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41.
Capillary electrophoretic analysis of individual submicrometer size particles has been previously done using custom-built instruments. Despite that these instruments provide an excellent signal-to-noise ratio for individual particle detection, they are not capable of performing automated analyses of particles. Here we report the use of a commercial Beckman P/ACE MDQ capillary electrophoresis (CE) instrument with on-column laser-induced fluorescence (LIF) detection for the automated analysis of individual particles. The CE instrument was modified with an external I/O board that allowed for faster data acquisition rates (e.g. 100 Hz) than those available with the standard instrument settings (e.g. 4 Hz). A series of eight hydrodynamic injections expected to contain 32 +/- 6 particles, each followed by an electrophoretic separation at -300 V cm(-1) with data acquired at 100 Hz, showed 28 +/- 5 peaks corresponding to 31.9 particles as predicted by the statistical overlap theory. In contrast, a similar series of hydrodynamic injections followed by data acquisition at 4 Hz revealed only 8 +/- 3 peaks suggesting that the modified system is needed for individual particle analysis. Comparison of electropherograms obtained at both data acquisition rates also indicate: (i) similar migration time ranges; (ii) lower variation in the fluorescence intensity of individual peaks for 100 Hz; and (iii) a better signal-to-noise ratio for 4 Hz raw data. S/N improved for 100 Hz when data were smoothed with a binomial filter but did not reach the S/N values previously reported for post-column LIF detection. The proof-of-principle of automated analysis of individual particles using a commercially available CE system described here opens exciting possibilities for those interested in the study and analyses of organelles, liposomes, and nanoparticles.  相似文献   
42.
A review is presented of the calculation of photoionization spectra, particularly in the spectral range where electron autoionization of diatomic molecules takes place. In addition to some interesting results obtained over years that compare favourably with experiment, the emphasis here is put on the relation between the methods developed for the calculation of observables associated with the continuum energy spectrum of the electrons and the Alchemy system of programs. This system of programs serves as a basis for initial and intermediate calculations. The examples presented show that diatomic molecules not only in gas phase but also oriented in space or physisorbed at surfaces may be studied readily.  相似文献   
43.
In this paper, a number of theoretical and algorithmic issues concerning the solution of parametric nonconvex programs are presented. In particular, the need for defining a suitable overestimating subproblem is discussed in detail. The multiparametric case is also addressed, and a branch and bound (B&B) algorithm for the solution of parametric nonconvex programs is proposed.  相似文献   
44.
Aluminium alloy ultra-high vaccum system provides a convenient tool to access the UHV region due to short pump down time, its reduced weight, low cost etc. For UHV systems, aluminium and its alloys are preferred materials to stainless steel. A cylincrical discharge chamber of SS 304 with various ports on it, evacuated by turbomolecular pumping unit is used in the experimental system. A hollow cathode de glow discharge in argon for different time durations is used to treat chemically cleaned ASA 6063 aluminium alloy samples, keeping all other parameters constant. The scanning electron microscope (SEM) is used to examine processed surfaces and to study topographical features. The energy dispersive microanalysis by X-rays (EDX) is used to determine the elemental composition of the samples. The results indicate the physical sputtering taking place in Ar GDC. The etched area increases with discharge time duration. The EDX spectrum shows the inconsistency in weight percentage of various elements of Al-alloy.  相似文献   
45.
  • 1. The anions CH3O‐CO and CH3OCO‐CO are both methoxide anion donors. The processes CH3O‐CO → CH3O + CO and CH3OCO—CO → CH3O + 2CO have ΔG values of +8 and ?68 kJ mol?1, respectively, at the CCSD(T)/6‐311++G(2d, 2p)//B3LYP/6‐311++G(2d,2p) level of theory.
  • 2. The reactions CH3OCOCO → CH3OCO + CO (ΔG = ?22 kJ mol?1) and CH3COCH(O)CO2CH3 → CH3COCH(O)OCH3 + CO (ΔG = +19 kJ mol?1) proceed directly from the precursor anions via the transition states (CH3OCO…CO2) and (CH3COCHO…CH3OCO), respectively.
  • 3. Anion CH3COCH(O)CO2CH3 undergoes methoxide anion transfer and loss of two molecules of CO in the reaction sequence CH3COCH(O)CO2CH3 → CH3CH(O)COCO2CH3 → [CH3CHO (CH3OCO‐CO)] → CH3CH(O)OCH3 + 2CO (ΔG = +9 kJ mol?1). The hydride ion transfer in the first step is a key feature of the reaction sequence.
Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
46.
The present study fabricates biogenic zinc oxide nanoparticles (ZnO NPs) with the aqueous leaf extract of Annona muricata (Am) plant collected from semi-evergreen forests of Odisha, India. The synthesized Am-ZnO NPs were physicochemically characterized. The ultraviolet/visible spectrum showed the maximum optical absorbance of Am-ZnO NPs at 355 nm. High-resolution transmission electron microscopy analysis presented the nearly spherical shape of Am-ZnO NPs with an average particle size of 80 nm. The net surface charge and hydrodynamic size of Am-ZnO NPs were measured to be ~?2.59 mV and ~417 nm, respectively. Am-ZnO NPs were found to be biocompatible and hemocompatible nature. Furthermore, Am-ZnO NPs displayed strong anticancer effects on both 2D and 3D tumor models. We observed a dose-dependent toxicity on both A549 and MOLT4 cells and observed a size reduction in the A549 tumor spheroids. Subsequently, we observed a depolarization in mitochondrial membrane potential of Am-ZnO NP–treated cancer cells leading to the apoptosis induction in cancer cells.  相似文献   
47.
Biomolecular homochirality, the origin of which is still a puzzle, has challenged scientists to design chemical systems that provide chiral molecules through absolute asymmetric synthesis and to amplify a small stereochemical bias in such systems. The photoresolution of the enantiomers of helical-shaped, sterically overcrowded alkene 1 with circularly polarized light and the transduction of the stereochemical information by triggering the helical arrangement of a large collection of achiral molecules in a twisted nematic liquid crystalline phase (2) are examples of control and amplification of chirality.  相似文献   
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Sensitive and rapid monitoring of cholesterol levels in the human body are highly desirable as they are directly related to the diagnosis of cardiovascular diseases. By using the nanoarchitectonic approach, a novel fluorescent conjugated oligofluorene (OFP-CD) functionalized with β-cyclodextrin (β-CD) was assembled for “Turn-On” fluorescence sensing of cholesterol. The appended β-CD units in OFP-CD enabled the forming of host-guest complexes with dabsyl chloride moieties in water, resulting in fluorescence quenching of the oligofluorene through intermolecular energy transfer. In the presence of cholesterol molecules, a more favorable host-guest complex with stoichiometry 1 cholesterol: 2 β-CD units was formed, replacing dabsyl chloride in β-CD’s cavities. This process resulted in fluorescence recovery of OFP-CD, owing to disruption of energy transfer. The potential of this nanoarchitectonic system for “Turn-On” sensing of cholesterol was extensively studied by fluorescence spectroscopy. The high selectivity of the sensor for cholesterol was demonstrated using biologically relevant interfering compounds, such as carbohydrates, amino acids, metal ions, and anions. The detection limit (LOD value) was as low as 68 nM, affirming the high sensitivity of the current system.  相似文献   
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