共查询到20条相似文献,搜索用时 12 毫秒
1.
Larisa Starovoytova Jiří Spěváček Lenka Hanyková Michal Ilavský 《Macromolecular Symposia》2003,203(1):239-246
1H NMR spectroscopy has been applied to the analysis of dynamic-structural changes during temperature-induced phase transition of non-ionized poly(N-isopropylmethacrylamide) (PIPMAm) and ionized copolymers of N-isopropylmethacrylamide with sodium methacrylate, all in D2O solutions with various polymer concentrations (c = 0.1-10 wt.-%) and ionic comonomer mole fractions (i = 0-10 mole %). It was found that the formation of compact globular-like structures during the phase transition is independent of polymer concentration for non-ionized samples; the presence of negative charges on the polymer chains leads to a dependence of the phase transition temperature on c and i. Virtually all PIPMAm segments are in globular-like structures for low polymer concentrations; for c ⩾ 1 wt.-%, this holds only for low content i of the ionic comonomer. An increase in c and i leads to a decrease in the fraction of polymer segments in globular-like structures; for samples with highest values of c and i, the phase transition was not observed. 相似文献
2.
Some possibilities of NMR spectroscopy (mainly spin-spin relaxation) in investigations of hydration and other polymer-solvent interactions during the temperature-induced phase separation in aqueous polymer solutions are described. A certain portion of water molecules bound in phase-separated mesoglobules was revealed. The residence time of the bound HDO for poly(vinyl methyl ether) (PVME)/D2O solution (c = 6 wt%) is 1.2 ms. With time a slow release of originally bound water from the respective mesoglobules was observed. For highly concentrated PVME/D2O solutions (c = 20–60 wt%), the residence time of bound HDO ≫ 2.7 ms and fractions of bound water unchanged even for 70 h were found. A similar behaviour as described above for water (HDO) was also found for EtOH molecules in PVME/D2O/EtOH solutions. 相似文献
3.
A. Ajji L. Choplin R. E. Prud'Homme 《Journal of Polymer Science.Polymer Physics》1991,29(13):1573-1578
Mixtures are expected to show anomalous behavior in their viscoelastic properties close to a critical point. In this study, the reheological behavior of blends of polystyrene and poly (vinyl methyl ether) below, close to, and above the phase separation temperature Ts was investigated. Rheological measurements were carried out at three different compositions in the melt. Below and far from Ts, a satisfactory superposition of the storage and loss moduli G' and G″ was observed at all temperatures and frequencies. Close to Ts deviations were observed for G' at low frequencies (the so-called terminal zone). Above Ts G″ values was still observed over the whole range of frequencies and temperatures. The deviations observed for G' near Ts can be interpreted as due to the presence of significant concentration fluctuations. Plots of log (G'/G″2) as a function of temperature were shown to be sensitive to this anomalous behavior. 相似文献
4.
Jiří Spěváček Larisa Starovoytova Lenka Hanyková Hana Kouřilová 《Macromolecular Symposia》2008,273(1):17-24
Summary: NMR relaxation and diffusion coefficient measurements revealed that a portion of water molecules is bound in mesoglobules formed in poly(N-isopropylmethacrylamide) (PIPMAm) and poly(vinyl methyl ether) (PVME) aqueous solutions above the LCST, with fast exchange between bound and free states (residence time ∼1 ms). Two types of bound water molecules were assigned to water bound inside mesoglobules and on their surface. For highly concentrated PVME/D2O solutions (c ≥ 20 wt%) a slow exchange was detected by NMR for bound water (residence time = 2.1 s). For PIPMAm aqueous solution IR spectra indicate a two-steps character of the phase transition. For PIPMAm in D2O/ethanol (EtOH) mixtures the globular structures were observed by NMR at 298 K for certain compositions of the mixed solvent (cononsolvency effect). Virtually no EtOH is bound in these globular structures, in contrast to the temperature-induced globular structures. 相似文献
5.
C. Malveau W. E. Baille X. X. Zhu W. T. Ford 《Journal of Polymer Science.Polymer Physics》2003,41(22):2969-2975
The local dynamics of three poly(propylene imine) dendrimers with hydrophilic triethylenoxy methyl ether terminal groups were studied in D2O by the measurement of the 1H NMR relaxation times, which were treated with the Lipari–Szabo model‐free approach. The results showed that the overall mobility increased with temperature and decreased with increasing dendrimer size. An Arrhenius trend was observed for both overall and local motions. The activation energy of overall tumbling increased from 11.3 to 17.5 kJ/mol with the dendrimer size. The local mobility decreased from the outer part to the inner part of the dendrimer and with the dendrimer size. The spatial restriction of local motions decreased with increasing temperature up to 55 °C and remained constant above 55 °C. Local motions were more restricted when the dendrimer size increased. The results showed that the hydrophilic end groups of the dendrimers were located preferentially at the periphery of the molecules and were extended in the aqueous environment. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2969–2975, 2003 相似文献
6.
Spin-lattice relaxation time, spin-spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy (2D NOESY) experiments of polyoxyethylene lauryl ether (Brij-35) micelles in aqueous solutions at a concentration of 100 times the critical micellar concentration (cmc) give direct evidence that the hydrophilic polyoxyethylene chains, staying in the exterior of the micellar core, are coiled, bent and aligned around the micellar core with a certain number of water molecules included. This hydrophilic layer is in contact with the solvent, water, keeping the micellar solution stable. 1H NMR relaxation time measurements show that the first oxyethylene group next to the alkyl chain participates in the formation of the surface area of the micellar core. The motion of the hydrophilic polyoxyethylene chains is less restricted as compared with the hy-drophobic alkyl chains. 相似文献
7.
Jiří Spěváček 《Macromolecular Symposia》2005,222(1):1-14
Some possibilities of 1H NMR spectroscopy in investigations of structural-dynamic changes and polymer-solvent interactions during the temperature-induced phase transitions in aqueous polymer solutions are described. Results obtained recently on D2O solutions of poly(vinyl methyl ether) (PVME), poly(N-isopropylmethacrylamide) (PIPMAm), negatively charged copolymers of N-isopropylmethacrylamide and sodium methacrylate, and PIPMAm/PVME mixtures are discussed. A markedly different rate of dehydration process in dilute solutions on the one hand, and in semidilute and concentrated solutions on the other hand, was revealed from 1H spin-spin relaxation measurements. 相似文献
8.
1H NMR study of the phase behavior of aqueous eutectic solutions using the inverse Laplace transform analysis of T2 relaxation
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Jessi A. Baughman G. Joseph Ray Szabo M. Christina Jane O. Werling Peter L. Rinaldi 《Magnetic resonance in chemistry : MRC》2017,55(10):928-935
High‐field 1H NMR T2 relaxation studies were used to characterize the changes in the physical phases of water, NaCl, and dextrose solutions over a temperature range of ?65 to 15 °C. The data were analyzed with the inverse Laplace transform and with a linear fit to the logarithm of the time domain signal. Two liquid phases were detected for the NaCl and dextrose solutions at lower temperatures and assigned to low and high concentrated solution domains. The high concentrated solution domain was found to be present between ?30 and ?5 °C in the NaCl solution and between ?55 and ?5 °C in the dextrose solution. Copyright © 2017 John Wiley & Sons, Ltd. 相似文献
9.
Marc B. Taraban Daniel J. Deredge Margaret E. Smith Katharine T. Briggs Yu Li Zhong-Xing Jiang Patrick L. Wintrode Yihua Bruce Yu 《Magnetic resonance in chemistry : MRC》2019,57(10):861-872
The conformational transition of a fluorinated amphiphilic dendrimer is monitored by the 1H signal from water, alongside the 19F signal from the dendrimer. High-field NMR data (chemical shift δ, self-diffusion coefficient D, longitudinal relaxation rate R1, and transverse relaxation rate R2) for both dendrimer (19F) and water (1H) match each other in detecting the conformational transition. Among all parameters for both nuclei, the water proton transverse-relaxation rate R2(1H2O) displays the highest relative scale of change upon conformational transition of the dendrimer. Hydrogen/deuterium-exchange mass spectrometry reveals that the compact form of the dendrimer has slower proton exchange with water than the extended form. This result suggests that the sensitivity of R2(1H2O) toward dendrimer conformation originates, at least partially, from the difference in proton exchange efficiency between different dendrimer conformations. Finally, we also demonstrated that this conformational transition could be conveniently monitored using a low-field benchtop NMR spectrometer via R2(1H2O). The 1H2O signal thus offers a simple way to monitor structural changes of macromolecules using benchtop time-domain NMR. 相似文献
10.
Bakhmutov VI 《Magnetic resonance in chemistry : MRC》2004,42(1):66-70
The deuterium spin-lattice relaxation times in (D2) ligands of W, Ru and Os complexes are reviewed and analyzed in terms of the fast internal (D2) motions: free rotation, librations and 180 degrees jumps. The analysis was performed using quadrupolar coupling constant (DQCC) parameters taken from the solid-state 2H NMR spectra and density function theory calculations. It is shown that the calculated DQCC values can be corrected for further use in interpretations of deuterium relaxation times for Ru and Os dihydrogen complexes. The resulting data led to a criterion for using the relaxation data to distinguish fast-spinning dihydrogen ligands. It is shown that the principal components of electric field gradient tensors at D in the dihydrogen ligands are oriented closer to M-D directions. 相似文献
11.
The mechanical properties of radiation cross-linked poly(vinyl methyl ether) hydrogels below and above the volume phase transition (VPT) under isobar conditions were studied. The viscoelastic properties as a function of radiation dose, radiation source and polymer concentration at the state of irradiation were examined. Increased radiation doses led to higher cross-linking densities and higher moduli. Hydrogels irradiated with -rays were much harder than those obtained with electron beam irradiation at the same radiation dose. It was found that the modulus strongly increased by up to 1 order of magnitude at a temperature of the VPT of about 37 °C. In the collapsed state at temperatures well above the VPT a frequency dependence of the E() moduli in the range 0.1–22 Hz was detected, indicating viscoelastic behavior. To study the influence of solvent quality on the modulus of the hydrogels, rheological measurements were performed in water, 2-propanol and cyclohexane. A scaling exponent for the modulus according to de Gennes (G2.25) was not found. Possible reasons for deviations (G3.54) on poly(vinyl methyl ether) hydrogels were discussed in the context of deviations from ideal networks. 相似文献
12.
Spin-lattice relaxation time, spin-spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy (2D
NOESY) experiments of polyoxyethylene lauryl ether (Brij-35) micelles in aqueous solutions at a concentration of 100 times
the critical micellar concentration (cmc) give direct evidence that the hydrophilic polyoxyethylene chains, staying in the
exterior of the micellar core, are coiled, bent and aligned around the micellar core with a certain number of water molecules
included. This hydrophilic layer is in contact with the solvent, water, keeping the micellar solution stable. 1H NMR relaxation time measurements show that the first oxyethylene group next to the alkyl chain participates in the formation
of the surface area of the micellar core. The motion of the hydrophilic polyoxyethylene chains is less restricted as compared
with the hydrophobic alkyl chains. 相似文献
13.
Li Song Jiaxiang Lin Yang He Jingqing Li Jing Sheng Shichun Jiang Dinghai Huang 《Journal of Polymer Science.Polymer Physics》2019,57(6):323-330
In the lower critical solution temperature phase separation of poly(vinyl methyl ether) aqueous solutions, the process corresponding to the weakening of the hydrogen bond interaction with increasing temperature is dominant and occurs over the entire concentration region of solutions and over a broad temperature range from 30 to 41°C, giving rise to the energetic enthalpic effect during phase separation, while the conformational change, that is, collapse of the swollen polymer coils, occurs only in the swelling polymer solution when the water concentration is above 38.3 wt %, giving rise to the entropic effect during phase separation. In addition, the entropic process corresponding to the collapse of the polymer coils occurs in a much narrow theta temperature range from 35.5 to 37°C. If the solution is held at a constant temperature for a sufficiently long time, 90% collapse of the polymer coils occurs in only the 0.5 °C temperature region between 35.5 and 36°C. Accordingly, in the enthalpic process, the most dramatic blueshift of the νC‐O bond peak occurs in the temperature range between 35 and 41°C, while this blueshift is only approximately 2 cm?1 in the temperature range from 30 to 35°C, prior to the collapse of the polymer coils due to the entropic effect. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 323–330 相似文献
14.
Li Song Jiaxiang Lin Yang He Jingqing Li Jing Sheng Shichun Jiang Dinghai Huang 《Journal of Polymer Science.Polymer Physics》2019,57(3):142-151
Time‐dependent demixing enthalpy recovery behavior of aqueous poly(vinyl methyl ether) (PVME) solutions exhibits distinct recovery characteristics in three concentration regions. The absence of recovery behavior below a water concentration of 38.3 wt % indicates that the PVME coil is in a globular state. The typically sigmoidal recovery behavior of demixing enthalpy above 38.3 wt % is ascribed to the reswelling of the collapsed polymer coils induced by the entropic effect. The increase in difference between the upper and lower limits indicates the continued swelling of the PVME coils. Above 65 wt %, a dominant diluting effect can be observed, and a much longer phase separation time is needed to reach the expected lower limit. In contrast, the recovery of demixing enthalpy in a wide range of water concentration (from 38.3 to 90 wt %) exhibits the same feature. The infrared spectroscopy results are in agreement with the above macroscopic differential scanning calorimetry results. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 142–151 相似文献
15.
J. M. Zhang G. B. Zhang J. J. Wang Y. L. Lu D. Y. Shen 《Journal of Polymer Science.Polymer Physics》2002,40(24):2772-2779
The Fourier transform infrared (FTIR) results are consistent with the differential scanning calorimetric results and verify the anomalous crystallization of water in 50% poly(vinyl methyl ether) aqueous solution during heating. Below about ?34 °C, the water/polymer complex was not damaged, and the water still associated with the polymer. When heating to about ?34 °C, the associated water started to free from the unpolar (methyl group) and polar‐site (ether‐oxygen group) interaction fields of polymer gradually. Then crystallization of water was induced in this system at temperatures ranging from ?34 to ?24 °C. The FTIR data also indicate that the structure of water started to change first upon forming strong H bonds among water molecules, and then the dehydration of the polymer began to proceed subsequently when the anomalous crystallization of water occurred. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2772–2779, 2002 相似文献
16.
2H NMR spin relaxation study of the soft segment motion in alternating ethylene–propylene copolymers
《Magnetic resonance in chemistry : MRC》2002,40(2):161-164
We synthesized three partially deuterated polymer samples, namely a poly(ethylene‐alt‐propylene) (EP) alternating copolymer, a poly(styrene‐b‐EP) diblock copolymer (SEP) and a poly(styrene‐b‐EP‐b‐styrene) triblock copolymer (SEPS). The 2H spin–lattice relaxation time, T1, of EP soft segments above their glass transition temperature was measured by solid‐state 2H NMR spectroscopy. It was found that the block copolymers had a fast and a slow T1 component whereas EP copolymer had only a fast component. The fast T1 components for SEP and SEPS are similar to the T1 value of EP above ca 20°C. The slow T1 component for SEP and SEPS exhibited a minimum at 60°C and approached the value of the fast component near the Tg of polystyrene. The motional behavior of the EP units for SEP is similar to that of SEPS over the entire range of temperature. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
17.
《Magnetic resonance in chemistry : MRC》2002,40(2):97-106
Solid‐state 1H → 19F and 19F → 1H cross‐polarization magic angle spinning (CP/MAS) NMR spectra have been investigated for a semicrystalline fluoropolymer, namely poly(vinylidene fluoride) (PVDF). The 1H → 19F CP/MAS spectra can be fitted by five Lorentzian functions, and the amorphous peaks were selectively observed by the DIVAM CP pulse sequences. Solid‐state spin‐lock experiments showed significant differences in T1ρF and T1ρH between the crystalline and amorphous domains, and the effective time constants, THF* and T1ρ*, which were estimated from the 1H → 19F CP curves, also clarify the difference in the strengths of dipolar interactions. Heteronuclear dipolar oscillation behaviour is observed in both standard CP and 1H → 19F inversion recovery CP (IRCP) experiments. The inverse 19F → 1H CP‐MAS and 1H → 19F CP‐drain MAS experiments gave complementary information to the standard 1H → 19F CP/MAS spectra in a manner reported in our previous papers for other fluoropolymers. The value of NF/NH (where N is a spin density) estimated from the CP‐drain curve is within experimental error equal to unity, which is consistent with the chemical structure. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
18.
H. Yuan L. Luo L. Zhang S. Zhao S. Mao J. Yu L. Shen Y. Du 《Colloid and polymer science》2002,280(5):479-484
1H NMR self-diffusion coefficient, spin–spin relaxation and two-dimensional nuclear Overhauser enhancement spectroscopy measurements
of sodium dodecyl sulfate (SDS) in poly(ethylene glycol) (PEG) aqueous solution show that SDS molecules start to self-aggregate
at a concentration of 3.3 mM, which is well below the normal critical micellar concentration (cmc). SDS micelles are formed
when the cmc is reached with PEG solubilized in their hydrophobic micellar cores.
Electronic Publication 相似文献
19.
S.-Z. Mao L.-Y. Zhu T.-Z. Wang M.-Z. Li E.-J. Wang X.-J. Miao X.-W. Fang H.-Z. Yuan Y.-R. Du 《Colloid and polymer science》2002,280(1):90-94
The dynamic properties of the micelles of a novel synthesized amphiphilic block copolymer, dendritic poly(benzyl ether)–poly(acrylic
acid) (Dendr.PBE-PAA), formed in aqueous solutions were studied by the 1H self-diffusion coefficient, relaxation measurements and 2D nuclear Overhauser enhancement spectroscopy. The experimental
results show that Dendr.PBE-PAA molecules self-aggregate in aqueous solution. The dynamic properties of the Dendr.PBE-PAA
micelles vary with their total concentration in the solution. The motion of the molecules in the micelles of a concentrated
solution is more restricted than that in a less concentrated one. The main chains of PAA are densely packed in the surface
layer of the hydrophobic core with the carboxyl side chain pointing to the aqueous medium and the hydrophobic phenoxy rings
stay in the interior. The self-aggregate becomes larger as the degree of polymerization of PAA increases. However the phenoxy
rings situated in the interior of the hydrophobic core become more loosely packed. n-Hexadecane is solubilized in the micelles. The optimal position of n-hexadecane is between the phenoxy rings next to the PAA chains.
Received: 25 January 2001 Accepted: 18 July 2001 相似文献
20.
1H NMR and IR spectroscopies were used to investigate the temperature-induced phase transition behaviour of poly(N-isopropylmethacrylamide-co-sodium methacrylate) [P(IPMAAm/MNa)] copolymers, containing in aqueous solutions negatively charged MNa units (i = 1-10 mol%), and the obtained results were compared with those obtained for poly(N-isopropylmethacrylamide) (PIPMAAm) homopolymer. For PIPMAAm/H2O solution, IR spectra indicate that the transition temperatures for the hydrophilic CO groups are slightly higher (by ∼ 2 K) in comparison with hydrophobic CH3 groups. The decreasing values of phase-separated fraction pmax and the decrescent hysteresis during gradual heating and cooling, both with increasing content of MNa units i in the copolymer, show that for copolymers with i ? 5 mol% the globular-like structures formed at temperatures above the respective LCST are rather porous and disordered with relatively low degree of polymer-polymer hydrogen bonding. While for P(IPMAAm/MNa) copolymers with i ? 5 mol% most water molecules are expelled from globular structures, for i < 5 mol% a certain portion of water (HDO) molecules is rather tightly bound in globular structures; at the same time no releasing process was detected for the bound water even for 90 h. 相似文献