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21.
Kirill P. Birin Yulia G. Gorbunova Aslan Yu. Tsivadze 《Magnetic resonance in chemistry : MRC》2010,48(7):505-515
A novel approach for the structural analysis of heteroleptic triple‐decker (porphyrinato)(phthalocyaninato) lanthanides(III) in solutions is developed. The developed approach consists in molecular mechanics (MM+) optimization of the geometry of the complex taking into account the lanthanide‐induced shift (LIS) datasets. LISs of the resonance peaks in 1H NMR spectra of a series of symmetric complexes [An4P]Ln[(15C5)4Pc]Ln[An4P], where An4P2? is 5,10,15,20‐tetrakis(4‐methoxyphenyl)porphyrinato‐dianion, [(15C5)4Pc]2? is 2,3,9,10,16,17,24,25‐tetrakis(15‐crown‐5)phthalocyaninato‐dianion and Ln = La, Ce, Pr, Nd, Sm, Eu, are analyzed. Analysis of LISs showed two sets of protons in the molecule with opposite signs of shift. Two‐nuclei analysis of LISs testifies isostructurality of the whole series of investigated complexes in solution despite contraction of the lanthanide ions. Model‐free separation of contact and dipolar contributions of LISs was performed with one‐nucleus technique and did not show changes in contact and dipolar terms within the investigated series. MM+ optimization of the molecular structure allowed the interpretation of features of LIS for each particular group of protons. Parameterization of MM + ‐optimized model of molecule with values of structure‐dependent dipolar contributions of LIS allows the development of the precise structural model of the triple‐decker complex in solution. This approach allows the determination of the geometry and structure of the sandwich macrocyclic tetrapyrrolic complexes together with conformational analysis of flexible peripheral substituents in solutions. The developed method can be applied with minor modifications for the determination of structural parameters of other types of lanthanides(III) complexes with tetrapyrrolic ligands and also supramolecular systems based on them. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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We describe a platform technology, called metal-assisted and microwave-assisted evaporative crystallization (MA-MAEC), based on the combined use of silver nanoparticles and microwave heating for selective and rapid crystallization of small molecules. In this regard, the crystallization of a model small molecule (glycine) was achieved in several seconds. Glycine crystals grown on silver nanostructures with and without microwave heating were found to be larger than those grown on blank glass slides. The MA-MAEC technique has the potential to selectively grow the desired polymorphs of small molecules "on-demand" in a fraction of the time as compared to the conventional evaporative crystallization. 相似文献
24.
Sema Ekici Pinar IlginSelahattin Yilmaz Nahit AktasNurettin Sahiner 《Applied Surface Science》2011,257(7):2669-2676
We report the preparation and characterization of thiolated-temperature-responsive hyaluronic acid-cysteamine-N-isopropyl acrylamide (HA-CYs-NIPAm) particles and thiolated-magnetic-responsive hyaluronic acid (HA-Fe-CYs) particles. Linear hyaluronic acid (HA) crosslinked with divinyl sulfone as HA particles was prepared using a water-in-oil micro emulsion system which were then oxidized HA-O with NaIO4 to develop aldehyde groups on the particle surface. HA-O hydrogel particles were then reacted with cysteamine (CYs) which interacted with aldehydes on the HA surface to form HA particles with cysteamine (HA-CYs) functionality on the surface. HA-CYs particles were further exposed to radical polymerization with NIPAm to obtain temperature responsive HA-CYs-NIPAm hydrogel particles. To acquire magnetic field responsive HA composites, magnetic iron particles were included in HA to form HA-Fe during HA particle preparation. HA-Fe hydrogel particles were also chemically modified. The prepared HA-CYs-NIPAm demonstrated temperature dependent size variations and phase transition temperature. HA-CYs-NIPAm and HA-Fe-CYs particles can be used as drug delivery vehicles. Sulfamethoxazole (SMZ), an antibacterial drug, was used as a model drug for temperature-induced release studies from these particles. 相似文献
25.
?smail Aslan 《Physics letters. A》2011,375(47):4214-4217
We analyze the discrete nonlinear Schrödinger equation with a saturable nonlinearity through the (G′/G)-expansion method to present some improved results. Three types of analytic solutions with arbitrary parameters are constructed; hyperbolic, trigonometric, and rational which have not been explicitly computed before. 相似文献
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D. Aslan F. Kuralay T. Tanyalsin M. Topraksu 《Accreditation and quality assurance》1999,4(9-10):431-433
Applicability of Hoffman's average of normals (AON) method was evaluated in quality control (QC) for twenty clinical chemistry assays (ALT, Alb, ALP, AMY, AST, T. Bil, inP, Glu, Ca, Cl, T. Chol, Creat, CK, K, LD, T. Prot., Na, TG, BUN, Uric. A.) performed routinely in the Hospital of Medical Faculty of 9 Eylül University. Consecutive Texas Instruments XL-Dacos patient data were accumulated over 10 days. According to the guidelines developed by Cembrowsky et. al. for the implementation of average of patients (AOP) (also known as AON) procedure, the patient population mean, *p, population standard deviation, Sp, the ratio of Sp/Sa (Sa, the analytical standard deviation), and the approximate number of patient results averaged. Np (with Ped=0.50) were determined from the nomogram constructed by Cembrowsky et. al., illustrating the relationship between Np, Sp/Sa, and the probability of detecting a 2Sa shift (Ped) when the probability of false rejection, Pfr, is 0.01. The control limits and the truncation limits were selected as *p±2Sp and *p±2.58×Sp√Np, respectively. The estimated values were assessed for the applicability of AOP procedures in the clinical laboratory. We conclude that the AOP procedure is a valuable tool for instrument monitoring as an adjunct to more costly standard QC procedures and is also an efficient, cost-effective and rapid way of collecting appropriate information on large number of patients. 相似文献
28.
We demonstrate the influence of electrical current on the ability of surface plasmons to amplify fluorescence signatures.
An applied direct current across Silver Island Films (SIFs) of low electrical resistance perturbs the fluorescence enhancement.
For a given applied current, surface plasmons in just-continuous films are sparsely available for fluorophore dipole-coupling
and hence the enhanced fluorescence is gated as a function of the applied current. For thicker, low resistance films, sufficient
charge carriers are now present in the metal that metal-enhanced fluorescence (MEF) is perturbed to a lesser extent, induced
surface plasmons readily formed on the surface by the close-proximity dipole. 相似文献
29.