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151.
Yu P Strug I Cafarella TR Seaton BA Krantz A 《Organic & biomolecular chemistry》2012,10(23):4500-4504
Annexin V (1) specifically binds to phosphatidylserine on apoptotic and necrotic cells as well as certain cancer cells, making it an attractive vehicle for the delivery of therapeutically-relevant conjugates to such sites. The wild-type protein possesses a single thiol at Cys316, which is difficultly accessible to site-specific labeling by simple maleimides. By contrast, 1,4-benzoquinone site-specifically labels annexin V in minutes. The resulting conjugate (5) serves as an intermediate for crosslinking annexin molecules, which can be accomplished within hours either directly for linking annexin V-128 (19), or via an extended sequence involving the crosslinking of two units of (5) by the symmetrical α,ω-dithiol (20). Besides its ability to mediate protein dimer formation while retaining annexin V's ability to bind phosphatidylserine, (5) possesses classic 1,4-benzoquinone reactivity. Various nucleophiles and Diels-Alder dienes form adducts with (5) in reactions that may have general utility for the synthesis of novel biologically active entities. The present work presents the first example of thiol-specific crosslinking of proteins by 1,4-quinone-based methodology designed to exploit the reactivity of this versatile chemical entity. 相似文献
152.
Ghitti M Spitaleri A Valentinis B Mari S Asperti C Traversari C Rizzardi GP Musco G 《Angewandte Chemie (International ed. in English)》2012,51(31):7702-7705
Ain't got that swing(-out): The cyclopeptide isoDGR is emerging as a new αvβ3 integrin binding motif. Agreement between the results of computational and biochemical studies reveals that isoDGR-containing cyclopeptides are true αvβ3 integrin antagonists that block αvβ3 in its inactive conformation (see scheme). isoDGR-based ligands may give αvβ3 antagonists without paradoxical effects. 相似文献
153.
Paolo Dapporto Paola Paoli Carla Bazzicalupi Andrea Bencini Nicoletta Nardi Barbara Valtancoli 《Supramolecular chemistry》2013,25(3):195-200
Abstract In preceding works, which have dealt with the synthesis and characterisation of a series of macrobicyclic compounds with five donor atoms, the unusually high basicity constants of these polyaminic cage-like molecules have been ascribed to the inclusion of the proton inside the macrobicyclic cavity which results in a very efficient hydrogen-bond network. The present paper, based on previously reported X-ray crystal structures regarding five-atoms bridging units and on molecular modelling studies shows that the disposition of the five donor atoms in the monoprotonated species is related to the protonation site. Precisely, if the protonation occurs on a bridge-head nitrogen the resulting geometry of the donors is a trigonal bipyramid, whereas it is square pyramidal when the proton is bound to a nitrogen belonging to a macrobicyclic chain. For what concerns the geometrical array of the donor atoms in the free amines, the favoured array seems to be the trigonal bipyramidal. 相似文献
154.
InIII-Phthalocyanines: Synthesis, Properties, and Crystal Structure of Tetra(n-butyl)ammonium-cis-di(nitrito-O,O')phthalocyaninato(2–)indate(III) [In(Cl)Pc2?] reacts with (nBu4N)NO2 in acetone yielding green-blue (nBu4N)cis[In(NO2)2Pc2?], which crystallizes in the monoclinic space group P21/n (No. 14). Both nitrite anions are coordinated as chelating nitrito-O,O'(NO2) ligands to InIII in cis-geometry. Consequently InIII is octa-coordinated within a distorted “quadratic” antiprism and directed towards the Pc2?-ligand. One of the NO2 ligands has equivalent N? O bonds similar to free nitrite, while the other has asymmetric N? O bonds. Both (In,O,N,O) rings are approximately planar with a dihedral angle of 80°. The Pc2? ligand is distorted in an asymmetrically convex manner. Partially overlapping pairs of Pc2? ligands related by an inversion center form double layers, which are separated by layers containing the (nBu4N)+ cations. The cyclic voltammogram shows three electrode processes, which are assigned to the redox pairs: Pc3?/Pc2? (?0.94 V) < InI/InIII (-0.78 V) < Pc2?/Pc? (0.64 V). The UV-VIS-NIR spectra and vibrational spectra are discussed. 相似文献
155.
Clay A. Henry Mel Judy Barbara Dyer Martin Wagner James L. Matthews 《Photochemistry and photobiology》1995,61(4):410-413
Abstract— The phototoxicity of argon laser irradiation was studied in aqueous suspensions of Porphyromonas endodontalis (American Type Culture Collection [ATCC] 35406), Porphyromonas gingivalis (ATCC 33277), Prevotella denticola (ATCC 33184) and two strains of Prevotella intermedia (ATCC 15033 and 49046), all "black-pigmented bacteria," BPB, that accumulate cellular porphyrins. Several of these species have been implicated in the etiology of Periodontol disease. Non-black-pigmented bacteria were also studied to test the specificity of irradiation as a potential photodynamic treatment for Periodontol infections. Cell suspensions were irradiated with an argon laser at fluences of 20–200 J/cm2 . When cultured in hemin-supplemented media, ATCC 15033 was the most sensitive to irradiation. However, a second strain of the same species (ATCC 49046) was resistant. The photosensitivity of other species ranked ATCC 33277 > 35406 = 33184 = 35496. When hemin was replaced in media by hemoglobin, ATCC 33277 became resistant to irradiation. Protoporphyrin IX content in BPB cells was shown not to be a major factor determining photosensitivity. Oxygen was required during irradiation for BPB species to be affected. Non-black-pigmented bacteria were much less sensitive to irradiation than BPB. 相似文献
156.
David Kessel Kathryn Woodburn† Barbara W. Henderson C. K. Chang 《Photochemistry and photobiology》1995,62(5):875-881
Abstract— Localization and photodynamic efficacy of a monocationic porphyrin (MCP) were assessed using murine leukemia cells in culture. This sensitizer localized at surface membrane loci and catalyzed selective photodamage to membrane structures. Although both cationic and hydrophobic, this porphyrin was not recognized by the multidrug transporter, which excludes many cationic agents from cells that express multidrug resistance. Photodynamic studies with the murine radiation-induced fibrosarcoma tumor model indicated moderate photosensitization of neoplastic lesions in vivo at 3 h, but not at 24 h after sensitizer administration. Pharmacokinetic studies indicate that plasma levels, not tissue levels were the major determinant of photodynamic therapy (PDT) response. Consistent with this observation, vascular damage and disturbances of tissue perfusion followed PDT. These effects were more pronounced in tumor-bearing skin than in normal skin. The therapeutic response to MCP appeared to be related mainly to secondary, probably vascular, effects. 相似文献
157.
PHOTOSENSITIZATION OF MURINE TUMOR, VASCULATURE and SKIN BY 5-AMINOLEVULINIC ACID-INDUCED PORPHYRIN 总被引:2,自引:0,他引:2
Barbara W. Henderson Lurink Vaughan David A. Bellnier Henricus van Leengoed Patricia G. Johnson Allan R. Oseroff 《Photochemistry and photobiology》1995,62(4):780-789
Abstract— The effects of topical and systemic administration of 5-aminolevulinic acid (ALA) were examined in several murine tumor systems with regard to porphyrin accumulation kinetics in tumor, skin and blood, vascular and tumor cell photosensitization and tumor response after light exposure. Marked, transient increases in porphyrin levels were observed in tumor and skin after systemic and topical ALA. Rapid, transient, dose-dependent porphyrin increases were also observed in blood; these were pronounced after systemic ALA injection and mild after topical application. They were highest within 1 h after ALA injection, thereafter declining rapidly. This matched the clearing kinetics of injected exogenous protoporphyrin IX (PpIX). Initially, vascular photosensitivity changed inversely to blood porphyrin levels, increasing gradually up to 5 h post-ALA, as porphyrin was clearing from the bloodstream. This pattern was again matched by injected, exogenous PpIX. After therapeutic tumor treatment vascular disruption of the tumor bed, while observed, was incomplete, especially at the tumor base. Minimal direct tumor cell kill was found at low photodynamic therapy (PDT) doses (250 mg/kg ALA, 135 J/cm2 light). Significant, but limited (<1 log) direct photodynamic tumor cell kill was obtained when the PDT dose was raised to 500 mg/kg systemic ALA, followed 3 h later by 270 J/cm2 , a dose that was however toxic to the animals. The further reduction of clonogenic tumor cells over 24 h following treatment was moderate and probably limited by the incomplete disruption of the vasculature. Tumor responses were highest when light treatment was carried out at the time of highest tumor porphyrin content rather than at the time of highest vascular photosensitivity. Tumor destruction did not reach the tumor base, regardless of treatment conditions. 相似文献
158.
159.
Studies are constantly being conducted on the elaboration of efficient methods to confirm the compatibility of active pharmaceutical ingredients (APIs) and excipients, since medicinal products, apart from their APIs, also contain numerous excipients that not only have important functions in pharmaceutical preparations but can also initiate or participate in interactions with drug substances, which eventually lead to a decline in drug quality. With this in mind, research was undertaken to evaluate two of the most often applied pattern recognition methods, hierarchical cluster analysis (HCA) and principal component analysis (PCA), as supporting techniques in the identification of potential physicochemical interactions that may occur during the preformulation of solid dosage forms. The investigation performed with the use of baclofen and selected excipients has shown that with thermogravimetric analysis, HCA and PCA fulfill their role as supporting techniques in the interpretation of the data obtained. Based on these methods, it is possible to detect incompatibilities between baclofen and excipients, and the data obtained concur strongly with the results of differential scanning calorimetry and IR spectrometry analyses. 相似文献
160.
Ventura B Barbieri A Degli Esposti A Seneclauze JB Ziessel R 《Inorganic chemistry》2012,51(5):2832-2840
The synthesis, characterization, photophysics, and time-dependent density functional theory (TD-DFT) calculations of spirobifluorene-bipyridine based iridium(III), osmium(II), and mixed Ir/Os complexes are presented. The preparation of the reference and mixed complexes proceeded step-by-step and microwave irradiation facilitated the complexation of osmium. The absorption of the target heterobimetallic derivative, Ir-L-Os, is described by linear combination of half of the absorption spectra of the homobimetallic analogues, Ir-L-Ir and Os-L-Os, due to the occurrence of mixed ligand and metal based transitions when the spirobifluorene-(bpy)(2) bridging ligand L is linked to the metal, confirming a negligible interaction between the substituted metallic chromophores. TD-DFT calculations on monometallic, homo- and hetero-bimetallic complexes fully disentangled the origin of the absorption features. Noticeably, in the mixed Ir-L-Os complex an almost quantitative energy transfer from the (3)Ir to the (3)Os MLCT state is occurring, with a rate constant of 4.1 × 10(8) s(-1) and nearly exclusively via a Dexter-type mechanism mediated by the orbitals of the spiroconjugated ligand. This result, together with the outcomes of the TD-DFT calculations, supports the existence of spiroconjugation and evidences the interesting role of this kind of bridge in the energy transfer dynamics of the arrays. In all the complexes, moreover, the ligand fluorescence is heavily quenched by energy transfer processes toward the metallic appended units; the rate constant is estimated in the order of 10(10) s(-1) for Ir-L-Os and higher than 10(12) s(-1) for the other complexes. In the heterometallic array, both at room temperature and at 77 K, all photons are thus funneled to the emissive Os (3)MLCT state, which acts as energy trap for the antenna cascade. 相似文献