodium sulfosuccinate (AOT) and alpha-phosphatidylcholine (lecithin), with comparable volume fractions of isooctane and water, was characterized by Fourier transform (31)P and (1)H NMR spectroscopy. Shear alignment was reflected through both (31)P NMR and (1)H NMR spectra. A complicated (31)P spectrum was observed as a result of superposition of chemical shifts according to the distribution of crystalline domains prior to shear. The initially disordered samples with polydomain structures become macroscopically aligned after Couette shear. (31)P NMR chemical shift anisotropy characteristics are used to elucidate orientation of the hexagonal phase. Interestingly, (1)H NMR spectra exhibit spectral changes upon shear alignment closely corresponding with that of (31)P NMR spectra. These observations complement the findings of mesophase alignment obtained using SANS and imply that (31)P and (1)H NMR spectroscopy can be used as probes to define microstructure and monitor orientation changes in this binary surfactant system. This is especially beneficial if these mesophases are used as templates for materials synthesis. 相似文献
52.
Brett Ammundsen Gary R. Burns Ali Amran Stig E. Friberg 《Journal of Sol-Gel Science and Technology》1995,4(1):23-29
The effects of thermal treatment on composite materials prepared by the gelation of sols comprising large concentrations of metal oxide precursor salts have been investigated, in order to determine the compositional and thermal requirements for forming spinel magnesium manganates in such systems. The preparative technique has been found to give rise to derived gel materials in which the metal oxide phase, in the form of regular spherical particles, is dispersed throughout a continuous silica matrix. Silica-supported mixed magnesium and manganese spinel oxide phases were obtained for systems comprising at least 30 wt% metal nitrate after heating to temperatures between 700 and 850°C, but not without concomitant formation of Mn2O3 and modification of the silica network by magnesium. 相似文献
53.
Gary W Caldwell John A Masucci Mary Evangelisto Robert White 《Journal of chromatography. A》1998,800(2):1071-169
Chromatographic retention factors (k′) of a series of eight β-adrenoceptor antagonist compounds (β-adrenolytic drugs) were determined employing an immobilized artificial membrane column (IAM.PC.DD). The influence of mobile phase pH, ionic strength, and organic modifier composition was studied in order to examine column performance. After the IAM.PC.DD columns were exposed to approximately 7000 column volumes of a 0.01 M PBS mobile phase, five out of six columns tested showed significant peak broadening and decreased k′ values indicative of premature column failure. The data suggested that the immobilized phospholipids stationary phase was removed by the 0.01 M PBS mobile phase. The β-adrenolytic drug's log k′IAM values obtained with an IAM.PC.DD column were compared to an esterIAM.PC.MG column for predicting drug membrane interactions. For the linear regression analysis between log k′IAM and the logarithm of the n-octanol–water partition coefficients (rIAM.PC.DD=0.8710 vs. rIAM.PC.MG=0.9538), the C18 HPLC retention factors (rIAM.PC.DD=0.8408 vs. rIAM.PC.MG=0.9380), the liposome partition coefficients (rIAM.PC.DD=0.8887 vs. rIAM.PC.MG=0.9187), and various pharmacokinetic parameters, significantly better correlations were obtained with the esterIAM.PC.MG column than the IAM.PC.DD column. 相似文献
54.
Kritsana Jitmanee Jaroon Jakmunee Somchai Lapanantnoppakhun Sunanta Wangkarn Norio Teshima Tadao Sakai Gary D. Christian Kate Grudpan 《Microchemical Journal》2007,86(2):195-203
Derivative techniques for analytical signal processing are useful for solving some noise and signal resolution problems in various fields of study such as titrimetry, spectrophotometry, chromatography and electrochemistry. The broad use of these techniques, however, is often limited by costly inflexible built-in software packages in commercial analytical instruments. We propose here the application of commercial simple software packages such as Microsoft® Excel and Microcal Origin for signal smoothing and fitting, and for obtaining derivative analytical signals in batch and flow-based analyses, including potentiometric titration, spectrophotometry, chromatography, voltammetry and sequential injection analysis (SIA). The worldwide (especially Excel) software packages are easy-to-use for less experienced users and have also capabilities for advanced users, and therefore employing such packages can result in expansion of useful derivative techniques. We demonstrate application of the available package-aided derivative capabilities for enhancing some chemical analyses, including potentiometric acid–base titration, Bradford assay of protein, chromatographic separation of ajmaline and reserpine and anodic stripping voltammetry of copper. The derivative signals from smoothed and fitted curves offer better accuracy and precision, even for non-resolving peaks and tailing peaks. In some cases, the optimization of experimental conditions is not further required, which can lead to fast method development. 相似文献
55.
Jiann-Kuan Luo Andrew S. Zektzer Raymond N. Castle Ronald C. Crouch John P. Shockcor Gary E. Martin 《Journal of heterocyclic chemistry》1993,30(2):453-460
Two novel heterocyclic ring systems, namely, [1]benzothieno[2,3-c]naphtho[1,2-f]quinoline and [1]benzothieno[2,3-c]naphtho[2,1-g]quinoline have been synthesized and characterized by inverse detected two-dimensional nmr methods. Unequivocal total assignments of the proton and carbon nmr spectra were made through the concerted utilization of HMQC (Heteronuclear Multiple Quantum Correlation) and a combination of HMBC (Heteronuclear Multiple Bond Correlation) and HMQC-TOCSY (HMQC with proton TOtal Correlation Spectroscopy). 相似文献
56.
M. J. Musmar M. Robert Willcott Gary E. Martin Robert T. Gampe Masatomo Iwao Milton L. Lee Ralph E. Hurd Leroy F. Johnson Raymond N. Castle 《Journal of heterocyclic chemistry》1983,20(6):1661-1669
Development of successively higher field nmr spectrometers has facilitated the study of increasingly more complex molecules, although smaller molecules such as phenanthro[3,4-b]thiophene still offer very substantial assignment problems because of the highly congested nature of their 1H- and 13C-nmr spectra. Assignments of such spectra, if they are to be unequivocal, frequently require the utilization of two-dimensional nmr spectroscopic techniques. Total assignments of the 1H- and 13C-nmr spectra of phenanthro[3,4-b]thiophene are reported. Assignments were based on a conventional high resolution 500 MHz 1H-nmr spectrum, autocorrelated two-dimensional 1H-nmr spectra (COSY), two-dimensional 1H-13C chemical shift correlation spectra and a modified version of autocorrelated 13C-13C double quantum coherence two-dimensional nmr spectroscopy. From NOE measurements, a separation of 1.99 Å between H1 and H11 was computed, suggesting that phenanthro[3,4-b]thiophene has a pronounced helical conformation in solution. 相似文献
57.
The axially chiral bicyclic thioketones 11 and 15 were prepared and investigated for suitability as chiroptical triggers in a liquid crystal optical switch. Irradiation of partially resolved 15 with unpolarized light leads to its conversion to the racemic form (photoracemization). However, irradiation of racemic thioketones 11 and 15 with circularly polarized light does not lead to detectable photoresolution. The lack of photoresolution was traced to inefficiency in intramolecular, through-bond triplet energy transfer. These thioketones are not suitable for use as phototriggers. 相似文献
58.
Synthesis, characterization, and stability of Fe-MCM-41 for production of carbon nanotubes by acetylene pyrolysis 总被引:3,自引:0,他引:3
Amama PB Lim S Ciuparu D Yang Y Pfefferle L Haller GL 《The journal of physical chemistry. B》2005,109(7):2645-2656
Fe-substituted MCM-41 molecular sieves with ca. 1, 2, and 3 wt % Fe were synthesized hydrothermally using different sources of colloidal silica (HiSil and Cab-O-Sil) and characterized by ICP, XRD, N2 physisorption, UV-vis, EPR, TPR, and X-ray absorption. Catalysts synthesized from Cab-O-Sil showed higher structural order and stability than those from HiSil. The local environment of Fe in the mesoporous material as studied by UV-vis reveals the dominance of framework Fe in all the as-synthesized Fe-MCM-41 samples. Dislodgement of some Fe species to extraframework location occurs upon calcination, and this effect is more severe for Fe-MCM-41 (2 wt %) and Fe-MCM-41 (3 wt %), as confirmed by EPR and X-ray absorption. These materials have been used as catalytic templates for the production of carbon nanotubes (CNTs) by acetylene pyrolysis at atmospheric pressure. A relationship between the Fe loading in MCM-41 and the carbon species produced during this reaction has been established. Using our optimized conditions for this system, Fe-MCM-41 with ca. 2 wt % Fe showed the best results with particularly high selectivity for single-wall carbon nanotube (SWNT) production. This catalyst was selective for carbon nanotubes with a low amount of amorphous carbon for a narrow range of temperatures from 1073 to 1123 K. To account for the different selectivity of these catalysts for CNTs production, the local environment and chemical state of Fe in the used catalyst was further probed by X-band EPR. 相似文献
59.
Hamilton BH Cardon TB Lorigan GA Ziegler CJ 《Dalton transactions (Cambridge, England : 2003)》2005,(17):2941-2944
Metal-organic frameworks based on the Pb[B(Im)(4)](+) unit form layered structures analogous to those observed in clays and double layered hydroxide minerals. These layers can act as scaffolds for the organization of anionic organic guests. In this report, we use this scaffold to assemble TEMPO and PROXYL carboxylates in the interlayer spacings of Pb[B(Im)(4)](4-carboxy-TEMPO) 1 and Pb[B(Im)(4)](3-carboxy-PROXYL)(H(2)O)2, respectively. The resultant materials are paramagnetic, and the organization of the radical units differs between the two compounds. This results in changes in electronic structure of the radical unit, as observed by EPR spectroscopy. 相似文献
60.
R. Dustan Myrex Gary M. Gray Young-Jin Wright Prakash C. Bharara Keith E. Branham 《European Polymer Journal》2003,39(6):1105-1115
Polymeric phosphonate esters are an interesting class of organophosphorus polymers because both the polymer backbone and phosphorus substituents can be modified. These polymers have been prepared by ring-opening polymerizations of cyclic phosphites, stoichiometric polycondensations of dimethyl phosphonate with diols in conjunction with diazomethane treatment and by transesterification of polyphosphonate oligomers. Our initial attempts to prepare high molecular weight polymeric phosphonate esters by the transesterification methods were unsuccessful. Results indicate that the reactions of dimethyl phosphonate with diols to form polyphosphonate oligomers with only methyl phosphonate end groups are plagued by a serious side reaction that forms phosphonic acid end groups. These end groups do not participate in the transesterification reaction and limit the molecular weights of the polymers that can be obtained. The phosphonic acid end groups can be converted into reactive methyl phosphonate end groups by treatment with diazomethane, however diazomethane is explosive and the polymerization is slow. An alternative route for the production of high molecular weight polymers is the transesterification of the 1,12-bis(methyl phosphonato)dodecane, formed by the reaction of excess dimethyl phosphonate and 1,12-dodecanediol, with a Na2CO3 promoter. This allows polymers with molecular weights of up to 4.5×104 to be prepared, and no phosphonic acid end groups are observed in these polymers. Thermal analyses of the poly(1,12-dodecamethylene phosphonate) have shown that this polymer has reasonable thermal stability (onset of thermal decomposition at 273 °C). This polymer also undergoes a cold crystallization process at 15 °C similar to that which has been observed in some polyesters, polyamides and elastomers. 相似文献