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11.
Vukomanović M Skapin SD Poljanšek I Zagar E Kralj B Ignjatović N Uskoković D 《Colloids and surfaces. B, Biointerfaces》2011,82(2):414-421
The novel concept of a simultaneous, controlled release of a drug and a prodrug with different physico-chemical properties was applied in order to prolong the release period of antibiotics and estimate their high local concentrations, which are the necessary preconditions for the treatment of some chronic infection diseases. For this purpose poly(D,L-lactide-co-glycolide)/hydroxyapatite (PLGA/HAp) core-shell nanostructures were used as the carrier of clindamycin-base, as a drug, and clindamycin-2-phosphate, as a prodrug model. As a result, a two-step release was observed: the controlled release of the more soluble phosphate form and the sustained release of the less-soluble base form of clindamycin, resulting in a high overall concentration of the released drug during the period of 30 days in vitro. The HAp phase within the PLGA core-shells, applied as a drug carrier, delayed the process of the degradation of the polymer; however, the presence of the drug affected the process of degradation and this influence was the dominant factor in the control over the degradation of the polymer phase of PLGA/HAp and the consequent kinetics of the drug release. 相似文献
12.
Ketoprofen (KP) is a nonsteroidal anti-inflammatory drug, which during UV irradiation rapidly transforms into benzophenone derivatives. Such transformation products may occur after topical application of KP, which is then exposed to sunlight resulting in a photo-allergic reaction. These reactions are mediated by the benzophenone moiety independently of the amount of allergen. The same reactions will also occur during wastewater or drinking water treatment albeit their effect in the aqueous environment is yet to be ascertained. In addition, only a few such transformation products have been recognised. To enable the detection and structural elucidation of the widest range of KP transformation products, this study applies complementary chromatographic and mass spectrometric techniques including gas chromatography coupled to single quadrupole or ion trap mass spectrometry and liquid chromatography hyphenated with quadrupole-time-of-flight mass spectrometry. Based on structural information gained in tandem and multiple MS experiments, and on highly accurate molecular mass measurements, chemical structures of 22 transformation products are proposed and used to construct an overall breakdown pathway. Among the identified transformation products all but two compounds retained the benzophenone moiety--a result, which raises important issues concerning the possible toxic synergistic effects of KP and its transformation products. These findings trigger further research into water treatment technologies that would limit their entrance into environmental or drinking waters. 相似文献
13.
Gröger K Baretić D Piantanida I Marjanović M Kralj M Grabar M Tomić S Schmuck C 《Organic & biomolecular chemistry》2011,9(1):198-209
Two novel guanidiniocarbonyl pyrrole-pyrene conjugates 3 and 4 as spectroscopic probes for ds-polynucleotides were synthesized and their interaction with different ds-DNAs/RNAs studied. Compared to a previously reported first set of conjugates (1 and 2) the significant extension and increased rigidity of the central part of the structure resulted in a switch of DNA binding mode from intercalative (previously studied derivatives 1 and 2 with a nonbinding and flexible linker) to minor groove binding of the two novel guanidiniocarbonyl-pyrrole-pyrene conjugates 3 and 4. These two compounds interact strongly with ds-DNAs, but only weakly with ds-RNA. The newly incorporated heterocyclic moieties within the central part of the structure of 3 and 4 were able to control by steric and hydrogen-bonding effects the alignment of the molecules within various, structurally different forms of DNA minor grooves, whereby even small differences in the position of the attached pyrene within the groove were reflected in different fluorimetric responses. In addition, 3 and 4 revealed intriguing in vitro selectivity among various human tumour cell lines. 相似文献
14.
The losses of CO, hydrogen and CO, OH and HNOH radicals from the benzophenone oxime molecular ion have been studied by means of deuterium labelled compounds. Hydrogen scrambling and/or exchange and rearrangement reactions of interest, taking place prior to fragmentation, were observed. 相似文献
15.
We present details of calculations of the core structure of a screw dislocation in a smectic A liquid crystal, using the phenomenological Landau-de Gennes free energy functional. The order parameter frustration created by topological constraints far from the dislocation core is resolved in one of three qualitatively different ways. The three types of dislocation core solution are the DT (double twist), CL (classical), and BP (broken polar symmetry) solutions, respectively. The stability requirements for these structures are discussed, as a function of temperature, smectic elastic properties, and coupling between smectic and nematic order. The effect of possible inhomogeneity between left- and right-handed conformers is also examined. 相似文献
16.
Relative stabilities (ΔGc) of ammonium-bound monomers and dimers of anomeric β-
-pentofuranosyl 1α- and 1β-azide derivates are determinate using the kinetic method by measuring relative rates of competitive collision-induced dissociations of dimeric [ANH4B]+ and trimeric [A2NH4B]+ or [ANH4B2]+ cluster ions. Comparison between calculated ammonium affinities (AAs) and relative stabilities (ΔGc) of ammonium-bound monomers shows qualitative correlations between both thermochemical quantities, but in two examples the activation barrier differences of competitive fragmentation channels cause a large disparity between both thermochemical data. Therefore, the most stable ammonium-bound monomers of the anomeric lα- and lβ-2,3,5-tri-O-benzyl-β-
-arabino-pento-furanosyl azides possess the lowest ammonium affinities and the highest relative stabilities. Two different relative stabilities measured for the same ammonium-bound homo- or hetero-dimers indicate dissimilar activated barriers of trimers transition states for dimer formations. The activated barriers of trimers depend on the relative stabilities of ammonium-bound monomer within the trimeric cluster ions. 相似文献
17.
Starcević K Karminski-Zamola G Piantanida I Zinić M Suman L Kralj M 《Journal of the American Chemical Society》2005,127(4):1074-1075
Spectroscopic titrations and thermal denaturation experiments show that "acyclic" analogue 1 does not bind to ds-DNA, but under same conditions "cyclic" 2 strongly interacts with ds-DNA and ds-RNA by intercalation into the double helix. Besides, 2 is significantly more effective in inhibition of the tumor cell growth in vitro than 1. We have shown that it is possible to efficiently and irreversibly convert "DNA inactive" compound 1 into "DNA active" compound 2 by light irradiation of the aqueous solutions of the former. This strategy offers a new and attractive approach to photoinduced anticancer therapy. 相似文献
18.
D. Krstić M. Çolović M. B. Kralj P. Trebše K. Krinulović V. Vasić 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2008,82(4):663-668
The influence of malathion and its four main degradation products found in irradiated solutions (malaoxon, isomalathion, diethyl
maleate and O,O-dimethyl phosphate) on acetylcholinesterase (AChE) of free and immobilized bovine erythrocytes was investigated.
The concentration-dependent responses to malathion and related organophosphates, malaoxon and isomalathion, of both AChE bioassays
used were obtained. The IC
50 values for free and immobilized AChE (3.7 ± 0.2) × 10−4 M/(1.6 ± 0.1) × 10−4, (2.4 ± 0.3) × 10−6/(3.4 ± 0.1) × 10−6 M, and (3.2 ± 0.3) × 10−6 M/(2.7 ± 0.2) × 10−6 M were obtained in the presence of malathion, malaoxon and isomalathion, respectively. However, diethyl maleate inhibited
AChE activity at concentrations ≥ 10 mM, while O,O-dimethyl phosphate did not noticeably affect enzyme activity at all investigated
concentrations. The relation between the structure of the compounds and their ability to inhibit enzyme activity was discussed.
The article is published in the original. 相似文献
19.
Kralj S Cordoyiannis G Zidansek A Lahajnar G Amenitsch H Zumer S Kutnjak Z 《The Journal of chemical physics》2007,127(15):154905
The influence of controlled-pore glass (CPG) confinement on the phase behavior of octylcyanobiphenyl liquid crystal (LC) is studied by means of x-ray scattering and high precision calorimetry. For CPG samples with pore diameter 2R>24 nm, the smectic order parameter temperature dependence eta(T) reveals apparent presmectic ordering far above the bulk smectic A-nematic (SmA-N) phase transition for both nontreated and silane-treated CPG matrices. The behavior of eta(T) is qualitatively similar in all samples, well obeying the mean field approach (MFA) in which the surface wetting tendency plays the dominant role. In contrast, the critical fluctuations remain important in the specific heat data, which cannot be described within the MFA. We show experimentally that randomness and surface wetting become dominant over finite-size effects for 2R approximately<10 nm, in agreement with theoretical analysis. In nontreated samples, the noncritical character of the static disorder and the interfacial LC-CPG coupling almost completely suppress the quasi-SmA-N and nematic-isotropic phase transitions at 2R approximately 15.1 and approximately 7.5 nm, respectively. 相似文献
20.
Amsden JJ Kralj JM Chieffo LR Wang X Erramilli S Spudich EN Spudich JL Ziegler LD Rothschild KJ 《The journal of physical chemistry. B》2007,111(40):11824-11831
Recent studies demonstrate that photoactive proteins can react within several picoseconds to photon absorption by their chromophores. Faster subpicosecond protein responses have been suggested to occur in rhodopsin-like proteins where retinal photoisomerization may impulsively drive structural changes in nearby protein groups. Here, we test this possibility by investigating the earliest protein structural changes occurring in proteorhodopsin (PR) using ultrafast transient infrared (TIR) spectroscopy with approximately 200 fs time resolution combined with nonperturbing isotope labeling. PR is a recently discovered microbial rhodopsin similar to bacteriorhodopsin (BR) found in marine proteobacteria and functions as a proton pump. Vibrational bands in the retinal fingerprint (1175-1215 cm(-1)) and ethylenic stretching (1500-1570 cm(-1)) regions characteristic of all-trans to 13-cis chromophore isomerization and formation of a red-shifted photointermediate appear with a 500-700 fs time constant after photoexcitation. Bands characteristic of partial return to the ground state evolve with a 2.0-3.5 ps time constant. In addition, a negative band appears at 1548 cm(-1) with a time constant of 500-700 fs, which on the basis of total-15N and retinal C15D (retinal with a deuterium on carbon 15) isotope labeling is assigned to an amide II peptide backbone mode that shifts to near 1538 cm(-1) concomitantly with chromophore isomerization. Our results demonstrate that one or more peptide backbone groups in PR respond with a time constant of 500-700 fs, almost coincident with the light-driven retinylidene chromophore isomerization. The protein changes we observe on a subpicosecond time scale may be involved in storage of the absorbed photon energy subsequently utilized for proton transport. 相似文献