Some concepts of convergence used in mathematical chemistry are briefly reviewed: number convergence, uniform and non-uniform function convergence, convergence in norm and binary product, operator convergence, computer convergence, etc. Some properties of the abstract Hilbert space and some of its realizations in mathematical chemistry are discussed. Finally, it is pointed out that the scattering wave functions of importance in the theory of chemical reactions are limit points of theL2Hilbert space — not in the norm, but in the sense of a non-uniform point-by-point convergence, which is of essential value in practical applications. 相似文献
We report a novel, fast, and automatic SPME-based method capable of extracting a small molecule-drug conjugate (SMDC) from biological matrices. Our method relies on the extraction of the drug conjugate followed by direct elution into an electrospray mass spectrometer (ESI-MS) source for qualitative and quantitative analysis. We designed a tool for extracting the targeting head of a recently synthesized SMDC, which includes acetazolamide (AAZ) as high-affinity ligand specific to carbonic anhydrase IX. Specificity of the extraction was achieved through systematic optimization. The design of the extraction tool is based on noncovalent and reversible interaction between AAZ and CAII that is immobilized on the SPME extraction phase. Using this approach, we showed a 330% rise in extracted AAZ signal intensity compared to a control, which was performed in the absence of CAII. A linear dynamic range from 1.2 to 25 μg/ml was found. The limits of detection (LOD) of extracted AAZ from phosphate-buffered saline (PBS) and human plasma were 0.4 and 1.2 μg/ml, respectively. This with a relative standard deviation of less than 14% (n = 40) covers the therapeutic range.
The micellization behavior of an anionic gemini surfactant, GA with nonionic surfactants C12E8 and C12E5 in presence of 0.1 M NaCl at 298 K temperature, has been studied tensiometrically in pure and mixed states, and the related
physicochemical parameters (cmc, γcmc, pC20, Γmax, and Amin) have been evaluated. Tensiometric profile (γ vs log [surfactant]), for conventional surfactants, generally consists of a single point of intersection; a gradually decreasing
line (normally linear, or with slight curvature) ultimately saturates in γ at a particular [surfactant], corresponding to complete monolayer saturation. The gemini, in this report, led to two unequivocal
breaks in the tensiometric isotherm. An attempt to the interpretation of the two breaks from molecular point of view is provided,
depending solely on the chemical structure of the surfactant. The gemini, even in mixed state with the conventional nonionic
surfactants C12E5 and C12E8, manifested the dual breaks; of course, the dominance of the feature decreases with increasing mole fraction of the nonionics
in the mixture. Theories of Clint, Rosen, Rubingh, Motomura, Georgiev, Maeda, and Nagarajan have been used to determine the
interaction between surfactants at the interface and micellar state of aggregation, the composition of the aggregates, the
theoretical cmc in pure and mixed states, and the structural parameters according to Tanford and Israelachvili. Several thermodynamic
parameters have also been predicted from those theories. 相似文献
[Figure: see text]. A quantum chemical study has been performed to assess changes in aromaticity along the T1 state Z/E-isomerization pathways of annulenyl-substituted olefins. It is argued that the point on the T1 energy surface with highest substituent aromaticity corresponds to the minimum. According to Baird (J. Am. Chem. Soc. 1972, 94, 4941), aromaticity and antiaromaticity are interchanged when going from S0 to T1. Thus, olefins with S0 aromatic substituents (set A olefins) will be partially antiaromatic in T1 and vice versa for olefins with S0 antiaromatic substituents (set B olefins). Twist of the C=C bond to a structure with a perpendicular orientation of the 2p(C) orbitals (3p*) in T1 should lead to regaining substituent aromaticity in set A and loss of aromaticity in set B olefins. This hypothesis is verified through quantum chemical calculations of T1 energies, geometries (bond lengths and harmonic oscillator measure of aromaticity), spin densities, and nucleus independent chemical shifts whose differences along the T1 PES display zigzag dependencies on the number of -electrons in the annulenyl substituent of the olefin. Aromaticity changes are reflected in the profiles of the T1 potential energy surfaces (T1 PESs) for Z/E-isomerizations because olefins in set A have minima at 3p* whereas those in set B have maxima at such structures. The proper combination (fusion) of the substituents of set A and B olefins could allow for design of novel optical switch compounds that isomerize adiabatically with high isomerization quantum yields. 相似文献
Fine particles were modified with a thin film of SnO2 by using a barrel sputtering system that is a dry process. The conditions for the preparation of SnO2 were studied by reactive sputtering onto a glass plate substrate. The optimal conditions for the preparation of tetragonal
SnO2 were identified as 60% partial oxygen pressure and 1.0 Pa total gas pressure with the substrate at room temperature. Under
the optimized conditions, the surfaces of Al flake particles were modified with a thin film of SnO2. XRD and SEM/EDS analysis of the prepared samples showed that the Al particle surfaces were uniformly modified by a thin
film of SnO2 in all cases. The film thicknesses were 80, 130, and 180 nm at RF outputs of 195, 350, and 490 W. These measured thicknesses
coincided with the values estimated from the interference colors of the samples. 相似文献
Chromatographia - Ausgehend von den thermodynamischen Grundlagen wird die Siedepunktsabhängigkeit der Retentionszeiten diskutiert. Über eine Formel vonKlages, nach der sich das Quadrat... 相似文献
The energy of a disubstituted molecule has often been approximated by simple electrostatic formulas that represent the substituents as poles or dipoles. Herein, we test this approach on a new model system that is more direct and more efficient than testing on acid-base properties. The energies of 27 1,4-derivatives of bicyclo[2.2.2]octane were calculated within the framework of the density functional theory at the B3LYP/6-311+G(d,p) level; interaction of the two substituents was evaluated in terms of isodesmic homodesmotic reactions. This interaction energy, checked previously on some experimental gas-phase acidities, was considered to be accurate and served as reference to test the electrostatic approximation. This approximation works well in the qualitative sense as far as the sign and the order of magnitude are concerned: beginning with the strongest interaction between two poles, a weaker interaction between pole and dipole, and the weakest between two dipoles. However, all the electrostatic calculations yield energies that are too small, particularly for weak interaction, and this fundamental defect is not remedied by some possible improvements. In particular, variation of the effective permittivity would require a physically impossible value less than unity. The explanation must lie in a more complex distribution of electron density than anticipated in the electrostatic model. It also follows that possible conclusions about the transmission of substituent effects "through space" have little validity. 相似文献