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991.
This review summarizes the contributions of a number of groups working in the rapidly growing area of monolithic columns for capillary electrochromatography (CEC), with a focus on those prepared from synthetic polymers. Monoliths have quickly become a well-established stationary phase format in the field of CEC. The simplicity of their in situ preparation method as well as the good control over their porous properties and surface chemistries make the monolithic separation media an attractive alternative to capillary columns packed with particulate materials. A wide variety of approaches as well as materials used for the preparation of the monolithic stationary phases are detailed. Their excellent chromatographic performance is demonstrated by numerous separations of different analytes. 相似文献
992.
Austria C Zhang J Valle H Zhang Q Chew E Nguyen DT Gu JY Feng P Bu X 《Inorganic chemistry》2007,46(16):6283-6290
Whereas open-framework materials have been made in a variety of chemical compositions, few are known in which 3-connected SO3(2)- anions serve as basic building units. Here, we report four new metal-sulfite polymeric structures, (ZnSO3)Py (1, py = pyridine), (ZnSO3)2(2,2'-bipy)H2O (2, 2,2'-bipy = 2,2'-bipyridine), (ZnSO3)2(TMDPy) (3, TMDPy = 4,4'-trimethylenedipyridine), and (MnSO3)2en (4, en = ethylenediamine) that have been synthesized hydrothermally and structurally characterized. In these compounds, low-dimensional 1D and 2D inorganic subunits are assembled into higher 2D or 3D covalent frameworks by organic ligands. In addition to the structure-directing effect of organic ligands, the flexible coordination chemistry of Zn2+ and SO3(2)- also contributes to the observed structural diversity. In compounds 1-3, Zn2+ sites alternate with trigonal pyramidal SO3(2)- anions to form three types of [ZnSO3]n chains, whereas in compound 4, a 2D-corrugated [MnSO3]n layer is present. Compound 1 features a rail-like chain with pendant pyridine rings. The pi-pi interaction between 2,2'-bipy ligands is found between adjacent chains in compound 2, resulting in 2D sheets that are further stacked through interlayer hydrogen bonds. Compound 3 exhibits a very interesting inorganic [(ZnSO3)2]n chain constructed from two chairlike subunits, and such chains are bridged by TMDPy ligands into a 2D sheet. In compound 4, side-by-side helical chains permeate through 2D-corrugated [MnSO3]n layers, which are pillared by neutral ethylenediamine molecules into a 3D framework that can be topologically represented as a (3,6)-connected net. The results presented here illustrate the rich structural chemistry of metal-sulfites and the potential of sulfite anions as a unique structural building block for the construction of novel open-framework materials, in particular, those containing polymeric inorganic subunits that may have interesting physical properties such as low-dimensional magnetism or electronic properties. 相似文献
993.
Emily R. Schenk Frederic Nau Christopher J. Thompson Yuk‐Ching Tse‐Dinh Francisco Fernandez‐Lima 《Journal of mass spectrometry : JMS》2015,50(1):88-94
Bacterial resistance to antibiotics has become an increasing threat, requiring not only the development of new targets in drug discovery, but more importantly, a better understanding of cellular response. In the current study, three closely related Escherichia coli strains, a wild type (MG1655) and an isogenic pair derived from the wild type (DPB635 and DPB636) are studied following exposure to sub lethal concentrations of antibiotic (norfloxacin) over time. In particular, genotype similarities between the three strains were assessed based on the lipid regulation response (e.g. presence/absence and up/down regulation). Lipid identification was performed using direct surface probe analysis (matrix‐assisted laser desorption/ionization, MALDI), coupled to high‐resolution mass spectrometry (Fourier transform ion cyclotron resonance mass spectrometry, FT‐ICR MS) followed by statistical analysis of variability and reproducibility across batches using internal standards. Inspection of the lipid profile showed that for the MG1655, DPB635 and DPB636 E. coli strains, a similar distribution of the altered lipids was observed after exposure to norfloxacin antibiotic (e.g. fatty acids and glycerol phospholipids are up and down regulated, respectively). Additionally, variations in the lipid distribution resemble the extent to which each strain can combat the antibiotic exposure. That is, the topA66 topoisomerase I mutation of DPB636 translates into diminished response related to antibiotic sensitivity when compared to MG1655 and the DPB635 strains. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
994.
Taketoshi Fujimoto Nariyoshi Kawabata Junji Furukawa 《Journal of polymer science. Part A, Polymer chemistry》1968,6(5):1209-1215
Infrared spectra of reaction mixtures of methyl methacrylate or methacrylonitrile with an equimolar amount of organometallic compounds were investigated in relation to the stereoregulating ability of the catalysts in polymerization. It was found that the carbonyl or nitrile stretching frequency correlated with the stereoregularity of polymers prepared with the corresponding catalysts; i.e., the higher the frequency, the higher the isotacticity. From these results a mechanism of isotactic polymer formation was proposed, in which catalyst counterion was located near the carbonyl group in polymer terminal and that of monomer to be reacted, and consequently the isotactic polymerization is facilitated. 相似文献
995.
Cristiano Soleo Funari Renato Lajarim Carneiro Manish M. Khandagale Alberto José Cavalheiro Emily F. Hilder 《Journal of separation science》2015,38(9):1458-1465
A considerable amount of chemical waste from liquid chromatography analysis is generated worldwide. Acetonitrile is the most employed solvent in liquid chromatography analyses since it exhibits favorable physicochemical properties for separation and detection, but it is an unwelcome solvent from an environmental point of view. Acetone might be a much greener alternative to replace acetonitrile in reversed‐phase liquid chromatography, since both share similar physicochemical properties, but its applicability with ultraviolet absorbance‐based detectors is limited. In this work, a reference method using acetonitrile and high‐performance liquid chromatography coupled to an ultraviolet photodiode array detector coupled to a corona charged aerosol detector system was developed to fingerprint a complex sample. The possibility of effectively substituting acetonitrile with acetone was investigated. Design of experiments was adopted to maximize the number of peaks acquired in both fingerprint developments. The methods with acetonitrile or acetone were successfully optimized and proved to be statistically similar when only the number of peaks or peak capacity was taken into consideration. However, the superiority of the latter was evidenced when parameters of separation and those related to greenness were heuristically combined. A green, comprehensive, time‐ and resource‐saving approach is presented here, which is generic and applicable to other complex matrices. Furthermore, it is in line with environmental legislation and analytical trends. 相似文献
996.
Dr. Aldo Peschiulli Veerle Smout Dr. Thomas E. Storr Dr. Emily A. Mitchell Zdeněk Eliáš Prof. Dr. Wouter Herrebout Dr. Didier Berthelot Dr. Lieven Meerpoel Prof. Dr. Bert U. W. Maes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(31):10378-10387
Transition‐metal‐catalyzed sp3 C? H activation has emerged as a powerful approach to functionalize saturated cyclic amines. Our group recently disclosed a direct catalytic arylation reaction of piperidines at the α position to the nitrogen atom. 1‐(Pyridin‐2‐yl)piperidine could be smoothly α‐arylated if treated with an arylboronic ester in the presence of a catalytic amount of [Ru3(CO)12] and one equivalent of 3‐ethyl‐3‐pentanol. A systematic study on the substrate and reagent scope of this transformation is disclosed in this paper. The effect of substitution on both the piperidine ring and the arylboronic ester has been investigated. Smaller (pyrrolidine) and larger (azepane) saturated ring systems, as well as benzoannulated derivatives, were found to be compatible substrates with the α‐arylation protocol. The successful use of a variety of heteroarylboronic esters as coupling partners further proved the power of this direct functionalization method. Mechanistic studies have allowed for a better understanding of the catalytic cycle of this remarkable transformation featuring an unprecedented direct transmetalation on a RuII? H species. 相似文献
997.
This study investigated the relationship among the magnitude of jaw opening, intrinsic fundamental frequency (F0), and glottal parameters in natural speech. Acoustic, jaw opening, and electroglottographic (EGG) signals were simultaneously recorded. The subjects were 10 healthy men with New Zealand English as their native language. Subjects were asked to repeat a standard nonemphasized sentence in which one of the target vowels (/a/, /e/, /i/, /o/, and /u/) was embedded in various contexts. The glottal parameters F0, open quotient (OQ), and speed quotient (SQ) were measured from the EGG signal. Results of a series of one-way repeated-measures analyses of variance (ANOVA) showed a significant vowel effect on the magnitude of jaw opening [F(4, 24) = 25.512, P < .001], F0 [F(4, 28) = 45.415, P < .001] and speed quotient [F(4, 28) = 5.233, P = .003], but not on the open quotient [F(4, 28) = 0.501, P = .735]. The magnitude of jaw opening was found to be inversely related with F0 (r = -0.624, n = 25, P = .0009). These findings showed that the magnitude of jaw opening was related to F0 and that jaw opening might be a control signal for simulation of long-term F0 variation to achieve a higher degree of naturalness in artificial voice. 相似文献
998.
Nature's repertoire of biosynthetic transformations has recently been recognized to include the Diels-Alder cycloaddition reaction. Evidence now exists that there are enzymes that mediate the Diels-Alder reaction in secondary metabolic biosynthetic pathways. 2002 marked the 100th anniversary of Alder's birth and 75 years since the discovery of the Diels-Alder reaction. It would appear that living systems discovered and made use of this ubiquitously useful ring-forming reaction eons ago for the construction of complex natural products. In this Review an overview is given of all of the known classes of natural products (polyketides, isoprenoids, phenylpropanoids, alkaloids) that have been speculated to arise by a biological Diels-Alder reaction. 相似文献
999.
1000.
The present study sought to clarify the role of non-simultaneous masking in the binaural masking level difference for maskers that fluctuate in level. In the first experiment the signal was a brief 500-Hz tone, and the masker was a bandpass noise (100-2000 Hz), with the initial and final 200-ms bursts presented at 40-dB spectrum level and the inter-burst gap presented at 20-dB spectrum level. Temporal windows were fitted to thresholds measured for a range of gap durations and signal positions within the gap. In the second experiment, individual differences in out of phase (NoSπ) thresholds were compared for a brief signal in a gapped bandpass masker, a brief signal in a steady bandpass masker, and a long signal in a narrowband (50-Hz-wide) noise masker. The third experiment measured brief tone detection thresholds in forward, simultaneous, and backward masking conditions for a 50- and for a 1900-Hz-wide noise masker centered on the 500-Hz signal frequency. Results are consistent with comparable temporal resolution in the in phase (NoSo) and NoSπ conditions and no effect of temporal resolution on individual observers' ability to utilize binaural cues in narrowband noise. The large masking release observed for a narrowband noise masker may be due to binaural masking release from non-simultaneous, informational masking. 相似文献