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111.
Continuous chromatographic protein refolding 总被引:2,自引:0,他引:2
Column-based protein refolding requires a continuous processing capability if reasonable quantities of protein are to be produced. A popular column-based method, size-exclusion chromatography (SEC) refolding, employs size-exclusion matrices to separate unfolded protein from denaturant, thus refolding the protein. In this work, we conduct a comparison of SEC refolding with refolding by batch dilution, using lysozyme as a model protein. Lysozyme refolding yield was found to be extremely sensitive to the chemical composition of the refolding buffer and particularly the concentration of dithiothreitol (DTT) introduced from the denatured protein mixture. SEC refolding was not adversely affected by DTT carry-over as small contaminants in the denatured solution are separated from protein during the refolding operation. We also find that, contrary to previous reports, size-exclusion refolding on batch columns leads to refolding yields slightly better than batch dilution refolding yields at low protein concentrations but this advantage disappears at higher protein concentrations. As batch-mode chromatography would be the limiting step in a column based refolding downstream process, the batch column refolding method was translated to a continuously operating chromatography system (preparative continuous annular chromatography, P-CAC). It was shown that the P-CAC elution profile is similar to that of a stationary column, making scale-up and translation to P-CAC relatively simple. Moreover, it was shown that high refolding yields (72%) at high protein concentration (>1 mg ml(-1)) could be obtained. 相似文献
112.
Kaisa Helttunen Riia Annala Aku Suhonen Juho Iloniemi Elina Kalenius Gemma Aragay Pablo Ballester Heikki M. Tuononen Maija Nissinen 《化学:亚洲杂志》2019,14(5):647-654
The anion‐binding properties of three closely related oligoamide foldamers were studied using NMR spectroscopy, isothermal titration calorimetry and mass spectrometry, as well as DFT calculations. The 1H NMR spectra of the foldamers in [D6]acetone solution revealed partial preorganization by intramolecular hydrogen bonding, which creates a suitable cavity for anion binding. The limited size of the cavity, however, enabled efficient binding by the inner amide protons only for the chloride anion resulting in the formation of a thermodynamically stable 1:1 complex. All 1:1 chloride complexes displayed a significant favourable contribution of the entropy term. Most likely, this is due to the release of ordered solvent molecules solvating the free foldamer and the anion to the bulk solution upon complex formation. The introduction of electron‐withdrawing substituents in foldamers 2 and 3 had only a slight effect on the thermodynamic constants for chloride binding compared to the parent receptor. Remarkably, the binding of chloride to foldamer 3 not only produced the expected 1:1 complex but also open aggregates with 1:2 (host:anion) stoichiometry. 相似文献
113.
Schatte G Chivers T Tuononen HM Suontamo R Laitinen R Valkonen J 《Inorganic chemistry》2005,44(2):443-451
The hydrolysis of (t)BuNTe(mu-N(t)Bu)(2)TeN(t)Bu (1) with 1 or 2 equiv of (C(6)F(5))(3)B.H(2)O results in the successive replacement of terminal imido groups by oxo ligands to give the telluroxane-Lewis acid adducts (C(6)F(5))(3)B.OTe(mu-N(t)Bu)(2)TeN(t)Bu (2) and [(C(6)F(5))(3)B.OTe(mu-N(t)Bu)(2)Te(mu-O)](2) (3), which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. The Te=O distance in 2 is 1.870(2) A. The di-adduct 3 involves the association of four (t)()BuNTeO monomers to give a tetramer in which both terminal Te=O groups [d(TeO) = 1.866(3) A] are coordinated to B(C(6)F(5))(3). The central Te(2)O(2) ring in 3 is distinctly unsymmetrical [d(TeO) = 1.912(3) and 2.088(2) A]. The X-ray structure of (C(6)F(5))(3)B.NH(2)(t)()Bu (4), the byproduct of these hydrolysis reactions, is also reported. The geometries and energies of tellurium(IV) diimides and imido telluroxanes were determined using quantum chemical calculations. The calculated energies for the reactions E(NR)(2) + Te(NR)(2) (E = S, Se, Te; R = H, Me, (t)Bu, SiMe(3)) confirm that cyclodimerization of tellurium(IV) diimides is strongly exothermic. In the mixed-chalcogen systems, the cycloaddition is energetically favorable for the Se/Te combination. The calculated energies for the further oligomerization of the dimers XE(mu-NMe)(2)EX (E = Se, Te; X = NMe, O) indicate that the formation of tetramers is strongly exothermic for the tellurium systems but endothermic (X = NMe) or thermoneutral (X = O) for the selenium systems, consistent with experimental observations. 相似文献
114.
Holappa S Kantonen L Andersson T Winnik F Tenhu H 《Langmuir : the ACS journal of surfaces and colloids》2005,21(24):11431-11438
Polyion complexes (PICs) of anionic block copolymer poly(ethylene oxide)-block-poly(sodium methacrylate), PEO-block-(PMA)Na, and a cationic homopolymer, poly((methacryloyloxyethyl)trimethylammonium chloride), PMOTAC, have been studied by fluorescence spectroscopy. Pyrene and naphthalene singly labeled block copolymers were used with two different sodium methacrylate block lengths. The chain exchange between the stoichiometric PICs at the equilibrium state and the formation of the negatively charged PICs on addition of excess PEO-block-(PMA)Na to stoichiometric PIC solution were of interest. The chain exchange between the stoichiometric complexes was observed to occur via two mechanisms. The faster chain exchange occurs via insertion and expulsion of single chains, while merging and splitting of the PIC particles is behind the slower chain exchange event. Incorporation of an excess amount of the guest polyion into a stoichiometric PIC took place on further addition of the PEO-block-(PMA)Na. The same mechanisms were recognized in the overcharging process of the PICs as in the chain exchange between the stoichiometric PICs. 相似文献
115.
Dr. Ashley J. Holding Jingwen Xia Prof. Dr. Michael Hummel Harry Zwiers Matti Leskinen Dr. Daniel Rico del Cerro Dr. Sami Hietala Dr. Martin Nieger Dr. Marianna Kemell Jussi K. J. Helminen Dr. Vladimir Aseyev Prof. Dr. Heikki Tenhu Prof. Dr. Ilkka Kilpeläinen Dr. Alistair W. T. King 《Chemphyschem》2022,23(7):e202100635
We have identified cellulose solvents, comprised of binary mixtures of molecular solvents and ionic liquids that rapidly dissolve cellulose to high concentration and show upper-critical solution temperature (UCST)-like thermodynamic behaviour - upon cooling and micro phase-separation to roughly spherical microparticle particle-gel mixtures. This is a result of an entropy-dominant process, controllable by changing temperature, with an overall exothermic regeneration step. However, the initial dissolution of cellulose in this system, from the majority cellulose I allomorph upon increasing temperature, is also exothermic. The mixtures essentially act as ‘thermo-switchable’ gels. Upon initial dissolution and cooling, micro-scaled spherical particles are formed, the formation onset and size of which are dependent on the presence of traces of water. Wide-angle X-ray scattering (WAXS) and 13C cross-polarisation magic-angle spinning (CP-MAS) NMR spectroscopy have identified that the cellulose micro phase-separates with no remaining cellulose I allomorph and eventually forms a proportion of the cellulose II allomorph after water washing and drying. The rheological properties of these solutions demonstrate the possibility of a new type of cellulose processing, whereby morphology can be influenced by changing temperature. 相似文献
116.
Tina Borke Antti Korpi Fabian Pooch Heikki Tenhu Sami Hietala 《Journal of polymer science. Part A, Polymer chemistry》2017,55(11):1822-1830
The synthesis of poly(glyceryl glycerol) (PGG), a polymer featuring a polyethylene oxide backbone and 1,2‐diol groups in every repeating unit, is presented. PGG was prepared by monomer‐activated ring‐opening polymerization of (dl ?1,2‐isopropylidene glyceryl) glycidyl ether, introducing a functional azido‐ or bromo‐head group to each chain. The 1,2‐diol groups, which were released by acidic deprotection, readily reacted with boronic acid derivatives, enabling the attachment of functional moieties under mild aqueous conditions. PGG was conjugated to poly(l ‐lactide) (PLLA) via azide‐alkyne cycloaddition and the resulting copolymer assembled into nanoparticles of 70 nm diameter in aqueous solution. Labeling of the PGG–PLLA particles was achieved by simple mixing with a boronic acid‐functional fluorophore. The labeling efficiency was determined by fluorescence spectroscopy to be 85.5% for boronic acid‐functional rhodamine B compared with 0.2% for plain rhodamine B. The strong interaction of PGG with boronic acids is ascribed to its polyol structure. This study demonstrates the usefulness and versatility of PGG as a hydrophilic polymer for possible biomedical applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1822–1830 相似文献
117.
The synthesis and structural characterization of dicationic selenium and tellurium analogues of the carbodiphosphorane and triphosphenium families of compounds are reported. These complexes, [Ch(dppe)][OTf](2) [Ch = Se, Te; dppe = 1,2-bis(diphenylphosphino)ethane; OTf = trifluoromethanesulfonate], are formed using [Ch](2+) reagents via a ligand-exchange protocol and represent extremely rare examples of homoleptic pnictogen → chalcogen coordination complexes. The corresponding arsenic compounds were also prepared, [Ch(dpAse)][OTf](2) [Ch = Se, Te; dpAse = 1,2-bis(diphenylarsino)ethane], exhibiting the first instance of an arsenic → chalcogen dative bond. The electronic structures of these unique compounds were determined and compared to previously reported chalcogen dications. 相似文献
118.
Brown ZD Vasko P Fettinger JC Tuononen HM Power PP 《Journal of the American Chemical Society》2012,134(9):4045-4048
Reaction of the diarylgermylene Ge(Ar(Me(6)))(2) [Ar(Me(6)) = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(CH(3))(3))(2)] with tert-butyl isocyanide gave the Lewis adduct species (Ar(Me(6)))(2)GeCNBu(t), in which the isocyanide ligand displays a decreased C-N stretching frequency consistent with an n → π* back-bonding interaction. Density functional theory confirmed that the HOMO is a Ge-C bonding combination between the lone pair of electrons on the germanium atom and the C-N π* orbital of the isocyanide ligand. The complex undergoes facile C-H bond activation to produce a new diarylgermanium hydride/cyanide species and isobutene via heterolytic cleavage of the N-Bu(t) bond. 相似文献
119.
Individual and group loudness relations were obtained at a frequency in the region of impaired hearing for 100 people, 98 with bilateral cochlear impairment. Slope distributions were determined from absolute magnitude estimation (AME) and absolute magnitude production (AMP) of loudness; they were also derived from cross-modality matching (CMM) and AME of apparent length. With respect to both the means and the individual slope values, the two distributions closely agree. More than half of the measured deviations are less than 20%, with an overall average of -1.5%, meaning that transitivity is preserved for bilaterally impaired individuals. Moreover, over the stimulus range where cochlear impairment steepens the loudness function, both the group means and the individual slope values are clearly larger than in normal hearing. The results also show that, for groups of people with approximately similar losses, the standard deviation is a nearly constant proportion of the mean slope value giving a coefficient of variation of about 27% in normal and impaired hearing. This indicates, in accord with loudness matching, that the size of the slopes depends directly on the degree of hearing loss. The results disclose that loudness measurements obtained by magnitude scaling are able to reveal the operating characteristic of the ear for individuals. 相似文献
120.