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1.
Amphiphilic polyurethane (PU) ionomer networks were synthesized by urethane acrylate anionomer (UAA) precursor chains. These networks were prepared with water, dioxane (DO), and dimethyl sulfoxide (DMSO) and exhibited very different swelling behaviors in water/DO (UAADG) and water/DMSO (UAASG) solvent mixtures, which was due to the different solvent interactions between water/DO and water/DMSO. The additional important factor influencing the swelling behavior in water/aprotic solvent mixtures was the hydrophilicity of the UAA networks, which was different than the water–UAA network interaction. The microstructure of UAA networks prepared with the water/aprotic solvent mixtures was greatly influenced by the water–solvent interactions. Unlike the water/DO mixtures, which had a relatively weak water–DO interaction, the strong water–DMSO interaction largely restricted the ability of DMSO to solvate the UAA chain, which resulted in an increase in the aggregation of the hydrophobic segment and the hydrophilic/hydrophobic microphase separation. Thus, UAASG and UAADG networks showed very different swelling behaviors in the same swelling medium because of the microstructural difference between these gels, which was confirmed by dynamic mechanical measurements. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 608–620, 2001 相似文献
2.
Knowledge about the orientation of ligands or inhibitors bound to a protein is vital for the development of new drugs. It was recently shown that solvent accessibility epitopes for protein ligands can be mapped by transferring magnetization from water molecules to the ligand to derive the ligand orientation. This is based on the fact that NMR signals of ligands arising from magnetization transferred from solvent molecules via the protein have a different sign from those arising from direct magnetization transfer from bulk water. Herein we critically evaluate the applicability of solvent accessibility mapping to derive binding orientations for ligands of two dehydrogenases (AKR1C3 and HSD17beta1) with very different binding pockets, including complexes in which the ligand is buried more deeply inside the protein. We also evaluate the possibility of using co-solvents, such as DMSO, for magnetization transfer. 相似文献
3.
Suzuki Masashi; Gerstein Mark; Johnson Tony 《Protein engineering, design & selection : PEDS》1993,6(6):565-574
The solution structure of one and two repeats of the SPKKDNA-binding motif is reported on the basis of NMR measurements.In dimethylsulphoxide (DMSO) the major population (approximately90%) of peptides, SPRKSPRK(S2) and GSPKKSPRK(S2b), adopts aconformation, which has two trans pralines. The two SP(R/K)Kunits hi these peptides are equivalent and each adopts a turnstructure exchanging with an extended structure. This is suggestedby an NOE connectivity of the /3-turn type, between the backboneamide protons of residues (j+2) and (j+3) and NOE connectivitiesof the Asx(a)-turn type, between protons of the tth Ser andthe backbone amide proton on residue (i+2). This suggests thateach SP(R/K)K unit has a structural intermediate between (ora combination of) a /3-turn and an Asx(a)-turn. In 90-10% DMSO/H2Oat 4C the two units of S2 are connected more tightly by foldinginto a short 3t0 helix, broken at the second proline. For anotherpeptide, Thr-Pro-Arg-Lys(Tl), the major population (75%) in100% DMSO comprises a /3-turn in rapid exchange with an extendedstructure. We did not observe an NOE connectivity of the Asx()type with the Tl peptide. A possible structure of the SPKK motifhi the complex with DNA is discussed. 相似文献
4.
In this study, the solvent adsorption phenomena of poly(vinyl alcohol) (PVA) in cosolvent mixtures of dimethylsulfoxide (DMSO; solvent 1) and water (solvent 2) were investigated. Typically, this cosolvent mixture could form hydrogen‐bonded DMSO/(water)2 complexes, involving one DMSO and two water molecules. Because of the complex formation in the cosolvent mixtures, PVA chains preferentially adsorb water molecules at DMSO mole fraction X1 < 0.33, but preferentially adsorb DMSO molecules at X1 > 0.33. The preferential adsorption of DMSO (a good solvent for PVA) could cause the relatively extended conformation of PVA chains in solutions because of the increase in excluded volume effect. Because of various interactions between PVA chains and cosolvent mixtures, the aggregation and gelation behaviors of PVA solutions were significantly affected by the composition of cosolvent mixture. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3211–3217, 2004 相似文献
5.
Enhancement of flux and solvent stability of Matrimid® thin‐film composite membranes for organic solvent nanofiltration
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Shi‐Peng Sun Tai‐Shung Chung Kang‐Jia Lu Sui‐Yung Chan 《American Institute of Chemical Engineers》2014,60(10):3623-3633
The development of high flux and solvent‐stable thin‐film composite (TFC) organic solvent nanofiltration (OSN) membranes was reported. A novel cross‐linked polyimide substrate, consisting of a thin skin layer with minimum solvent transport resistance and a sponge‐like sublayer structure that could withstand membrane compaction under high‐pressure was first fabricated. Then the solvent flux was significantly enhanced without compromising the solute rejection by the coupling effects of (1) the addition of triethylamine/camphorsulfonic acid into the monomer solution, and (2) the combined post‐treatments of glycerol/sodium dodecyl sulphate immersion and dimethyl sulfoxide (DMSO) filtration. Finally, the long‐term stability of the TFC membrane in aprotic solvents such as DMSO was improved by post‐crosslink thermal annealing. The novel TFC OSN membrane developed was found to have superior rejection to tetracycline (MW: 444 g/mol) but was very permeable to alcohols such as methanol (5.12 lm?2h?1bar?1) and aprotic solvents such as dimethylformamide (3.92 lm?2h?1bar?1) and DMSO (3.34 lm?2h?1bar?1). © 2014 American Institute of Chemical Engineers AIChE J, 60: 3623–3633, 2014 相似文献
6.
Sánchez-Sixto C Prazeres VF Castedo L Suh SW Lamb H Hawkins AR Cañada FJ Jiménez-Barbero J González-Bello C 《ChemMedChem》2008,3(5):756-770
Several 3-heteroaryl analogs of the known dehydroquinase inhibitor (1R,4R,5R)-1,4,5-trihydroxy-2-cyclohexene-1-carboxylic acid (4) were synthesized and tested as inhibitors of Helicobacter pylori type II dehydroquinase, the third enzyme of the shikimic acid pathway. All of these compounds proved to be reversible competitive inhibitiors of this enzyme and proved to be, with the exception of nitrile 8 e, more potent than the parent inhibitor 4 (K(i)=370 microM). The 2-thienyl derivative 8 b was found to be the most potent inhibitor of the series and has a K(i) value of 540 nM, which is almost seven hundred times lower than that of the parent inhibitor. The 3-nitrothienyl derivative 8 d and 2-furanyl derivative 8 a also had a good affinity of 1 microM. The conformation of the potent competitive inhibitor 8 b, when bound in the active site of the H. pylori enzyme, was elucidated by 1D-selective inversion NOE, Saturation Transfer Difference (STD) and transferred NOESY NMR experiments. One of the conformations that exists in solution for the potent competitive inhibitor 2-thienyl derivative 8 b is selected when it is bound to the active site of the enzyme. In the bound conformation derivative 8 b has the sulfur atom of its thienyl group oriented towards the double bond of the cyclohexene moiety. The large STD effects observed for the aromatic protons of 8 b show that it is the thiophene side of the ligand that makes closest contact with enzyme protons. Docking studies using GOLD3.0.1 suggest that the conformation determined by NMR allows strong lipophilic interactions with the enzyme residues Pro9, Asn10, Ile11, Gly78 and Ala 79. Competitive STD experiments carried out with high-, medium- and low-affinity ligands 8 b, 5 d and 5 f show that they all bind in the same site of Helicobacter pylori dehydroquinase. 相似文献
7.
8.
Sarah A. Allman Henrik H. Jensen Drs. Balakumar Vijayakrishnan James A. Garnett Ester Leon Yan Liu Dr. Daniel C. Anthony Dr. Nicola R. Sibson Dr. Ten Feizi Prof. Stephen Matthews Prof. Benjamin G. Davis Prof. 《Chembiochem : a European journal of chemical biology》2009,10(15):2522-2529
Unnatural, NMR‐ and MRI‐active fluorinated sugar probes, designed and synthesised to bind to the pathogenic protein TgMIC1 from Toxoplasma gondii, were found to display binding potency equal to and above that of the natural ligand. Dissection of the binding mechanism and modes, including the first X‐ray crystal structures of a fluoro‐oligosaccharide bound to a lectin, demonstrate that it is possible to create effective fluorinated probe ligands for the study of, and perhaps intervention in, sugar–protein binding events. 相似文献
9.
Ritchie A. Wessling 《应用聚合物科学杂志》1970,14(9):2263-2277
Effective solvents for poly(vinylidene chloride) (PVDC) were obtained by mixing a polar aprotic solvent with a less polar solvent of cyclic structure. The polar components included sulfoxides, N,N-dialkylamides, and N-alkyl lactams. The cyclic cosolvents included aliphatic and aromatic hydrocarbons, ketones, ethers, and thioethers. The problem of solubility of a crystalline polymer in a mixed solvent was analyzed by extending the Flory theory of melting point depression to three component mixtures. The results predict that favorable mixtures arise when at least one of the components interacts strongly with the polymer but is nearly incompatible with the cosolvent. This is in qualitative agreement with the observed behavior of PVDC. 相似文献
10.
Sriraj Srinivasan George Kalfas Violeta I. Petkovska Christopher Bruni Michael C. Grady Masoud Soroush 《应用聚合物科学杂志》2010,118(4):1898-1909
This article presents an experimental study of the spontaneous thermal homopolymerization of methyl acrylate (MA) and n‐butyl acrylate (nBA) in the absence of any known added initiators at 120 and 140°C in a batch reactor. The effects of the solvent type, oxygen level, and reaction temperature on the monomer conversion and polymer average molecular weights were investigated. Three solvents, dimethyl sulfoxide (DMSO; polar, aprotic), cyclohexanone (polar, aprotic), and xylene (nonpolar) were used. The spontaneous thermal polymerization of MA and nBA in DMSO resulted in a lower conversion and higher average molecular weights in comparison to polymerization in cyclohexanone and xylene under the same conditions. The highest final conversion of both monomers was obtained in cyclohexanone. The high polymerization rate in cyclohexanone was most likely due to an additional initiation mechanism where cyclohexanone complexed with the monomer to generate free radicals. Bubbling air through the mixture led to a higher monomer conversion during the early stage of the polymerization and a lower polymer average molecular weight in xylene and cyclohexanone; this indicated the existence of a distinct behavior between the air‐ and nitrogen‐purged systems. Matrix‐assisted laser desorption/ionization time‐of‐flight analysis of the polymer samples taken from nitrogen‐bubbled batches did not reveal fragments from initiating impurities. On the basis of the identified families of peaks, monomer self‐initiation is suggested as the principal mode of initiation in the spontaneous thermal polymerization of MA and nBA at temperatures above 100°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
11.
Tolibjon S. Omonov Ereddad Kharraz Jonathan M. Curtis 《Journal of the American Oil Chemists' Society》2011,88(5):689-705
The use of ozonolysis has been proposed as a step in the production of vegetable-oil-based polyols as replacements for the
equivalent petrochemicals. As part of an evaluation of the commercial viability of ozonolysis, the intermediates and products
formed from the ozonolysis of canola oil using different protic and aprotic solvents and solvent mixtures were systematically
studied by GC-FID and size-exclusion chromatography with refractive index detection (SEC-RI). It was found that the use of
an aprotic solvent (ethyl acetate) leads to the formation of oligomeric ozonolysis products whereas alcohols and/or mixtures
of ethyl acetate with alcohols for the ozonolysis of canola oil do not form high molecular weight compounds. In addition,
when ethyl acetate is used as the solvent, the formation of carboxylic acids is observed in the early stages of ozonolysis
whereas the use of alcohols significantly reduces acid formation. As expected, extending the ozonolysis time led to extensive
carboxylic acid formation, especially using ethyl acetate as a solvent. It was found that the optimum time for the complete
ozonolysis of canola oil was largely independent of the solvent used for ozonolysis. However, the yield of ozonolysis products
differs considerably depending on the solvents employed. Overall, a clear correlation between the ozonolysis time, product
yields and the reaction exothermicity was observed. 相似文献
12.
The present article deals with super‐swelling behavior of crosslinked homopolymer of 2‐acrylamido‐2‐methylpropane sulfonic acid, poly(AMPS), in binary mixtures of dimethyl sulfoxide (DMSO) and various polar solvents including water, mono‐, and polyhydric alcohols, and amide solvents such as N‐methyl pyrrolidone. Extraordinary phase transition sequences including a new unusual swelling phenomenon, referred to as “overentrant” swelling, was observed for this polymeric organogel in the solvent/DMSO mixtures. The swelling behaviors were preliminarily explained based on the major interactions involved in the solvation process and dielectric constant of the swelling media. It was established that the “overentrant” region of the swelling profiles was progressed with the increase of dielectric constant of the mixed solvent media. The overentrant region was disappeared with partial replacement of AMPS units with acrylic acid. This was taken as an additional practical evidence for a major role of the sulfonic acid as the main interactive group involved in the solvation process. The unusual phase transitions were also explained via a semiquantitative approach based on the Gutmann's acceptor number and donor number values to emphasis on the key effect of dissociation degree of the sulfonic acid group (as a function of the solvent type and composition) on the swelling behaviors. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
13.
Copolyimides were prepared by reacting 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BPTD) with mixtures of various proportions of 3,3′-sulfonylbis (phenyl isocyanate) (SDI) and 4,4′-methylenebis (phenyl isocyanate) (MDI) in an aprotic polar solvent. The nature and properties of these copolyimides were studied. 相似文献
14.
Aboitiz N Vila-Perelló M Groves P Asensio JL Andreu D Cañada FJ Jiménez-Barbero J 《Chembiochem : a European journal of chemical biology》2004,5(9):1245-1255
HEV32, a 32-residue, truncated hevein lacking eleven C-terminal amino acids, was synthesized by solid-phase methodology and correctly folded with three cysteine bridge pairs. The affinities of HEV32 for small chitin fragments--in the forms of N,N',N"-triacetylchitotriose ((GlcNAc)3) (millimolar) and N,N',N",N"',N",N"'-hexaacetylchitohexaose ((GlcNAc)6) (micromolar)--as measured by NMR and fluorescence methods, are comparable with those of native hevein. The HEV32 ligand-binding process is enthalpy driven, while entropy opposes binding. The NMR structure of ligand-bound HEV32 in aqueous solution was determined to be highly similar to the NMR structure of ligand-bound hevein. Solvated molecular-dynamics simulations were performed in order to monitor the changes in side-chain conformation of the binding site of HEV32 and hevein upon interaction with ligands. The calculations suggest that the Trp21 side-chain orientation of HEV32 in the free form differs from that in the bound state; this agrees with fluorescence and thermodynamic data. HEV32 provides a simple molecular model for studying protein-carbohydrate interactions and for understanding the physiological relevance of small native hevein domains lacking C-terminal residues. 相似文献
15.
Núria Parera Pera Dr. Hilbert M. Branderhorst Dr. Raymond Kooij Caroline Maierhofer Dr. Marjolein van der Kaaden Rob M. J. Liskamp Prof. Dr. Valentin Wittmann Prof. Dr. Rob Ruijtenbeek Dr. Roland J. Pieters Dr. 《Chembiochem : a European journal of chemical biology》2010,11(13):1896-1904
Multivalency is an important phenomenon in protein–carbohydrate interactions. In order to evaluate glycodendrimers as multivalent inhibitors of carbohydrate binding proteins, we displayed them on a microarray surface. Valencies were varied from 1 to 8, and corrections were made for the valencies so that all surfaces contained the same amount of the sugar ligand. Five different carbohydrates were attached to the dendrimers. A series of fluorescent lectins was evaluated, and for each of them a binding profile was obtained from a single experiment showing both the specificity of the lectin for a certain sugar and whether it prefers multivalent ligands or not. Very distinct binding patterns were seen for the various lectins. The results were rationalized with respect to the interbinding distances of the lectins. 相似文献
16.
Poly(L-ornithine)s having various azo-contents in the side chains were synthesized by the water-soluble carbodiimide procedure. The photochemical properties of the polypeptides poly[Nδ-p-(phenylazo)benzoyl-L-ornithine] (PPABLO) containing 3–77 mol% azobenzene were investigated by absorption and circular dichroism spectroscopy in hexafluoro-2-propanol (HFIP) or water, and in HFIP-water or methanol-water solvent mixtures. The photochromism of the dichroic bands of the PPABLOs containing 20–77 mol% azobenzene in the visible and ultraviolet wavelength regions was found to be mostly reversible as a function of irradiation time at different wavelengths due to the photostationary state (above 80% trans-cis photoisomerization) of the azo aromatic moieties. The PPABLO containing 3.2 mol% azobenzene in water exhibited conformational changes from random coil to helix by the addition of methanol or sodium dodecyl sulphate (SDS). The photo-induced conformational change was observed in HFIP-water-SDS solvent mixtures, while no conformational change was seen in water and HFIP-water solvent mixtures. 相似文献
17.
Paolo Tosatti Joachim Horn Amanda J. Campbell David House Adam Nelson Stephen P. Marsden 《Advanced Synthesis \u0026amp; Catalysis》2010,352(18):3153-3157
The combination of an air‐stable iridium catalyst and the dipolar aprotic solvent dimethyl sulfoxide (DMSO) allowed, for the first time, the systematic exploitation of highly polar, functionalized amines in asymmetric allylic substitutions: low molecular weight, sp3‐rich chiral building blocks were obtained with physicochemical properties that will be valuable in the synthesis of lead‐like small molecules. 相似文献
18.
Extractive distillation is an important and useful technique for separating close boiling and azeotropic liquid mixtures. Solvent selectivity is the key to achieving success. In this paper, the relation of solvent selectivity uersus temperature for different mixed systems (C6H6 C6H12 DMSO,C6H6 C6H12 DMF, EtOH EA DMF DMSO, C6H6 C6 H12 DMF DMSO) was examined by the modified UNIFAC model, which is a well-tested method to select a solvent for extractive distillation.With increasing temperature, solvent selectivity was decreased. In addition, the influence of temperature on solvent selectivity was set forth for the first time by using the Clausius-Mosotti equation. 相似文献
19.
Tetrathiafulvalene tetrabenzoate (TTFTB) and several lanthanide ions self-assemble into metal-organic frameworks (MOFs) that exhibit a novel topology, a (3,3,3,6,6)-coordinated net, which features an unusual ligand coordination mode and stacking motif. The Yb and Lu MOFs are electrically conductive, with pellet conductivity values of 9(7) × 10−7 and 3(2) × 10−7 S/cm, respectively. The crystallographically-determined bond lengths indicate partial oxidation of the ligand, with close S ⋅ ⋅ ⋅ S contacts between ligands providing likely charge transport pathways in the material. Magnetometry reveals temperature-independent paramagnetism, consistent with the presence of ligand-based radicals, as well as weak antiferromagnetic coupling between Yb3+ centers. These results illustrate the diversity of MOF structures and properties that are accessible with the TTFTB ligand owing to its electroactive nature, propensity for intermolecular interactions, and conformational flexibility. 相似文献
20.
《The Journal of Supercritical Fluids》2010,54(1-3):121-130
Anti-solvent precipitation of xylans and mannans from dimethylsulfoxide (DMSO) or DMSO/water mixtures, and subsequent drying with supercritical carbon dioxide (scCO2) were developed into a useful technique for preparing spherical hemicellulose micro-particles. Depending on the type of hemicellulose, water content of DMSO, precipitation pressure and temperature, the particle size can be adjusted within a wide range from less than 0.1 to more than 5 μm. For example, fast super-saturation which can be achieved by applying supercritical conditions results in the formation of very small particles as mass transfer between the solvent DMSO and anti-solvent scCO2 is reduced to a minimum.Anti-solvent precipitation from aqueous DMSO (e.g., 10% water) allows for processing distinctly larger amounts of hemicelluloses compared to pure DMSO without the necessity of increasing the precipitation pressure. The formation of an additional inert aqueous phase increases the mass transfer resistance, which results in the formation of larger, stable agglomerates.Curiepoint pyrolysis GC/MS, gel permeation chromatography (GPC) and analysis of the monosaccharide composition of both the parent hemicellulosic material and the corresponding precipitates demonstrated that hemicelluloses can be purified from residual lignin by supercritical anti-solvent precipitation with carbon dioxide without altering the structure of the biopolymers. 相似文献