抗凝血生物材料*

本文对抗凝血材料的研究进展进行了综述,着重介绍了血栓形成及凝血机理、提高生物材料表面抗凝血性能的改性材料和改性技术、抗凝血材料的表征等几方面的内容;分析了当前抗凝血材料研究中存在的问题,并对今后从分子水平上设计新型抗凝血材料进行了展望。     

The standardization of Ammonium vanadate solutions with Sodium Oxalate .

The results of a study of the reaction between ammonium m-vanadate and sodium oxalate in strong sulfuric acid solution are given. It has been found that the latter is a suitable and convenient primary standard for solutions of quinquevalent vanadium.     

抗凝血灭鼠剂杀它仗的合成

以苯乙酰氯和苯甲醚为起始原料,经酰化、缩合、消除、水解、成环、脱保护、氢化还原等反应合成了抗凝血灭鼠剂杀它仗——3-{3-[4-(4-三氟甲基苄氧基)苯基]-1,2,3,4-四氢化萘基}-4-羟基香豆素,总收率8.4%,其结构经1H NMR和IR确证。     

Modified Coumarins. 17. Synthesis and Anticoagulant Activity of 3,4-Cycloannelated Coumarin D-Glycopyranosides

3,4-Cyclocondensed coumarin O-glycopyranosides containing glucose, galactose, xylose, and arabinose were synthesized by condensation of potassium salts of hydroxycoumarins and acetobromosugars. 7-(β-D-Galactopyranosyloxy)-2,3-dihydrocyclopenta[c]chromen-4-one, 3-(β-D-xylopyranosyloxy)-7,8,9,10-tetrahydrobenzo[c]chromen-6-one, and 3-(α-D-arabinopyranosyloxy)benzo[c]chromen-6-one exhibited distinct anticoagulant activity. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 416–419, September–October, 2005.     

Anticoagulant activity of immobilized thrombomodulin

Bovine lung thrombomodulin was partially purified, and immobilized on agarose gel (Sepharose 4B). Immobilized thrombomodulin inhibited the procoagulant activity of thrombin, and enhanced the thrombin-catalyzed protein C activation. The plasma recalcification time test showed that immobilized thrombomodulin prolonged plasma clotting time. It is suggested that the immobilization of thrombomodulin will provide an antithrombogenic biomaterial able to convert thrombin from a procoagulant to an anticoagulant enzyme.     

Effect of vanadate on gill cilia: switching mechanism in ciliary beat.

Lateral (L) cilia of freshwater mussel (Margaritana margaritifera and Elliptio complanatus) gills can be arrested in one of two unique positions. When treated with 12.5 mM CaCl2 and 10(-5) M A23187 they arrest in a "hands up" position, ie, pointing frontally. When treated with approximately 10 mM vanadate (V) they arrest in a "hands down" position, ie, pointing abfrontally. L-cilia treated with 12.5 mM CaCl2 and 1 mM NaN3 also arrest in a "hands down" position; substitution of 20 mM KCl and 1 mM NaN3 causes cilia to move rapidly and simultaneously to a "hands up" position. The observations suggest that there are two switching mechanisms for activation of active sliding in ciliary beat one at the end of the recovery stroke and the other at the end of the effective stroke; the first is inhibited by calcium and the second by vanadate or azide. This is consistent with a model of ciliary beating where microtubule doublet numbers 1, 2, 3, and 4 are active during the effective stroke while microtubule doublets numbers 6, 7, 8, and 9 are passive, and the converse occurs during the recovery stroke.     

Spectrophotometric determination of some penicillins with ammonium vanadate

A spectrophotometric method for determining some penicillins has been developed. A known volume of the penicillin solution-in phosphate buffer of pH 6.8 is boiled with ammonium vanadate solution-in sulphuric acid medium-for 10 min and the absorbance of the colour formed is measured at 750 nm. The excess of vanadate can also be determined volumetrically. The method has been successfully applied for the determination of penicillin G sodium, phenoxymethyl penicillin, ampicillin sodium, phenethicillin potassium, cloxacillin sodium and methicillin sodium. The procedure is also used for analysing some pharmaceutical preparations of these drugs, e.g., injections. The results obtained are in agreement with those of the B P 1973 methods.     

Selectivities of bismuth vanadate catalysts for toluene oxidation

Oxidation of toluene vapors over fused bismuth vanadate catalysts of various compositions in fixed bed has been studied. The optimum conversion of toluene to benzaldehyde is related to the Bi₂O₃ content of the catalyst. The composition Bi₂O₃–V₂O₅(2575) and Bi₂O₃–V₂O₅ (4060) are highly active and selective for the oxidation of toluene to benzaldehyde.

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. Bi₂O₃ . Bi₂O₃V₂O₅, 2575 4060, .

     

Luminescence of aluminum vanadate (AlVO4)

Aluminum vanadate (AlVO₄) shows a broad-band emission peaking at 620 nm at temperatures below 100°K. The luminescence is discussed in connection with the crystal structure.     

Infrared spectra of arsenate and vanadate strontium apatites

The i.r. spectra of some phosphate—arsenate strontium apatites and phosphate—vanadate strontium apatites have been studied and the assignments of their bands realized. It is shown that the symmetry of the distinct anions depends on the apatitic composition and it is suggested the existence of a mechanism of continuous anion migration throughout the apatite lattice.     

Studies on thermal properties of bismuth vanadate catalysts

Physicochemical properties of bismuth vanadate catalysts with varying compositions, e.g., Bi₄V₆O₂₁-6 1/2H₂O·1 ₂ ¹ NH₃; Bi₆V₂O₁₄·3 H₂O; Bi₆V₄O₁₉·6 H₂O have been studied by chemical analysis, differential thermal analysis, thermogravimetry, infrared, X-ray diffraction, surface area and magnetic susceptibility techniques.The endotherms, in all the cases, prior to exo ones are due to stepwise dehydration and those following exochanges are due to decomposition of adsorbed impurities, sintering and melting, etc. The last endopeak, in all the cases, however is due to melting. The exochanges are attributed to stepwise phase transitions. The V-0 stretching in all the compounds is characteristic of polyvanadates. Two types of vanadium-oxygen bonds e.g., V=O and V-O -V are characterized by IR analysis. The fresh first and third vanadates are amorphous whereas the second one is crystalline. The exochanges (presumably due to disorder-order transitions) are suggested to be related to displacement of oxygen anions. The precipitated vanadates are similar with their corresponding solid state reaction products of Bi₂O₃ and V₂O₅ when they are heated at elevated temperature. The fresh as well as treated vanadates are diamagnetic. These systems display maximum surface area at the temperature corresponding to complete dehydration. The composition of the precipitated vanadates is not ultimately defined by Bi/V ratio and the binary compound consequently formed.

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Zusammenfassung Die physikalisch-chemischen Eigenschaften von Bismuthvanadat-Katalysatoren verschiedener Zusammensetzung, z.B. Bi₄V₆O₂₁·6 ₂ ¹ H₂O·1 ₂ ¹ NH₃; Bi₆V₂O₁₄·3 H₂O; Bi₆V₄O₁₉·6 H₂O wurden durch chemische Analyse, Differentialthermoanalyse, Thermogravimetrie, Infrarot, Röntgendiffraktion, Oberflächenmessung und magnetische Susceptibilitätsmessung untersucht. In jedem Fall werden die den Exo-Änderungen vorangehenden Endo-Änderungen durch stufenweise Dehydratisierung verursacht und diejenigen, welche den Exo-Änderungen folgen, durch Zersetzung adsorbierter Verunreinigungen, Sinterung und Schmelzen. Der letzte Endopeak ist jedoch in jedem Falle dem Schmelzen zuzuschreiben. Die Exo-Änderungen werden stufenweisen Phasenübergängen zugeschrieben. In allen Verbindungen ist die V-O Dehnung für die Polyvanadate charakteristisch. Zwei Typen von Vanadium-Sauerstoff Bindungen, z. B. V=O und V-O-V wurden durch IR-Analyse charakterisiert. Die frisch synthetisierten ersten und dritten Vanadate sind amorph, während das zweite kristallin ist. Die (vermutlich durch Unordnung-Ordnungs Übergänge verursachten) Exo-Änderungen sind wahrscheinlich mit der Bewegung der Sauerstoff-Anionen verbunden. Die gefällten Vanadate sind — wenn sie auf hohe Temperaturen erhitzt werden — ihren entsprechenden Festphasen-Reaktionsprodukten Bi₂O₃ und V₂O₅ ähnlich. Die ursprünglichen wie die behandelten Vanadate sind diamagnetisch. Diese Systeme weisen die maximale Oberfläche bei der ihrer vollständigen Dehydratisierung entsprechenden Temperature auf. Die Zusammensetzung der gefällten Vanadate wird letzten Endes nicht durch. ihr Bi-V-Verhältnis und die in der Folge entstandene Binärverbindung bestimmt.

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Résumé Les propriétés physico-chimiques des catalyseurs au vanadate de bismuth, de diverses compositions, par ex. Bi₄V₆O₂₁ · 6 ₂ ¹ H₂O · 1 ₂ ¹ NH₃,Bi₆V₂Oi₁₄ · 3H₂O, Bi₆V₄O₁₉ · 6H₂O, ont été étudiées par analyse chimique, analyse thermique différentielle, thermogravimétrie, spectroscopie infrarouge, diffraction des rayons X, mesures de surfaces spécifiques et de susceptibilité magnétique.Dans tous les cas, les phénomènes endothermiques qui précèdent ceux de nature exothermique sont dus à la déshydratation par étapes; les phénomènes endothermiques qui suivent ceux de nature exothermique sont dus aux impuretés adsorbées, au frittage, à la fusion, etc ... Cependant, le dernier pic endothermique est toujours dû à la fusion. Les changements exothermiques sont attribués à des transitions de phases par étapes. La déformation V-0 dans tous les composés est caractéristique des polyvanadates. Deux types de liaisons vanadium-oxygène, par ex. V=O et V-O-V ont été caractérisés par analyse infrarouge. Le premier et le troisième vanadate, fraîchement préparés, sont amorphes alors que le second est cristallisé. Les. phénomènes exothermiques (probablement dus à des transitions désordre-ordre) sont sans doute en rapport avec le déplacement des anions oxygène. Les vanadates précipités — si on les. chauffe jusqu'à une température élevée — sont similaires aux produits correspondants, obtenus par réaction à l'état solide entre Bi₂O₃ et V₂O₅. Les vanadates fraîchement préparés ainsi que ceux qui ont subi un traitement thermique, sont diamagnétiques. Ces systèmesmontrent une surface spécifique maximalé à la température correspondant à la déshydratation complète. La composition des vanadates précipités n'est pas finalement définie par le rapport Bi/V et le composé binaire formé par la suite.

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- - , , Bi₄V₆O₂₁ · 6.5 ₂ ·1.5 NH₃; Bi₆V₂O₁₄ · ₂; Bi₆V₄O₁₉· 6H₂O , , , , - , . , , , , , . . . . V- . - : V= V--V. , — . , (-, -) . , Bi₂O₃ V₂O₅ . , . , . Bi/V, a, , .

     

香豆素类抗凝血药及其类似物的合成

香豆素类抗凝血药及其类似物的合成;羟基香豆素;取代苯丁烯酮;缩合;香豆素类似物     

A One-pot-synthesized Double-layered Anticoagulant Hydrogel Tube

Extracorporeal membrane oxygenation(ECMO) has emerged as a viable treatment in severe cases of acute respiratory distress syndrome, acute respiratory failure, and adult respiratory distress syndrome. However, thromboembolic events stemming from the use of ECMO devices results in significant morbidity and mortality rates; the inner surface of the ECMO tubing comes into contact with the blood and can readily initiate coagulation. In addition, the tubing needs to be continually replaced due to thromboses on the inner tube wall, which not only increases the risk of infection but also the economic burden. Despite considerable effort, a surface modification strategy that effectively addresses these challenges has not yet been realized. In this study, we developed an integrated hollow core-shell-shell hydrogel tube of gelatin/alginate/acrylamide-bacterial nanocellulose(GAA) that meets the anticoagulant requirements for the inner tubing layer as well as the highly elastic soft material needed for the outer layer. Using static blood from healthy volunteers, we confirmed that the platelets or coagulation is not stimulated by the GAA tubing. Importantly, experiments with dynamic blood also demonstrated that the inner layer of the tubing does not elicit blood clotting. The one-pot-synthesized process may provide guidance for the design of anticoagulation tubes used clinically.     

Synthesis and structure of alkali metal zirconium vanadate phosphates

Mixed vanadate phosphates in the systems MZr₂(VO₄) _x (PO₄)_{3 ? x} , where M is an alkali metal, were synthesized and studied by X-ray diffraction, electron probe microanalysis, and IR spectroscopy. Substitutional solid solutions with the structure of the mineral kosnarite (NZP) are formed at the compositions 0 ≤ x ≤ 0.2 for M = Li; 0 ≤ x ≤ 0.4 for M = Na; 0 ≤ x ≤ 0.5 for M = K; 0 ≤ x ≤ 0.3 for M = Rb; and 0 ≤ x ≤ 0.2 for M = Cs. Apart from the high-temperature NZP modification, lithium vanadate phosphates LiZr₂(VO₄) _x (PO₄)_{3 ? x} with 0 ≤ x ≤ 0.8 synthesized at temperatures not exceeding 840°C crystallize in the scandium tungstate type structure. The crystal structures of LiZr₂(VO₄)_0.8(PO₄)_2.2 (space group P2₁/n, a = 8.8447(6) Å, b = 8.9876(7) Å, c = 12.3976(7) Å, β = 90.821(4)○, V = 985.4(1) ų, Z = 4) and NaZr₂(VO₄)_0.4(PO₄)_2.6 (space group $R\bar 3c$ = 8.8182(3) Å, c = 22.7814(6) Å, V = 1534.14(1) ų, Z = 6) were refined by the Rietvield method. The framework of the vanadate phosphate structure is composed of tetrahedra (that are statistically occupied by vanadium and phosphorus atoms) and ZrO₆ octahedra. The alkali metal atoms occupy extra-framework sites.