共查询到20条相似文献,搜索用时 15 毫秒
1.
Duarte MG Gil MH Peters JA Colet JM Elst LV Muller RN Geraldes CF 《Bioconjugate chemistry》2001,12(2):170-177
Two linear polyamide conjugates of Gd(DTPA)2- were synthesized and characterized by high-resolution nuclear magnetic resonance (NMR) spectroscopy and size exclusion chromatography (SEC). DTPA was copolymerized with two different diamines, 1,6-hexanediamine and trans-1,4-cyclohexanediamine, yielding the polymers DTPA-HMD and DTPA-CHD, with low polydispersity. Their molecular flexibility in solution was studied using 13C spin-lattice relaxation time measurements, indicating that the cyclohexanediamine linking moiety of the DTPA-HMD polymer is more rigid than that of DTPA-CHD. The influence of the flexibility of the linking functionalities on the relaxivity of the Gd3+-DTPA-polymer conjugates was studied by water nuclear magnetic relaxation dispersion (NMRD). The relaxivity of the Gd(DTPA-CHD) polymer was only slightly higher than that of the Gd(DTPA-HMD) polymer, and only two times higher than the usual values for small Gd-DTPA-like chelates. The low relaxivities obtained for both polymers, much lower than expected from the polymer apparent molecular weights, result from their substantial residual flexibility, and also from a too long, nonoptimal, value of the inner-sphere water exchange rate. These polymeric compounds are also cleared very quickly from the blood of rats, indicating that they are of limited value as blood pool contrast agents for MRA. 相似文献
2.
Affinity precipitation is fast emerging as a successful technique for the purification of proteins which can be introduced at an early stage of downstream processing. The technique applies the use of reversibly soluble-insoluble polymers which have either natural or synthetic origin. Apart from the successful use of some natural polymers, such as chitosan and alginate, the vast application of the technique depends upon the design of efficient synthetic polymers. In this laboratory, N-isopropylacrylamide (NIPAM) copolymers have been developed for metal chelate affinity precipitation of proteins. The copolymers of 1-vinylimidazole (VI) and iminodiacetic acid (IDA) with NIPAM were synthesized. The copolymers were thoroughly characterized with a view to designing an efficient soluble-insoluble polymer for metal chelate affinity precipitation of proteins. 相似文献
3.
Yen T. Tan Richard S. Judson Carl F. Melius John Toner Gang Wu 《Journal of molecular modeling》1996,2(6):160-174
We demonstrate the use of molecular dynamics and molecular mechanics methods to calculate properties and behavior of metal-chelate complexes that can be used as MRI contrast agents. Static and dynamic properties of several known agents were calculated and compared with experiment. We calculated the static properties such as the q-values (number of inner shell waters) and binding distances of chelate atoms to the metal ion for a set of chelates with known X-ray structure. The dynamic flexibility of the chelate arms was also calculated. These computations were extended to a series of exploratory chelate structures in order to estimate their potential as MRI contrast agents. We have also calculated for the first time the NMR relaxivity of an MRI contrast agent using a long (5 nsec) molecular dynamics simulation. Our predictions are promising enough that the method should prove useful for evaluating novel candidate compounds before they are synthesized. One novel static property, the projected area of chelate atoms onto a virtual surface centered on the metal ion (gnomonic projection), was found to give an effective measure of how well the chelate atoms use the free space around the metal ion. 相似文献
4.
Many models for the origin of life have focused on understanding how evolution can drive the refinement of a preexisting enzyme, such as the evolution of efficient replicase activity. Here we present a model for what was, arguably, an even earlier stage of chemical evolution, when polymer sequence diversity was generated and sustained before, and during, the onset of functional selection. The model includes regular environmental cycles (e.g. hydration-dehydration cycles) that drive polymers between times of replication and functional activity, which coincide with times of different monomer and polymer diffusivity. Template-directed replication of informational polymers, which takes place during the dehydration stage of each cycle, is considered to be sequence-independent. New sequences are generated by spontaneous polymer formation, and all sequences compete for a finite monomer resource that is recycled via reversible polymerization. Kinetic Monte Carlo simulations demonstrate that this proposed prebiotic scenario provides a robust mechanism for the exploration of sequence space. Introduction of a polymer sequence with monomer synthetase activity illustrates that functional sequences can become established in a preexisting pool of otherwise non-functional sequences. Functional selection does not dominate system dynamics and sequence diversity remains high, permitting the emergence and spread of more than one functional sequence. It is also observed that polymers spontaneously form clusters in simulations where polymers diffuse more slowly than monomers, a feature that is reminiscent of a previous proposal that the earliest stages of life could have been defined by the collective evolution of a system-wide cooperation of polymer aggregates. Overall, the results presented demonstrate the merits of considering plausible prebiotic polymer chemistries and environments that would have allowed for the rapid turnover of monomer resources and for regularly varying monomer/polymer diffusivities. 相似文献
5.
The chemistry of high-performance magnetic resonance imaging contrast agents remains an active area of research. In this work, we demonstrate that the potassium permanganate-based oxidative chemical procedures used to synthesize graphite oxide or graphene nanoparticles leads to the confinement (intercalation) of trace amounts of Mn(2+) ions between the graphene sheets, and that these manganese intercalated graphitic and graphene structures show disparate structural, chemical and magnetic properties, and high relaxivity (up to 2 order) and distinctly different nuclear magnetic resonance dispersion profiles compared to paramagnetic chelate compounds. The results taken together with other published reports on confinement of paramagnetic metal ions within single-walled carbon nanotubes (a rolled up graphene sheet) show that confinement (encapsulation or intercalation) of paramagnetic metal ions within graphene sheets, and not the size, shape or architecture of the graphitic carbon particles is the key determinant for increasing relaxivity, and thus, identifies nano confinement of paramagnetic ions as novel general strategy to develop paramagnetic metal-ion graphitic-carbon complexes as high relaxivity MRI contrast agents. 相似文献
6.
Simultaneously Enhancing the Thermal Stability,Mechanical Modulus,and Electrochemical Performance of Solid Polymer Electrolytes by Incorporating 2D Sheets
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Wenjing Tang Shan Tang Cuijuan Zhang Qingtao Ma Qian Xiang Ying‐Wei Yang Jiayan Luo 《Liver Transplantation》2018,8(24)
Solid state electrolytes are the key components for high energy density lithium ion batteries and especially for lithium metal batteries where lithium dendrite growth is an inevitable obstacle in liquid electrolytes. Solid polymer electrolytes based on a complex of polymers and lithium salts are intrinsically advantageous over inorganic electrolytes in terms of processability and film‐forming properties. But other properties such as ionic conductivity, thermal stability, mechanical modulus, and electrochemical stability need to be improved. Herein, for the first time, 2D additives using few‐layer vermiculite clay sheets as an example to comprehensively upgrade poly(ethylene oxide)‐based solid polymer electrolyte are introduced. With clay sheet additives, the polymer electrolyte exhibits improved thermal stability, mechanical modulus, ionic conductivity, and electrochemical stability along with reduced flammability and interface resistance. The composite polymer electrolyte can suppress the formation and growth of lithium dendrites in lithium metal batteries. It is anticipated that the clay sheets upgraded solid polymer electrolyte can be integrated to construct high performance solid state lithium ion and lithium metal batteries with higher energy and safety. 相似文献
7.
Zili Sideratou Dimitris Tsiourvas Theodossis Theodossiou Michael Fardis Constantinos M. Paleos 《Bioorganic & medicinal chemistry letters》2010,20(14):4177-4181
Based on a commercially available hyperbranched aliphatic polyester, novel multifunctional gadolinium complexes were prepared bearing protective PEG chains, a folate targeting ligand and EDTA or DTPA chelate moieties. Their relatively high water relaxivity values coupled with biodegradability of the hyperbranched scaffold, folate receptor specificity render these non-toxic dendritic polymers promising candidates for MRI applications. 相似文献
8.
The relaxometric properties of two biotinylated paramagnetic liposomes with different lipophilic complexes have been investigated by water proton nuclear magnetic resonance dispersion. The proton relaxivity was found to have a peak at the proton Larmor frequencies generally used in MRI, and to be largely affected by the residence lifetime of the water molecule in the coordination site of the metal chelate. The measurements also indicate that a local motion in the nanosecond time scale, i.e. much faster than the rotational time of the whole liposome, is effective. Possible explanations for this behavior are discussed, that may provide guidelines for the design of second-generation paramagnetic liposomes as contrast agents. 相似文献
9.
With a rising population, the demand for energy has increased over the years. As per the projections, both fossil fuel and renewables will remain as major energy source (678 quadrillion BTU) till 2030 with fossil fuel contributing 78% of total energy consumption. Hence, attempts are continuously made to make fossil fuel production more sustainable and cheaper. From the past 40 years, polymer flooding has been carried out in marginal oil fields and have proved to be successful in many cases. The common expectation from polymer flooding is to obtain 50% ultimate recovery with 15 to 20% incremental recovery over secondary water flooding. Both naturally derived polymers like xanthan gum and synthetic polymers like partially hydrolyzed polyacrylamide (HPAM) have been used for this purpose. Earlier laboratory and field trials revealed that salinity and temperature are the major issues with the synthetic polymers that lead to polymer degradation and adsorption on the rock surface. Microbial degradation and concentration are major issues with naturally derived polymers leading to loss of viscosity and pore throat plugging. Earlier studies also revealed that polymer flooding is successful in the fields where oil viscosity is quite higher (up to 126 cp) than injection water due to improvement in mobility ratio during polymer flooding. The largest successful polymer flood was reported in China in 1990 where both synthetic and naturally derived polymers were used in nearly 20 projects. The implementation of these projects provides valuable suggestions for further improving the available processes in future. This paper examines the selection criteria of polymer, field characteristics that support polymer floods and recommendation to design a large producing polymer flooding. 相似文献
10.
Affinity precipitation of proteins uses polymers capable of reversible soluble-insoluble transitions in response to small environmental changes (temperature, pH or solvent composition). Here we describe protocols for (i) the synthesis of responsive polymers with specific affinity to target proteins and (ii) the purification of proteins using these polymers. The purification is based on precipitation of the affinity complex between the protein and the polymer, which is induced by environmental changes. This separation strategy is simpler and more cost effective than conventional affinity column chromatography. Specifically, we describe the synthesis of thermoresponsive 1-vinylimidazole:N-isopropylacrylamide copolymers. The whole procedure takes 2-3 h when applied to purification of recombinant His-tag proteins or proteins with natural metal binding groups by means of metal chelate affinity precipitation. Optimization of the polymer composition and the type of chelating ions allows for target protein yields of 80% and higher. 相似文献
11.
Marrington R Small E Rodger A Dafforn TR Addinall SG 《The Journal of biological chemistry》2004,279(47):48821-48829
Polymer formation by the essential FtsZ protein plays a crucial role in the cytokinesis of most prokaryotes. Lateral associations between these FtsZ polymers to form bundles or sheets are widely predicted to be extremely important for FtsZ function in vivo. We have carried out a study in vitro of FtsZ polymer formation and bundling using linear dichroism (LD) to assess structural properties of the polymers. We demonstrate proof-of-principle experiments to show that LD can be used as a technique to follow FtsZ polymerization, and we present the LD spectra of FtsZ polymers. Our subsequent examination of FtsZ polymer bundling induced by calcium reveals a substantial increase in the LD signal indicative of increased polymer length and rigidity. We also detect a specific conformational change in the guanine moiety associated with bundling, whereas the conformation and configuration of the FtsZ monomers within the polymer remain largely unchanged. We demonstrate that other divalent cations can induce this conformational change in FtsZ-bound GTP coincident with polymer bundling. Therefore, we present "flipping" of the guanine moiety in FtsZ-bound GTP as a mechanism that explains the link between reduced GTPase activity, increased polymer stability, and polymer bundling. 相似文献
12.
壳聚糖-g-N.羧甲基-二(2-苯并眯唑)-1,2-乙二醇的制备及其性能 总被引:1,自引:0,他引:1
以2-溴乙酸、壳聚糖、二(2-苯并咪唑)-1,2-乙二醇为原料,利用接枝作用将化学修饰后的小分子药物二(2-苯并咪唑)-1,2-乙二醇连接在天然高分子壳聚糖(CTS)上。并以。HNMR,IR,热分析及XRD等方法对其结构进行表征并研究接枝聚合物的理化性质。本文采用络合滴定法测定了接枝聚合物对一系列重金属离子的吸附作用;采用震荡法进行悬菌定量杀菌实验;还以经典的静态失重法研究了合成的聚合物在腐蚀介质中对N80钢片腐蚀的抑制作用。结果表明:小分子药物-(2-苯并咪唑)-1,2-乙二醇在接枝到天然高分子壳聚糖后热稳定性提高,在酸中具有良好的溶解度,对金属离子吸附能力在一个较宽温度范围内得以保持;同时增强了抑菌力,降低了最小抑菌浓度;利用BBIE与CTS韵协同作用提高了聚合物对金属腐蚀的抑制能力。 相似文献
13.
《Journal of liposome research》2013,23(4):483-499
AbstractThe blood pool is among body compartments of a special interest for imaging using magnetic resonance (MR) and computed tomography (CT), since with the help of selective blood-pool contrast agents blood perfusion and various cardiac parameters as well as a status of the blood flow and vascular system in any organ can be evaluated. Blood pool-specific imaging agents can also provide minimally invasive angiography, image guidance of minimally invasive procedures, oncologic imaging of angiogenesis, ascertaining organ blood volume, and identifying hemorrhage. Particulate contrast agents (such as liposomes and micelles) whose distribution is limited to the blood pool, should have a size larger than fenestrated capillaries (> 10 nm), contain the reporter (paramagnetic or radiopaque) moiety structurally incorporated within the particulate, and be able to stay in the blood long enough to obtain clinically useful images. We describe here a new generation of long-circulating Gd-loaded liposomes and iodine-loaded micelles to provide an efficient blood pool MR and CT imaging, respectively. In this study, we developed the optimized protocol to prepare a liposomal MR contrast agent with high relaxivity and narrow size distribution. Liposomes were loaded with Gadolinium (Gd) via so called polychelating amphiphilic polymer (PAP) that represents a low-molecular-weight DTPA-polylysine linked via its N-terminus to a lipid anchor, NGPE-PE. Gd-containing liposomes were additionally modified with PEG to provide the longevity in vivo. We demonstrated also that upon the intravenous administration in rabbits and dogs, a new preparation causes prolonged decrease in the blood Tl value, permits to obtain sharp and clear MR images of the vasculature, and may be considered as a potential contrast agent for MRI of the blood pool. In addition, to prepare micellar contrast agents for CT blood-pool imaging, we synthesized an iodine-containing amphiphilic block-copolymer consisting of methoxypoly(ethyleneglycol) and polyl?,N-(triiodobenzoyl)]-L-lysine. In aqueous solutions, it forms stable micelles with an average diameter of 80 nm and an iodine content of 35–40% wt. Iodine-containing micelles were intravenously injected into rats and rabbits at a dose of 170 mg I/kg and produced significant and sustained enhancement of the blood pool (aorta and heart), liver and spleen for a period of at least 3 hours providing clear and informative CT images. 相似文献
14.
Barbara Matheson Herman E Kwansa Enrico Bucci Annette Rebel Raymond C Koehler 《Journal of applied physiology》2002,93(4):1479-1486
The clinical utility of cross-linked tetrameric hemoglobin solutions is limited by peripheral vasoconstriction thought to be due to scavenging of nitric oxide. In addition, transfusion of crude preparations of hemoglobin polymers can cause arterial hypertension. We tested the hypothesis that eliminating low-molecular-weight components from the polymer solution would prevent extravasation and its associated pressor response. A zero-link polymer of bovine hemoglobin was developed without chemical linkers left between the tetramers. Transfusion of unprocessed preparations of these polymers in rats resulted in appearance of the polymer in the renal hilar lymph. However, eliminating the low-molecular-weight components with a 300-kDa diafiltration resulted in an average hydrodynamic radius of 250 A and in undetectable levels of polymer in hilar lymph. Exchange transfusion in anesthetized rats and cats and in awake cats produced no increase in arterial pressure. In anesthetized cats, exchange transfusion with an albumin solution reduced hematocrit from 30 to 18%, increased cerebral blood flow, and dilated pial arterioles. In contrast, reducing hematocrit by transfusing the diafiltered polymer did not increase cerebral blood flow as pial arterioles constricted. These results are consistent with the hypothesis that the increase in arterial pressure associated with cell-free hemoglobin transfusion depends on hemoglobin extravasation. Constriction observed in the cerebrovascular bed with a nonextravasating hemoglobin polymer at low hematocrit is presumably a regulatory response to prevent overoxygenation at low blood viscosity. 相似文献
15.
Bacteria secrete effector proteins required for successful infection and expression of toxicity into host cells. The type III secretion apparatus is involved in these processes. Previously, we showed that the viscous polymer polyethylene glycol (PEG) 8000 suppressed effector secretion by Pseudomonas aeruginosa. We thus considered that other viscous polymers might also suppress secretion. We initially showed that PEG200 (formed from the same monomer (ethylene glycol) as PEG8000, but which forms solutions of lower viscosity than the latter compound) did not decrease effector secretion. By contrast, alginate, a high-viscous polymer formed from mannuronic and guluronic acid, unlike PEG8000, effectively inhibited secretion. The effectiveness of PEG8000 and alginate in this regard was closely associated with polymer viscosity, but the nature of viscosity dependence differed between the two polymers. Moreover, not only the natural polymer alginate, but also mucin, which protects against infection, suppressed secretion. We thus confirmed that polymer viscosity contributes to the suppression of effector secretion, but other factors (e.g. electrostatic interaction) may also be involved. Moreover, the results suggest that regulation of bacterial secretion by polymers may occur naturally via the action of components of biofilm or mucin layer. 相似文献
16.
An Arthrobacter sp. isolated from a glucose-sucrose agar plate was found to produce a neutral, extremely viscous, opalescent extracellular polymer. Growth, polymer production, and rheological properties and chemical composition of the isolated polymer were examined. The polymer was found to be substantially different from other arthrobacter polymers. Some unusual properties included irreversible loss of viscosity with high temperature and degradation of the polymer during fermentation and upon storage at 4 degrees C. Other characteristics included dependence on sucrose for polymer production, relative pH stability, increased viscosity with increased salt concentration, and pseudoplasticity. The polymer was found to be composed primarily (if not entirely) of d-fructose. The fructose content and other characteristics suggested that the polymer was a levan. 相似文献
17.
《Journal of liposome research》2013,23(2):909-936
AbstractPolymer-coated lipid vesicles labeled with either a radionuclide such as technetium-99m or a paramagnetic cation such as gadolinium or manganese, exhibit an extended half-life in the circulation and reduced reticuloendothelial uptake, and are of potential utility as vascular imaging agents for both nuclear medicine and magnetic resonance. For nuclear medicine applications, lipid vesicles may be prepared with radionuclide either attached to the membrane surface by means of a suitable chelate or else encapsulated within the vesicle and offer two principle advantages compared to radiolabeled red blood cells, (i) vesicle can be prepared prior to patient arrival thereby minimizing delays and scheduling difficulties and (ii) known drug interferences are eliminated. The surface-labeling approach is technically more simple and is better suited to the production of vesicles in a pharmaceutically-acceptable form ready for labeling, however encapsulation results in vesicles which exhibit less renal clearance of entrapped label. The limitations of each approach in real clinical practice are not yet evident. For magnetic resonance applications, paramagnetically-labeled vesicles would be a superior vascular marker compared to small molecular weight paramagnetic chelates and may prove useful for blood volume and perfusion measurements. Surface-associated chelates are the approach of choice for a variety of reasons including increased relaxivity and reduced lipid dose compared to vesicles with entrapped paramagnetic chelates. The presence of polymer on the membrane surface has no effect upon die relaxivity of paramagnetic chelates eitiier entrapped widiin the vesicle or bound to the membrane surface. 相似文献
18.
Proton spin-lattice relaxation rates (R1) have been measured in a variety of dark-adapted chloroplast suspensions over a range of field strengths between 1 and 15 kG (4–5 MHz). When the effects of EDTA or Tris washing on chloroplast relaxivities are compared, the pool of Mn associated with oxygen evolution is seen not to contribute significantly to relaxivity. Instead, nearly all of the observed relaxivity, which is characterized by a paramagnetic maximum near 20.7 MHz in the field dispersion profile of R1, appears to arise from contaminating non-functional Mn(II) that can be removed by EDTA during the isolation procedure. These observations, which contradict previous reports ascribing chloroplast relaxivity to the water-oxidizing system, require a reevaluation of proposed models, derived from NMR studies, of the state of Mn in the water-splitting reaction.Chloroplasts from which loosely bound non-functional Mn has been removed by EDTA washing do show an enhancement of relaxivity when exposed to NH2OH at concentrations known to inactivate water oxidation. This NH2OH-induced relaxivity is comprised of Mn(II) in two distinct paramagnetic sites. One site is chelatable by EDTA, whereas the other site is not. This finding suggests that some Mn(II) tightly bound to thylakoid membranes can contribute to relaxivity after inactivation of the oxygen-evolving reaction. 相似文献
19.
A method is suggested for the preparation of chelating polymers containing a single terminal reactive group capable of interaction with proteins. These polymers were synthesized from N-CBZ-polylysine and DTPA and contain a terminal SH or pyridyldisulfide group. A polymer molecule with MW 13,500 is able to carry up to 40 DTPA residues. Polymers easily and quantitatively bind with antibodies (Fab fragments of antimyosin antibodies R11D10) with minimal effect on antibody immunoreactivity as revealed in ELISA assay and in direct immunoanalysis. Conjugates prepared can chelate radioactive metal ions reaching very high specific radioactivity (greater than 1 mCi 111In/10 micrograms of protein). Perspectives for their application are discussed. 相似文献
20.
In the present study, we have investigated the in vitro polymerization of human plasma AGT (angiotensinogen), a non-inhibitory member of the serpin (SERine Protease INhibitor) family. Polymerization of AGT is thought to contribute to a high molecular mass form of the protein in plasma that is increased in pregnancy and pregnancy-associated hypertension. The results of the present study demonstrate that the polymerization of AGT occurs through a novel mechanism which is primarily dependent on non-covalent linkages, while additional disulfide linkages formed after prolonged incubation are not essential for either formation or stability of polymers. We present the first analyses of AGT polymers by electron microscopy, CD spectroscopy, stability assays and sensitivity to proteinases and we conclude that their structure differs from the 'loop-sheet' polymers typical of inhibitory serpins. Histidine residues within the unique N-terminal extension of AGT appear to influence polymer formation, although polymer formation can still take place after their removal by renin. At a functional level, we show that AGT polymers are not substrates for renin, so polymerization of AGT in plasma would predictably lead to decreased formation of AngI (angiotensin I) with blood pressure lowering. Polymerization may therefore be an appropriate response to hypertension. The ability of AGT to protect its renin cleavage site through polymerization may explain why the AngI decapeptide has remained linked to the large and apparently inactive serpin body throughout evolution. 相似文献