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1.
The electric field dependence (up to 21 kV/cm) of the steady-state and decay signals has been examined on the four well-fractionated samples of poly(γ-benzyl-L -glutamate), [Glu(OBzl)]n, in N,N-dimethylformamide at 535 nm and 20°C. Together with the data previously obtained from the reversing-pulse electric birefringence [Ueda, K., Nomura, M. & Yamaoka, K. (1983) Biopolymers 22 , 2077–2090], the steady-state birefringence and field-free relaxation time were analyzed by a method that takes into account the polydispersity of the chain length. The weight-average chain length, (lw), permanent dipole moment, (μw), electric polarizability anisotropy, (Δαw), and the length-independent optical anisotropy factor were evaluated. The axial translation per residue was calculated for the [Glu(OBzl)]n helix, but the uncertainly involved in the weight-average molecular weights, determined from light scattering by different investigators, makes the determination of the exact conformation of [Glu(OBzl)]n difficult. The contribution of Δαw to electric field orientation was found to be significant, since Δαw was approximately proportional to lw. A linear relationship also exists between μw and lw, when the [Glu(OBzl)]n helix is shorter than about 1200 Å.  相似文献   

2.
The reversing-pulse electric birefringence (RPEB) technique was applied to the study of the temperature effect on the electrooptical and hydrodynamic properties of a fractionated [Glu(OBzl)]n sample, which is molecularly dissolved in cyclohexanone. The aim was to develop a standard analytical method for thermal denaturation and temperature-induced conformational transitions. The field-on reverse and steady-state signal, and the field-off decay signal, were measured at 535 nm and at a constant low field strength (ca. 3 kV/cm) over a wide temperature range (5–90°C). The steady-state birefringence and the relaxation time in the decay process were also measured at two constant temperatures (5 and 70°C) over a wide field strength range (E ≤ 20 kV/cm). By the combination of these two different sets of RPEB measurements, the unwanted effect of the high pulse field on polymer conformation at elevated temperatures could be minimized. Together with the density and viscosity of cyclohexanone measured between 5 and 95°C, the following quantities could be evaluated: the weight-average permanent dipole moment and polarizability anisotropy, the reduced optical anisotropy factor (Δg/n), the weight-average length, and the degree of polydispersity. All these quantities, except for Δg/n, were found to be almost independent of temperature (5–90°C) and concentration (1.54–4.27 mM).  相似文献   

3.
The hydrodynamic properties of α-helical poly(L -glutamic acid), (Glu)n in aqueous solutions and in mixtures of water with organic solvents have been interpreted in terms of the persistence length of the macromolecule. A modification of the method of Vitovskaya and Tsvetkov has been proposed in order to allow a more accurate determination of this parameter. The addition of an organic solvent increases strongly the rigidity of the helical conformation of (Glu)n. A comparison is made with some data of the literature of poly[N5-(3-hydroxy propyl)L -glutamine], [Gln(CH2)3OH]n, and poly(γ-benzyl-L -glutamate), [Glu(OBzl)]n.  相似文献   

4.
Poly(γ-benzyl-L -glutamate) having a terminal dimethylaminoanilide group as an electron donor (D) and a terminal 3,5-dinitrobenzoyl group as an electron acceptor (A) (A-[Glu(OBzl)]n-D) was synthesized by the N-carboxyanhydride method. Polymer samples were fractionated by gel chromatography and their number-average degrees of polymerization n were determined by the absorbances of the terminal chromophores. These polymers in chloroform and dimethylformamide solutions showed a charge-transfer (CT) absorption band around 455 nm, and the fraction of the polymer forming the CT complex was evaluated as a function of the chain length. CT absorption for short chains (n = 5 ~ 20) was attributed to intramolecular CT complex in which the A-[Glu(OBzl)]n-D chain takes cyclic conformations. An optimum chain length for the intramolecular CT was found to be n ? 10, where the [Glu(OBzl)]n chain may most easily bend back to form cyclic conformations. Stronger CT absorption observed for longer chains than n = 20 was shown to be intermolecular, and an intermolecular head-to-tail aggregation was found to be a cause of the strong CT interaction. All helical A-[Glu(OBzl)]n-D chains were found to form the head-to-tail dimers in chloroform solution.  相似文献   

5.
C M Deber  P D Adawadkar 《Biopolymers》1979,18(10):2375-2396
We have synthesized and characterized a series of cation-binding cyclic octapeptides which may function as potential ionophoric substances. The materials contain varying degrees of hydrophobic character, which was controlled systematically through the incorporation of N-alkylglycine residues where N-alkyl = methyl, n-hexyl, cyclohexyl, or n-decyl. The peptides reported include cyclo(Phe-Sar-Gly-Sar)2, cyclo(Glu(OBzl)-Sar-Gly-Sar-Glu(OBzl)-Sar-Gly-(N-decyl)Gly), cyclo(Glu(OBzl)-Sar-Gly-(N-decyl)Gly)2, cyclo(Glu(OBzl)-Sar-Gly-(N-hexyl)Gly)2, cyclo(Glu(OBzl)-Sar-Gly-(N-cyclohexyl)Gly)2, and the corresponding free diacid forms of the Glu-containing compounds. Using 13C- and 1H-nmr spectra, we demonstrated that the mixture of cis/trans peptide bond-isomer conformers, characteristic of the free-peptide benzyl esters in solution, was converted to unique C2-symmetric, presumably all-trans conformers on complexation with calcium ions. Cation-transport experiments, using the thick-liquid model of transport in a Pressman cell, established that these compounds transport a variety of cations and that one peptide examined in detail, cyclo(Glu(OBzl)-Sar-Gly-(N-decyl)Gly)2 (selectivity Ca2+ > Na+ > K+ > Mn2+ > Cu2+ > Mg2+ > Co2+ > Zn2+), transports calcium about an order of magnitude more efficiently than magnesium.  相似文献   

6.
Synthetic cyclic octapeptides of general structure cyclo[Glu(γOBzl)-Sar-Gly-(N-R)Gly]2 (R = n-hexyl and cyclohexyl) transport calcium ions selectively across organic phases and phospholipid membranes. We have now used proton nmr spectroscopy (360 MHz) to study the solution conformation(s) of their calcium complexes. When Ca(ClO4)2 was added to solutions of these peptides in CDCl3, nmr spectra of the resulting calcium complexes were characteristic of a single C2-symmetric conformer. From a Karplus-Bystrov analysis of vicinal coupling constants in both the peptide backbone and Glu side chain (treated as an ABCCMX spin system), in conjuction with model-building studies, a structure was proposed in which the calcium ion is bound in an octahedral-type complex by the four (coplanar) carbonyl groups of the (all-trans) Glu-Sar and Gly-(N-R)Gly peptide bonds. Occurrence of preferred rotamers about Glu side chain Cα–Cβ bonds indicated that restricted rotation in peptide side chains arises upon calcium binding.  相似文献   

7.
Nps-[Glu(OBzl)]6-NHEt has been prepared by coupling Nps-[Glu(OBzl)]2-OH with HCl,H-[Glu(OBzl)]4-NHEt by means of dicyclohexylcarbodiimide. The ir spectra of its nujol mull show that the hexapeptide has the β-structure of antiparallel chains. When it is dissolved in dioxane or ethylene dichloride, the hexapeptide consists of a mixture of the β-form and the solvated σ-form, but the β-form can exist only above a certain critical concentration. The critical concentration is about 0.4g dl?1 in dioxane and 0.08g dl?1 in ethylene dichloride, and the content of β-form increases with increasing concentration above it. The CD of the dioxane and ethylene dichloride solutions shows concentration dependence in visible and uv regions.  相似文献   

8.
Three families of thiol peptides are induced by cadmium in maize   总被引:10,自引:0,他引:10  
Phytochelatins ((γGluCys)nGly) are synthesized from glutathione by plants exposed to metals like Cd2+, Cu2+ and Zn2+. An intracellular complex formed by phytochelatins with Cd2+ and sulfide is thought to detoxify the metal possibly by sequestration in the vacuole. It was found that maize seedlings exposed to Cd2+ produced phytochelatins and two additional families of cysteina-containing peptides, (γGluCys)n and (γGluCys)nGlu. All thiol peptides with n = 2 and 3 were purified and their structure characterized by tandem mass spectrometry. For maize plants exposed to Cd2+ for 7 days, phytochelatins were synthesized preferentially in the first 24 h whereas the amounts of (γGluCys)n and (γGluCys)nGlu were the highest thereafter. This was probably due to an initial large pool of glutathione available in control plants compared with a dearth of γGluCys and no detectable γGluCysGlu. The (γGluCys)nGlu peptides were induced exclusively by Cd2+ as they were below the detection limit in control seedlings that contained low amounts of phytochelatins and (γGluCys)n. Since the Cys moiety of the peptides is essential for binding Cd2+, a role for accumulated (γGluCys)n and (γGluCys)nGlu in detoxifying Cd2+ in plants must be considered.  相似文献   

9.
Small-angle x-ray scattering of poly(γ-methyl-L -glutamate), [Glu(OMe)]n, in m-cresol and in pyridine was measured to determine the mass per unit length, Mq, and the radius of gyration of the cross section, 〈S1/2. It was confirmed from the values of Mq that [Glu(OMe)]n exists in an α-helical conformation in these solvents. It was elucidated from the calculations on 〈S1/2 that the side chains come in moderately close contact with the main chain in these solvents. It was indicated from the analysis of the outer portion of the scattering curves that the side-chain conformation varied depending on the solvent.  相似文献   

10.
The cupric complexes of poly(Nε-acetoacetyl-L -lysine), [Lys(Acac)]n′ poly(Nδ-acetoacetyl-L -ornithine), [Orn(Acac)]n′ and poly(Nγ-acetoacetyl-L -diaminobutyric acid), [A2bu-(Acac)]n, as well as of the model compound n-hexyl acetoacetamide, have been investigated by means of absorption, potentiometric, equilibrium dialysis, and CD measurements. While in the complex of the model compound, one chelating group is bound to one cupric ion, in the polymeric complexes two β-ketoamide groups are bound to Cu(II) under the same experimental conditions. The binding constant of cupric ions to the three polymers and the formation constant of the Cu(II)-nhexylacetoacetamide complex have been evluated. Investigation on the chiroptical properties of the three polymeric complexes shows that the peptide backbone does not undergo conformational transitions, remaining α-helical when up to 20% of the side chains are bound to Cu(II). The optical activity of the β-ketoamide chromophores is substantially affected by complex formation and is discussed in terms of asymmetric induction from the chiral backbone.  相似文献   

11.
Poly(Glu(OBzl)-Gly)n, poly(Glu-Gly)n, poly(Gly)-(Glu(OBzl)-Gly), and poly(Gly-Glu-Gly) were synthesized from the pentachlorophenyl esters of the sequential monomer. Both of the polymers containing free glumatic-acid residues are soluble in water, as is the lower molecular weight fraction of the polytripeptides with the benzyl ester in place. Circular dichroism studies and infrared dichroism studies suggest that the 21 helix is favored for the polydipeptide with removal of the benzyl ester reducing the conformational integrity. The polytripeptide showed evidence of 31 helix in addition to the 21 form, depending on solvent. A rationale for the conformations observed is developed based on the bulkiness of the side-chain residues and conformational stabilization, in certain cases, by hydrophobic interactions between the benzyl ester groups.  相似文献   

12.
Poly-β-benzyl-L -aspartate (poly[Asp(OBzl)]) forms either a lefthanded α-helix, β-sheet, ω-helix, or random coil under appropriate conditions. In this paper the Raman spectra of the above poly[Asp(OBzl)] conformations are compared. The Raman active amide I line shifts from 1663 cm?1 to 1679 cm?1 upon thermal conversion of poly[Asp(OBzl)] from the α-helical to β-sheet conformation while an intense line appearing at 890 cm?1 in the spectrum of the α-helix decreases in intensity. The 890 cm?1 line also displays weak intensity when the polymer is dissolved in chloroform–dichloroacetic acid solution and therefore is converted to the random coil. This line probably arises from a skeletal vibration and is expected to be conformationally sensitive. Similar behavior in the intensity of skeletal vibrations is discussed for other polypeptides undergoing conformational transitions. The Raman spectra of two cross-β-sheet copolypeptides, poly(Ala-Gly) and poly(Ser-Gly), are examined. These sequential polypeptides are model compounds for the crystalline regions of Bombyx mori silk fibroin which forms an extensive β-sheet structure. The amide I, III, and skeletal vibrations appeared in the Raman spectra of these polypeptides at the frequencies and intensities associated with β-sheet homopolypeptides. Since the sequential copolypeptides are intermediate in complexity between the homopolypeptides and the proteins, these results indicate that Raman structure–frequency correlations obtained from homopolypeptide studies can now be applied to protein spectra with greater confidence. The perturbation scheme developed by Krimm and Abe for explaining the frequency splitting of the amide I vibrations in β-sheet polyglycine is applied to poly(L -valine), poly-(Ala-Gly), poly(Ser-Gly), and poly[Asp(OBzl)]. The value of the “unperturbed” frequency, V0, for poly[Asp(OBzl)] was significantly greater than the corresponding values for the other polypeptides. A structural origin for this difference may be displacement of adjacent hydrogen-bonded chains relative to the standard β-sheet conformation.  相似文献   

13.
14.
Antimycinone A3, which is a neutral fragment of mild alkaline hydrolysate of antimycin A3, and its stereoisomers were synthesized stereoselectively from methyl trans-2-n-butylpent-3-enoate or methyl cis-2-n-butylpent-3-enoate, and natural antimycinone A3 was proved to possess Hα-Hβ and Hβ-Hγ trans configuration.  相似文献   

15.
A A Ribeiro  R Saltman  M Goodman 《Biopolymers》1985,24(12):2431-2447
The syntheses of three series of glutamate oligopeptides attached to a macromolecular solubilizing polyoxyethylene (POE) group Boc-[Glu(OMe)]n-OPOE, Ac-[Glu(OMe)]n-OPOE, pGlu-[Glu(OMe)]n?1-OPOE (n ? 1–7) and their various analogs specifically deuterated at individual α-CH positions using the liquid-phase method of peptide synthesis are described. It was shown that stepwise synthesis using the symmetrical anhydride gave homo-oligopeptides that are analytically pure. Fragment condensation methods using DCC-HOBt yield POE-peptides with POE-HOBt impurities but the peptide synthesis may be carried stoichiometrically with smaller quantities of amino acid derivatives. 360 MHz 1H-nmr conformational studies of these homo-oligopeptides in DMSO-d6 are presented. The α-deuterated peptides are shown to allow unequivocal homoligopeptide backbone NH assignments.  相似文献   

16.
Abstract

The metabolism of Thiobacillus ferrooxidans involves electron transfer from the Fe+2 ions in the extracellular environment to the terminal oxygen in the bacterial cytoplasm through a series of periplasmic proteins like Rusticyanin (RCy), Cytochrome (Cyt c4), and Cytochrome oxidase (CcO). The energy minimization and MD studies reveal the stabilization of the three redox proteins in their ternary complex through the direct and water mediated H-bonds and electrostatic interaction. The surface exposed polar residues of the three proteins, i.e., RCy (His 143, Thr 146, Lys 81, Glu 20), Cyt c4 (Asp 5, 15, 52, Ser 14, Glu 61), and CcO (Asp 135, Glu 126, 140, 142, Thr 177) formed the intermolecular hydrogen bonds and stabilized the ternary complex. The oxygen (Oεl) of Glu 126, 140, and 142 on subunit II of the CcO interact to the exposed side-chain and Ob atoms of the Asp 52 of Cyt c4 and Glu 20 and Leu 12 of RCy. The Asp 135 of subunit II also forms H-bond with the Nε atom of Lys 81 of RCy. The Oεl of Glu 61 of Cyt c4 is also H-bonded to Oγ atom of Thr 177 of CcO. Solvation followed by MD studies of the ternary protein complex revealed the presence of seven water molecules in the interfacial region of the interacting proteins. Three of the seven water molecules (W 79, W 437, and W 606) bridged the three proteins by forming the hydrogen bonded network (with the distances ~ 2.10–2.95 Å) between the Lys 81 (RCy), Glu 61 (Cyt c4), and Asp 135 (CcO). Another water molecule W 603 was H-bonded to Tyr 122 (CcO) and interconnected the Lys 81 (RCy) and Asp 135 (CcO) through the water molecules W 606 and W 437. The other two water molecules (W 21 and W 455) bridged the RCy to Cyt c4 through H-bonds, whereas the remaining W 76 interconnected the His 53 (Cytc4) to Glu 126 (CcO) with distances ~ 2.95–3.0 Å.  相似文献   

17.
High poly(3-hydroxybutyrate) (PHB) content and volumetric productivity were achieved by fed-batch culture of Halomonas boliviensis using a defined medium. Initial shake flask cultivations in a minimal medium revealed that the growth of H. boliviensis was supported only when the medium was supplemented with aspartic acid, glycine, or glutamine. Addition of 0.1% (w/v) glutamine in the medium resulted in the highest cell dry weight (CDW; 3.9 g l−1). Glutamine was replaced by the less expensive monosodium glutamate (MSG) in the medium without any notable change in the final cell density. Effect of initial concentrations of NH4Cl and K2HPO4 on cell growth and PHB accumulation by H. boliviensis was then analyzed using a fed-batch fermentation system. The best conditions for PHB production by H. boliviensis were attained using 0.4% (w/v) NH4Cl and 0.22% (w/v) K2HPO4 and adding MSG intermittently to the fermentor. Poly(3-hydroxybutyrate) content and CDW reached 90 wt.% and 23 g l−1, respectively, after 18 h of cultivation. In order to increase CDW and PHB content, MSG, NH4Cl, and K2HPO4 were initially fed to the fermentor to maintain their concentrations at 2%, 0.4%, and 0.22% (w/v), respectively, and subsequently their feed was suppressed. This resulted in a CDW of 44 g l−1, PHB content of 81 wt.%, and PHB volumetric productivity of 1.1 g l−1 h−1.  相似文献   

18.
Marc Le Bret 《Biopolymers》1980,19(3):619-637
Closed random Gaussian polygonal chains of N (6 < N < 150) bonds of equal length b and thickness d have been generated on a computer. The knot type, the writhing number w, the radius of gyration, and the average of the inverse of the distance between two apices have been determined for each chain. For all the studied knot types—0, 31, 41, 51, and 52—the probability density of finding a given w is Gaussian. The Gaussian is centered about 0 for the amphichiral knots. Therefore, for long circular DNAs, the contribution to the supercoiling energy, which depends on w only, may be considered as purely entropic and may be expressed as ARTw2/N, in agreement with previous semiempirical considerations. The parameter A increases with chain thickness, it decreases as N gets larger but rapidly reaches a plateau. Comparison with experimental data from the literature would suggest that the ratio of the writhing to the constraint increases with ionic strength. The ratio of sedimentation constant of the supercoiled DNA to the sedimentation constant of the nicked DNA varies as N1/4 (w/N)2, and therefore depends on the writhing density and on the length of the DNA.  相似文献   

19.
Electric birefringence measurements of suspensions of T3 and T7 bacteriophages in 10?2 M phosphate buffer, pH 6.9, show that there is a difference in their rotational diffusion coefficient. The values corrected to 25°C and water viscosity are D25,w = 4630 ± 130 sec?1 and D25,w = 5290 ± 260 sec?1 for T3 and T7, respectively. The value obtained from shell model calculations (according to Filson and Bloomfield) is D25,w = 4500 ± 600 sec?1. The apparent permanent dipole moments are 4.5 × 10?26 C·m and 1.7 × 10?26 C·m for T3 and T7, respectively. For both phage particles the intrinsic optical anisotropy is +7.2 × 10?3. It is shown that this anisotropy is mainly due to the DNA molecule inside the head of the phage. Its positive value means that there exists an excess orientation of the DNA helix perpendicular to the symmetry axis of the particle. For T7 an unexpectedly large increase of Δns and Ksp occurs at a glycerol concentration of about 30% (v/v). This increase is interpreted as being caused by a change of the shape of the particle and/or a change in the secondary structure of the DNA inside the head of the bacteriophage.  相似文献   

20.
The α-helical from of poly(L -glutamic acid) [α-poly(Glu)] gives rise to the same amide I and III lines as α-poly(γ-benzyl-L -glutamate) at 1652 and 1296 cm?1, respectively. The latter is a superposition of the amide III line near 1290 cm?1 and a line deu to vibrational made of CH2 groups of the side chain near 1300 cm?1. A line at 924 cm?1 is tentatively identified as characteristics of α-poly(Glu). Both the β1- and β2- forms of poly(Glu) give rise to characteristic of β-amide. III frequencies that are similar because of their similar backbone structures. Differences in the conformations of their side chains and in the environments of the backbone are reflected in the region 800–1200 cm?1 and in the amide I. A line at 1042 cm?1 and a pair at 1021 and 1059 cm?1 are tentatively assigned as characteristic of β1-poly(Glu) and β2-poly(Glu), respectively. The α-β2 transition in poly(L -Glu78L -Val22) is shown by the appearance of all the β2-characteristic lines in the thermally transformed sample. The same features observed in poly(L -Glu95L -Val5) also indicate that the α-β2 transition of poly(Glu) is facilitated by the presence of L -valine and that the content of L -valine is not critical for this purpose. Investigation of the Raman spectra of the calcium, strontium, barium and sodium slats of poly(Glu) shows that these salts, under the conditions of preparation used, all the have random-coil conformations.  相似文献   

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