Mri measurements of T1, T2 and D for gels undergoing volume phase transition

Gels consist of crosslinked polymer network swollen in solvent. The network of flexible long-chain molecules traps the liquid medium they are immersed in. Some gels undergo abrupt volume change, a phase transition process, by swelling-shrinking in response to external stimuli changes in solvent composition, temperature, pH, electric field, etc. We report that during volume phase transition changes of NMR longitudinal relaxation time T(1), NMR transverse relaxation time T(2), and diffusion coefficient D of the PMMA gel, and D of the NIPA gel. We describe how the gels were synthesized and the reason of using the snapshot FLASH imaging sequence to measure T(1), T(2), and D. Since T(1), T(2) and D maps have identical field of view and data are extracted from identical areas from their respective maps, these values can be correlated quantitatively on a pixel-by-pixel basis. Thus a complete set of NMR parameters is measured in-situ: the gels are in their natural state, immersed in the liquid, during the phase transition. The results of spectroscopic method agree with that of snapshot FLASH imaging method. For the PMMA gel T(1), T(2) and D decrease when gels undergo volume phase transition between deuterated acetone concentration of 30% and 40%. At its contracted state, T(1) is reduced to a little less than one order of magnitude, T(2) over two orders of magnitude, and D over one order of magnitude, smaller from values of PMMA gel at the swollen state. At an elevated temperature of 54 degrees C the thermosensitive NIPA gel is at a contracted state, with its D reduced to almost one order of magnitude smaller from that of the swollen NIPA at room temperature.     

Evaluation of dual-frequency multi-angle ultrasound on physicochemical properties of tofu gel and its finished product by TOPSIS-entropy weight method

The effects of dual-frequency (40 + 20 kHz) and multi-angle ultrasound (0°, 30°, 45°) on the coagulation state, network structure, flavor and protein conformation of tofu gel were studied. The results showed that the gel flavor of 40 + 20 kHz 0° group was the best and fluorescence intensity was low. The gel flavor in the 40 + 20 kHz 30° group was better than the group without ultrasound, and hydrophobic interaction and disulfide bond content was the largest. Meanwhile, the degree of protein cross-link was increased. The gel in 40 + 20 kHz 45° group had tightly gel state, high thermal stability, but poor flavor. Combined with The Order Preference by Similarity to Ideal Solution (TOPSIS)-entropy weight method, the 40 + 20 kHz 30° group, was the best ultrasonic treatment of gel. It can change the interaction between proteins, promote protein cross-link, and form a uniform and dense gel network. Finally, the hardness and moisture content of finished tofu were increased significantly, and the quality was improved.     

Temperature Effect on the Elasticity of Acrylamide-n-Isopropylacrylamide Copolymers

Acrylamide (AAm) – N-isopropylacrylamide (NIPA) copolymers were prepared via free radical crosslinking copolymerization with various weight percentages (wt%) of AAm and NIPA. The temperature dependence of the compressive elastic modulus, G, and toughness, U_T, of the PAAm- NIPA copolymers due to a volume phase transition was found using a compressive testing technique. It was observed that the compressive elastic modulus increased comprehensively when the temperature was increased between 30°C and 60°C. The PAAm- NIPA copolymers presented higher values of the compressive elastic modulus than pure NIPA above the lower critical solution temperature (LCST) (NIPA exhibits a volume phase transition from hydrophilic to hydrophobic in water at 31°C) and their compressive elastic modulus and toughness had a strong temperature dependence.     

Thermo-sensitive N-n-propylacrylamide gels

Thermo-sensitive gels were prepared by irradiating aqueous solutions of poly(N-n-propylacrylamide) (NNPA) and its copolymers with acrylic acid (AA) with γ-rays from a ⁶⁰Co source. The equilibrium swelling volume of the gel in water was determined as a function of temperature. NNPA gel showed a discontinuous and reversible volume phase transition. The transition temperature and the volume change at the transition decreased with irradiation time. The transition temperature was approximately 12°C lower than that of poly(N-isopropylacrylamide) gel. A discontinuous volume transition was also observed in the copolymer gels of NNPA and AA. The dependence of the transition temperature on the concentration of carboxyl groups revealed a marked difference depending on whether they were protonated or dissociated. For gels having side groups of COONa, the transition temperature rose and the volume change at the transition was elevated as the COONa concentration increased. In contrast, an increase in the COOH concentration resulted in a decrease in the transition temperature. These results are discussed in terms of an equation of state constructed based on scaling theory.     

Phase transitions in lyotropic nematic gels

In this paper, we discuss the equilibrium phases and collapse transitions of a lyotropic nematic gel immersed in an isotropic solvent. A nematic gel consists of a cross-linked polymer network with rod-like molecules embedded in it. Upon decreasing the quality of the solvent, we find that a lyotropic nematic gel undergoes a discontinuous volume change accompanied by an isotropic-nematic transition. We also present phase diagrams that these systems may exhibit. In particular, we show that coexistence of two isotropic phases, of two nematic phases, or of an isotropic and a nematic phase can occur. Received 15 February 2002 and Received in final form 14 June 2002     

Phase coexistence and dynamic properties of water in nanopores

The dynamical properties of a confined fluid depend strongly on the (spatially varying) density. Its knowledge is therefore an important prerequisite for molecular-dynamics (MD) simulations and the analysis of experimental data. In a mixed Gibbs ensemble Monte Carlo (GEMC)/MD simulation approach we first apply the GEMC method to find possible phase states of water in hydrophilic and hydrophobic nanopores. The obtained phase diagrams evidence that a two-phase state is the most probable state of a fluid in incompletely filled pores in a wide range of temperature and level of pore filling. Pronounced variations of the average and local densities are observed. Subsequently, we apply constant-volume MD simulations to obtain water diffusion coefficients and to study their spatial variation along the pore radius. In general, water diffusivity slightly decreases in a hydrophilic pore and noticeably increases in a hydrophobic pore (up to about 40% with respect to the bulk value). In the range of gradual density variations the local diffusivity essentially follows the inverse density and the water binding energy. The diffusivity in the quasi-two-dimensional water layers near the hydrophilic wall decreases by 10 to 20% with respect to the bulk value. The average diffusivity of water in incompletely filled pore is discussed on the basis of the water diffusivities in the coexisting phases.Received: 1 January 2003, Published online: 14 October 2003PACS: 61.20.Ja Computer simulation of liquid structure - 64.70.Fx Liquid-vapor transitions     

Evaluation of Properties and Structural Transitions of Poly-L-lysine: Effects of pH and Temperature

Abstract

The structural response to temperature and pH changes of poly-l-lysine (PLL) has been studied by a variety of experimental methods including turbidimetry, dynamic light scattering, and Zeta potential analysis. The experimental results and the molecular dynamics simulations showed that the PLL structural transitions were a result of a competition between electrostatic repulsion, which promotes an extended state, and the hydrophobic effect, which favors a compact state. In fact, as the pH was decreased, the PLL conformation changed from α-helix to the random coil and the hydrophilic volume increases resulted in a transition to spherical micelles which then swelled due to charge-charge repulsions. Following a rise in temperature and/or at high pH, PLL undergoes the α-helix-to-β-sheet transition and reacted more rapidly to form hydrophobic aggregates.     

不同临界保留因子下天然有机物亲疏水组分光谱特性

吸附树脂层析法是表征环境水样有机物亲疏水组分分布的常用方法。作为柱层析的基本参数,临界保留因子对亲疏水物质的吸附及分离效果具有潜在影响。以河北某水库的水样为例,将有机物分为亲水物(HIS)、疏水酸(HOB)、疏水碱(HOA)和疏水中性物(HON),考察了在不同临界保留因子分离条件下(k′_cr=5, 10, 25, 50, 100)亲疏水组分有机物含量分布,并着重考察了其光谱学特性。研究发现,亲疏水组分的浓度分布取决于k′_cr值的设置,疏水组分的比例和疏水程度随k′_cr的增大而增大。在250~280 nm波长范围内,亲水组分HIS的紫外吸光度随k′_cr的增高而增高,而疏水组分HOA和HOB则呈现相反趋势,亲水与疏水组分之间的紫外光谱差异性随k′_cr增大而增大。此外,疏水组分单位质量浓度的吸光度对k′_cr的取值敏感,推测k′_cr可能影响所得组分的芳香族官能团性质。进一步考察了各组分的三维荧光光谱,并采用荧光区域积分和荧光指数对图谱进行解析。结果表明,亲疏水组分的荧光峰形态、荧光区域分布和荧光团密度与k′_cr值有关,荧光指数BIX,HIX_em和Peak T/C对k′_cr的取值敏感,说明k′_cr可能对所得组分的具体化学组成乃至迁移转化行为产生影响。因此在分离并表征环境水样的亲疏水组分分布时,应特别注意临界保留因子的设置并明确标明其取值。     

Fluorescence Investigations of “Smart” Microgel Systems

Fluorescence techniques, including lifetime, quenching, and time-resolved anisotropy measurements (TRAMS), were used to study microgel systems based upon N-isopropylacrylamide (NI-PAM) using pyrene as a fluorescent probe. These experiments have revealed that poly(N-isopropylacrylamide) (PNIPAM) nanoparticles undergo a phase transition at a lower critical solution temperature (LCST), of ca. 34°C, which involves collapse of the particles into compacted, hydrophobic spheres. A degree of control over the LCST has been achieved by copolymerization of NIPAM with varying amounts of dimethylacrylamide (DMAC). Incorporation of DMAC into the gel has the effect of changing the hydrophobic to hydrophilic balance and shifts the LCST to a higher temperature. Fluorescence methods indicate that the NIPAM/DMAC gels are of a more open, water-swollen nature above the LCST than that of their PNIPAM counterparts.     

荧光光谱研究含1,5取代萘刚性生色基双分子膜的相变

用荧光光谱研究了系列双亲物ＣｎＮａｐｈ（１,５）Ｃ６Ｎ＋（ｎ＝１６,１２,１０,８,６和４）聚集体的热致相变,发现荧光强度随温度升高发生了急剧变化,归因于聚集体从凝胶态到液晶态的相变。实验结果表明,尾链长短直接影响聚集体结构和相变温度Ｔｃ高低：尾链长,聚集体堆积密度大,荧光强度强,Ｔｃ高;反之亦反。荧光光谱的实验结果与透射电镜和ＤＳＣ研究结果一致。     

Selective interaction water-hydrophilic/hydrophobic impurities observed by four-photon Brillouin spectroscopy

The four-photon scattering spectra of water in the aqueous solution/suspension of various hydrophilic/hydrophobic impurities in the range ±3 cm^?1 (±90 GHz) have been observed. We have found the strong dependence of the Brillouin resonance frequency upon the connectivity of the impurities and water molecules. The Brillouin shift is attributed to the local restructuring of the hydrogen bond network in water inside the interface layer that is sensitive to the hydrophilic/hydrophobic properties. In fact, it results in variations in the isothermal compressibility and sound velocity.     

Water behavior in the neighborhood of hydrophilic and hydrophobic membranes: Lessons from molecular dynamics simulations

The study of properties of water in the vicinity of surfaces poses a fascinating challenge. In this article we studied the behavior of water molecules in the neighborhood of membranes. We addressed the question of how these water molecules are influenced by the membranes’ hydrophilicity. Three systems were studied through molecular dynamics simulations: water in the presence of a hydrophilic membrane (PL), water in the presence of a hydrophobic (PB) one and water in the absence of membranes (BULK). Additionally, in order to study the dependence of the effect of the membrane on the behavior of neighboring water molecules with temperature, each system was simulated at three different temperatures (K): 250, 300 and 350. For each condition, kinetic and structural features were studied. The first feature involved the calculation of diffusion coefficients and activation energy. The second feature was evaluated through the study of water density and hydrogen bond distribution. From the present study we concluded that: (1) density studies underestimate the influence of both hydrophilic and hydrophobic membranes on the neighboring water molecules; (2) the hydrophilic and hydrophobic membranes disturb the hydrogen bond network within distances ranging from 1 to 8 nm, depending on the nature of the membrane and the temperature conditions; (3) the presence of a hydrophobic surface results in an enhancement of the natural hydrogen bond network present in liquid water, to a greater extent than what even an ordered Ih ice structure is able to achieve (i.e. PL membrane); (4) the structural enhancement due to the presence of a hydrophobic surface involves roughly 18 to 24 water hydration layers, for ambient and above temperature conditions.     

Structure of a collapsed polymer chain with stickers: a single- or multiflower?

Using an amphiphilic copolymer with evenly spaced hydrophobic styrene segments (stickers), poly(N-isopropylacrylamide-s-styrene), we recently confirmed a long-standing prediction that such a copolymer chain in a solvent selectively poor for the stickers could self-fold from a random coil to a single-flowerlike core-shell nanostructure. Moreover, we found that the self-folding involves the movement of the sticks to the center and the transition from the random coil to the collapsed globule passes through a proposed ordered coil state.     

Interface water-induced hydrophobic carbon chain unfolding in water

The folding and unfolding of the carbon chain, which is the basic constitutional unit of polymers,are important to the performance of the material. However, it is difficult to regulate conformational transition of the carbon chain, especially in an aqueous environment. In this paper, we propose a strategy to regulate the conformational transition of the carbon chain in water based on the all-atom molecular dynamics simulations. It is shown that the unfolded carbon chain will spontaneously collapse into the folded state, while the folded carbon chain will unfold with an external electric field. The regulation ability of the electric field is attributed to the electric field-induced redistribution of interface water molecules near the carbon chain. The demonstrated method of regulating conformational transition of the carbon chain in water in this study provides an insight into regulating hydrophobic molecules in water, and has great potential in drug molecule design and new polymer material development.     

Core collapse supernovae in the QCD phase diagram

We compare two classes of hybrid equations of state with a hadron-to-quark matter phase transition in their application to core collapse supernova simulations. The first one uses the quark bag model and describes the transition to three-flavor quark matter at low critical densities. The second one employs a Polyakov-loop extended Nambu-Jona-Lasinio (PNJL) model with parameters describing a phase transition to two-flavor quark matter at higher critical densities. These models possess a distinctly different temperature dependence of their transition densities which turns out to be crucial for the possible appearance of quark matter in supernova cores. During the early post-bounce accretion phase quark matter is found only if the phase transition takes place at sufficiently low densities as in the study based on the bag model. The increase critical density with increasing temperature, as obtained for our PNJL parametrization, prevents the formation of quark matter. The further evolution of the core collapse supernova as obtained applying the quark bag model leads to a structural reconfiguration of the central protoneutron star where, in addition to a massive pure quark matter core, a strong hydrodynamic shock wave forms and a second neutrino burst is released during the shock propagation across the neutrinospheres. We discuss the severe constraints in the freedom of choice of quark matter models and their parametrization due to the recently observed 2M _?? pulsar and their implications for further studies of core collapse supernovae in the QCD phase diagram.     

Temperature and Redox Dual‐Responsive Biodegradable Nanogels for Optimizing Antitumor Drug Delivery

The strategy to efficiently deliver antitumor drugs via nanocarriers to targeted tumor sites and achieve controllable drug release is attracting great research interest in cancer therapy. In this study, a novel type of disulfide‐bonded poly(vinylcaprolactam) (PVCL)‐based nanogels with tunable volume phase transition temperature and excellent redox‐labile property are prepared. The nanogels are hydrophilic and swell at 37 °C, whereas under hyperthermia (e.g., 41 °C), the nanogels undergo sharp hydrophilic/hydrophobic transition and volume collapse, which enhances the cellular uptake and drug release. The incorporation of disulfide bond linkers endows the nanogels with an excellent disassembly property in reducing environments, which greatly facilitates drug release in tumor cells. Nanogels loaded with doxorubicin (DOX) (DOX‐NGs) (DOX‐NGs) are stable in physiological conditions with low drug leakage (15% in 48 h), while burst release of DOX (92% in 12 h) can be achieved in the presence of 10 × 10^?3 m glutathione and under hyperthermia. The DOX‐NGs possess improved cell killing efficiency under hyperthermia (IC₅₀ decreased from 1.58 μg mL^?1 under normothermia to 0.5 μg mL^?1). Further, the DOX‐NGs show a pronounced tumor inhibition rate of 46.6% compared with free DOX, demonstrating that this new dual‐responsive nanogels have great potential as drug delivery carriers for cancer therapy in vivo.     

Fluctuation assisted collapses of Bose–Einstein condensates

We study the collapse dynamics of a Bose–Einstein condensate subjected to a sudden change of the scattering length to a negative value by adopting the self-consistent Gaussian state theory for mixed states. Compared to the Gross–Pitaevskii and the Hartree–Fock–Bogoliubov approaches, both fluctuations and three-body loss are properly treated in our theory. We find a new type of collapse assisted by fluctuations that amplify the attractive interaction between atoms. Moreover, the calculation of the fluctuated atoms, the entropy, and the second-order correlation function showed that the collapsed gas significantly deviated from a pure state.     

Enhanced optical and hydrophilic properties of V and La co-doped ZnO thin films

V and La co-doped and undoped ZnO thin films were deposited on a glass substrate via the sol–gel method to investigate the structural, optical, and wettability of ZnO thin film by changing the V-doping concentration. Microstructure and water contact angles of the films were measured by SEM and contact angle goniometer, respectively. SEM studies revealed that the grain size and surface roughness of the film were changed by doping concentration. In addition, the contact angles were studied to find the possible effects of doping on the hydrophilicity of the film, indicating that the ZnO films were hydrophobic in nature. Finally, a good correlation was observed between the SEM micrographs and contact angle results, and the nature of ZnO film was found to be changed from hydrophobic to hydrophilic.     

亲水性微观粗糙表面润湿状态转变性能研究

以亲水性微观粗糙表面上不同几何形貌及分布的微柱阵列为对象, 讨论了液滴在亲水性粗糙表面上的润湿过程以及润湿状态的转变阶段. 从能量角度分别考察了微观粗糙结构几何形貌及分布、微柱几何参数、固体表面亲水性、接触角滞后作用等因素对液滴润湿状态转变的影响规律. 研究发现: 在亲水粗糙表面, 正方形微柱呈正六边形阵列分布时, 液滴更容易形成稳定的Cassie状态, 或者液滴仅发生Cassie状态向中间浸润状态的转变; 与此同时, 减小微柱间距、增大方柱宽度或圆柱直径、增大微柱高度、增强固体表面的亲水性将有利于液滴处于稳定的Cassie状态, 或阻止润湿状态向伪-Wenzel或Wenzel状态转变; 然而, 当液滴处于Cassie状态时, 较小的固-液界面面积分数或减弱固体表面亲水性能均有利于增大液滴的表观接触角, 因此在亲水表面设计粗糙结构时应综合考虑润湿状态稳定性和较大表观接触角两方面因素; 此外, 接触角滞后作用对于液滴状态的稳定性以及疏水性能的实现具有相反作用的影响. 研究结果为液滴在亲水表面获得稳定Cassie状态的粗糙结构设计方法提供了理论依据. 关键词： 亲水表面 微观粗糙结构 表面自由能 润湿状态转变