A comparative study of the target search of end monomers of real and Rouse chains under spherical confinement.

We study the dynamics of the end monomers of a real chain confined in a spherical cavity to search for a small target on the cavity surface using Langevin dynamics simulation. The results are compared and contrasted with those of a Rouse chain to understand the influence of excluded volume interactions on the search dynamics, as characterized by the first passage time (FPT). We analyze how the mean FPT depends on the cavity size Rb, the target size a, and the degree of confinement quantified by Rg/Rb, with Rg being the polymer radius of gyration in free space. As a basic finding, the equilibrium distribution of the end monomers of a real chain in a closed spherical cavity differs from that of a Rouse chain at a given Rg/Rb, which leads to the differences between the mean FPTs of real and Rouse chains. Fitting the survival probability S(t) by a multi-exponential form, we show that the S(t) of real chains exhibits multiple characteristic times at large Rg/Rb. Our simulation results indicate that the search dynamics of a real chain exhibit three characteristic regimes as a function of Rg/Rb, including the transition from the Markovian to non-Markovian process at Rg/Rb ≈ 0.39, along with two distinct regimes at 0.39 < Rg/Rb < 1.0 and Rg/Rb > 1.0, respectively, where S(t) exhibits a single characteristic time and multiple characteristic times.

Crystallization and melting of unentangled poly(ε-caprolactone) cycles containing pendants.

The Rouse model provides a basic framework to understand the chain dynamics of polymers, which is confirmed to be more suitable for exploring the linear dynamics of unentangled polymers. The crystalline morphology governed by chain dynamics and crystallization kinetics is expected to differ in linear and cyclic polymers. Cyclic poly(ε-caprolactone)s (c-PCLs) containing two bi-anthracenyl group pendants with molecular weights close to the critical molecular weight (Mc) were synthesized to investigate the chain dynamics based crystallization and melting behavior by DSC, POM, and in situ simultaneous small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) investigations during heating of the isothermally crystallized samples. Double endothermic peaks were observed in the DSC curves with a low heating rate of c-PCLs without entanglement after isothermal crystallization, especially for c-PCLs with Mc. The structure evolution of the crystalline structures observed from the in situ investigations during the heating and double endothermic peaks in DSC heating curves of the c-PCLs indicate the role of pendants in the chain dynamics, which leads to the reorganization of the metastable structures. Banded spherulites of c-PCL without entanglement were observed for the first time, and the uneven growth of spherulites along the radial direction may be caused by the mismatch between chain dynamics and crystallization kinetics.

Theory of mobility of inhomogeneous-polymer-grafted particles.

We develop a theory for the motion of a particle grafted with inhomogeneous bead-spring Rouse chains via the generalized Langevin equation (GLE), where individual grafted polymers are allowed to take different bead friction coefficients, spring constants, and chain lengths. An exact solution of the memory kernel K(t) is obtained for the particle in the time (t) domain in the GLE, which depends only on the relaxation of the grafted chains. The t-dependent mean square displacement g(t) of the polymer-grafted particle is then derived as a function of the friction coefficient γ0 of the bare particle and K(t). Our theory offers a direct way to quantify the contributions of the grafted chain relaxation to the mobility of the particle in terms of K(t). This powerful feature enables us to clarify the effect on g(t) of dynamical coupling between the particle and grafted chains, leading to the identification of a relaxation time of fundamental importance in polymer-grafted particles, namely, the particle relaxation time. This timescale quantifies the competition between the contributions of the solvent and grafted chains to the friction of the grafted particle and separates g(t) into the particle- and chain-dominated regimes. The monomer relaxation time and the grafted chain relaxation time further divide the chain-dominated regime of g(t) into subdiffusive and diffusive regimes. Analysis of the asymptotic behaviors of K(t) and g(t) provides a clear physical picture of the mobility of the particle in different dynamical regimes, shedding light on the complex dynamics of polymer-grafted particles.

Effects of end groups and entanglements on crystallization and melting behaviors of poly(ε-caprolactone).

The topology including end groups, entanglement loops, and tie molecules has a significant impact on the rheological and crystallization behavior and consequently on the functionality of a polymer. Unentangled, weakly entangled, and strongly entangled poly(ε-caprolactone)s (PCLs) with end groups and various molecular weights were synthesized. POM and DSC were used to observe spherulite growth and characterize thermal properties during crystallization and melting. The viscosity and structure of the samples were probed by rheology and X-ray analysis, respectively. The crossover of the scaling relationship of viscosity vs molecular weight demonstrates that the samples cover a wide range of entanglement density, and the bulky end groups cause deviations from the classical scaling laws. In situ simultaneous SAXS/WAXS investigations showed that the crystal structure of PCLs did not change with end groups and heating. The results of POM and DSC imply that the end groups and entanglements affect the crystallization rate and the spherulite morphology. The melting of PCLs containing end groups was found to be a multi-step process involving various nanoscale crystalline structures. The evolution of nanoscale crystalline structures of isothermally crystallized PCLs during heating was analyzed by fitting 1D SAXS profiles, and the continuous structural evolution was found to be a process influenced by end groups and entanglements. The results show that end groups and entanglements affect the chain dynamics and lead to constrained crystallization behavior and the formation of metastable structures, ultimately affecting the structure evolution during melting.

Explicit analytical form for memory kernel in the generalized Langevin equation for end-to-end vector of Rouse chains.

The generalized Langevin equation (GLE) provides an attractive theoretical framework for investigating the dynamics of conformational fluctuations of polymeric systems. While the memory kernel is a central function in the GLE, explicit analytical forms for this function have been challenging to obtain, even for the simple models of polymer dynamics. Here, we achieve an explicit analytical expression for the memory kernel in the GLE for the end-to-end vector of Rouse chains in the overdamped limit. Our derivation takes advantage of the finding that the dynamics of the end-to-end vector of Rouse chains with both free ends are equivalent to those of Rouse chains with one free end and the other fixed. For the latter model, we first show that the equations of motion of the Rouse modes as well as their statistical properties can be obtained under the boundary conditions where the free end is held fixed temporarily. We then analytically solve the terms associated with intrachain interactions in the GLE. By formally comparing these terms with the GLE based on the Rouse modes, we obtain an explicit expression for the memory kernel, along with analytical forms for the potential field and the random colored noise force. Our analytical memory kernel is confirmed by numerical calculations in the Laplace space and is shown to yield asymptotic behaviors that are consistent with previous studies. Finally, we utilize our analytical result to simulate the cyclization dynamics of Rouse chains and discuss the scaling of the cyclization time with chain length.

[Joint administration of acupuncture, western and herbal medicines and bamboo-jar-cupping for stroke patients of wind-phlegm obstructing collateral type in acute stage].

OBJECTIVE: To observe the curative effect of joint administration of acupuncture, western and herbal medicines and bamboo-jar-cupping in the treatment of locomotor dysfunction in patients with apoplexy (acute phase) of wind-phlegm blocking meridian-collateral type in acute stroke patients, and its influence on some relevant laboratory indexes. METHODS: A total of 100 cases of acute stroke patients of wind-phlegm blocking meridian-collateral type were recruited, and equally and randomly divided into control group and treatment group according to the random number table. The patients of both groups received treatment of conventional western medicines (for anti-platelet aggregation, blood-lipid regulation, arterial plaque-stabilization, cerebral cell protection and blood pressure-lowering), Chinese herbal medicines (for promoting blood circulation to dredge the meridian-collaterals), and acupuncture of Neiguan (PC6), Chize (LU5), Zusanli (ST36), Binao (LI14) and Sanyinjiao (SP6); and in addition, the patients of the treatment group also treated by cupping with bamboo-jar (kept for 10 min). The treatment was conducted once a day for 2 weeks. After the treatment, the National Institute of Health Stroke Scale (NIHSS), Fugl-Meyer assessment (FMA), Barthel Index (BI), and traditional Chinese medicine (TCM) syndrome score were used to assess the state of neurofunction, locomotor function, daily living ability, and TCM symptoms. The contents of serum C-reactive protein, D-dimer and blood homocysteine were detected using radical immunodiffusion, immunoturbidimetry, and enzymic methods, respectively. RESULTS: After the treatment, of the 50 and 50 cases in the control and treatment groups, 5 and 6 were cured, 7 and 18 experienced marked improvement, 23 and 20 were effective, and 15 and 6 ineffective, with the effective rate being significantly higher in the treatment group (88.0%) than in the control group (70.0%, P<0.05). Self-comparison showed that the FMA and BI scores were significantly increased (P<0.01), and the NIHSS score and TCM syndrome score notably decreased in both groups ( P<0.01) in comparison with their own pre-treatment. Comparison between the two groups showed that the FMA and BI scores were obviously higher in the treatment group than in the control group (P<0.05), whereas the NIHSS score and TCM syndrome score as well as the C-reaction protein content evidently lower in the treatment group than in the control group (P<0.05, P<0.01). CONCLUSION: Joint administration of acupuncture, western and Chinese herbal medicines and cupping can promote the recovery of nerve function, improve locomotor function, activities of daily living and quality of life, and reduce inflammatory state in acute stroke patients with wind-phlegm blocking collaterals.

Diffusive Escape of a Nanoparticle from a Porous Cavity.

Narrow escape from confinement through a nanochannel is the critical step of complex transport processes including size-exclusion-based separations, oil and gas extraction from the microporous subsurface environment, and ribonucleic acid translocation through nuclear pore complex channels. While narrow escape has been studied using theoretical and computational methods, experimental quantification is rare because of the difficulty in confining a particle into a microscopic space through a nanoscale hole. Here, we studied narrow escape in the context of continuous nanoparticle diffusion within the liquid-filled void space of an ordered porous material. Specifically, we quantified the spatial dependence of nanoparticle motion and the sojourn times of individual particles in the interconnected confined cavities of a liquid-filled inverse opal film. We found that nanoparticle motion was inhibited near cavity walls and cavity escape was slower than predicted by existing theories and random-walk simulations. A combined computational-experimental analysis indicated that translocation through a nanochannel is barrier controlled rather than diffusion controlled.

Individual circular polyelectrolytes under shear flow.

Individual circular polyelectrolytes in simple shear flow are studied by means of mesoscale hydrodynamic simulations, revealing the complex coupling effects of shear rate, electrostatic interaction, and circular architecture on their conformational and dynamical properties. Shear flow deforms the polyelectrolyte and strips condensed counterions from its backbone. A decrease in condensed counterions alters electrostatic interactions among charged particles, affecting shear-induced polymer deformation and orientation. Circular architecture determines the features of deformation and orientation. At weak electrostatic interaction strengths, the polyelectrolyte changes its shape from an oblate ring at small shear rates to a prolate ring at large shear rates, whereas strong electrostatic interaction strengths are associated with a transition from a prolate coil to a prolate ring. Circular polyelectrolytes exhibit tumbling and tank-treading motions in the range of large shear rates. Further study reveals a similarity between the roles of intramolecular electrostatic repulsion and chain rigidity in shear-induced dynamics.

Structural Mechanism for Viscosity of Semiflexible Polymer Melts in Shear Flow.

The viscosities of semiflexible polymers with different chain stiffnesses in shear flow are studied via nonequilibrium molecular dynamics techniques. The simulation reproduces the experimentally observed results, giving a complete picture of viscosity as chain stiffness increases. Analysis of flow-induced changes in chain conformation and local structure indicates two distinct mechanisms behind a variety of viscosity curves. For polymers of small stiffnesses, it is related to flow-induced changes in chain conformation and, for those of large stiffnesses, to flow-induced instabilities of nematic structures. The four-region flow curve is confirmed for polymers of contour length close to persistence length and understood by combining the two structural mechanisms. Thus, these findings clarify the microscopic structures indicated by the macroscopic viscosity.

Effect of functionality on unentangled star polymers at equilibrium and under shear flow.

The properties of unentangled star polymers with arm length Nf = 20 beads and functionality f (3 ≤ f ≤ 60) are investigated at equilibrium and under shear flow by coarse-grained molecular dynamics simulations. At equilibrium, the star polymer shows a crossover from a linear, freely penetrable, extremely soft object to a spherical, slightly hard object with an impenetrable center with increasing f. The results confirm that the arm relaxation is essentially independent of f and stars of large f form a liquid-like structure. In shear flow, the polymer deformation and alignment are calculated as well as the shear-induced rotational dynamics as function of shear rate. These properties are found to exhibit qualitative changes at an f-independent shear rate, γp, which is a consequence of competition between chain relaxation and imposed flow. Shear thinning is characterized by shear viscosity and normal stress differences. With increasing f, the critical shear rate for the onset of shear thinning decreases from γp for f = 3 to a smaller value. Our results also show that shear thinning of stars of large f arise from the collapse of liquid-like structures at low shear rates (γ̇≪γp), where chains have no deformation; at high shear rates (γ̇≫γp), shear thinning is mainly attributed to the chain stretching and orientation as linear polymers.

GPU-Accelerated Molecular Dynamics Simulation to Study Liquid Crystal Phase Transition Using Coarse-Grained Gay-Berne Anisotropic Potential.

Gay-Berne (GB) potential is regarded as an accurate model in the simulation of anisotropic particles, especially for liquid crystal (LC) mesogens. However, its computational complexity leads to an extremely time-consuming process for large systems. Here, we developed a GPU-accelerated molecular dynamics (MD) simulation with coarse-grained GB potential implemented in GALAMOST package to investigate the LC phase transitions for mesogens in small molecules, main-chain or side-chain polymers. For identical mesogens in three different molecules, on cooling from fully isotropic melts, the small molecules form a single-domain smectic-B phase, while the main-chain LC polymers prefer a single-domain nematic phase as a result of connective restraints in neighboring mesogens. The phase transition of side-chain LC polymers undergoes a two-step process: nucleation of nematic islands and formation of multi-domain nematic texture. The particular behavior originates in the fact that the rotational orientation of the mesogenes is hindered by the polymer backbones. Both the global distribution and the local orientation of mesogens are critical for the phase transition of anisotropic particles. Furthermore, compared with the MD simulation in LAMMPS, our GPU-accelerated code is about 4 times faster than the GPU version of LAMMPS and at least 200 times faster than the CPU version of LAMMPS. This study clearly shows that GPU-accelerated MD simulation with GB potential in GALAMOST can efficiently handle systems with anisotropic particles and interactions, and accurately explore phase differences originated from molecular structures.

Effects of excluded volume and hydrodynamic interaction on the deformation, orientation and motion of ring polymers in shear flow.

A ring polymer is a classical model to explore the behaviors of biomacromolecules. Compared with its linear counterpart in shear flow, the ring polymer should be more sensitive to excluded volume and hydrodynamic interaction attributed to the absence of chain ends. We carried out multiparticle collision dynamics combined with molecular dynamics simulation to study the effects of excluded volume and hydrodynamic interaction on the behaviors of ring polymers in shear flow. The results show that in the absence of the strong excluded volume interaction, the ring polymer prefers a two-strand linear conformation with high deformation and orientation in the flow-gradient plane, and the tank-treading motion is nearly negligible. Ring polymers without excluded volume show no significant difference from linear polymers in the scaling exponents for the deformation, orientation and tumbling motion. We also observed that the hydrodynamic interaction could efficiently slow down the relaxation of ring polymers while the scaling exponents against the Weissenberg number have rarely been affected.

Gold nanoparticles embedded in silica hollow nanospheres induced by compressed CO2 as an efficient catalyst for selective oxidation.

Metal nanoparticles embedded in hollow materials are important due to their wide applications in catalysis. In this work, we disclosed a nontraditional synthetic pathway to prepare silica hollow nanospheres by hydrothermal treatment in the presence of compressed CO2. Especially, the silica hollow nanospheres with an outer diameter of about 16 nm and an inner pore size of 7 nm were obtained using 1.0 MPa CO2. The formation mechanism of silica hollow nanospheres induced by CO2 was investigated by high-pressured UV/Vis spectroscopy. Moreover, gold nanoparticles (2.5 nm) embedded in the silica hollow nanospheres were prepared by a one-pot synthesis using HAuCl4 as a precursor. The current synthetic route of nano-catalysts was simple and facile, in which no etching agent was needed in the process of the hollow material preparation. Besides, this nano-catalyst showed an excellent catalytic performance in epoxidation of styrene with high conversion (82.2%) and selectivity (90.2%) toward styrene oxide, as well as in the selective oxidation of ethylbenzene with good conversion (26.6%) and selectivity (87.8%) toward acetophenone. Moreover, the Au nanoparticles (AuNPs) embedded in silica hollow nanospheres exhibited an excellent recyclability in both the oxidation reactions.

Simulation studies on architecture dependence of unentangled polymer melts.

The dependences of the properties of linear, ring, star, and H-shaped polymer melts on architecture are investigated by nonequilibrium molecular dynamics simulations. We find that zero-shear viscosities η0 for various architectures follow a universal relation, η0=Cη〈Rg0 (2)〉, where Cη is a constant and 〈Rg0 (2)〉 the equilibrium mean-square radius of gyration, in the unentangled regime. This law is also found valid for asymmetrical polymers but invalid for polymers with a hard core, such as stars with many arms and short arm lengths. In the unentangled regime, from the point of view of polymer size, the relaxation times show weak dependences on architecture, but the architecture dependence of the diffusion coefficient is still apparent. Then, we examine unentangled melts of various architectures having the same size over a wide range of shear rates covering linear and nonlinear viscoelastic regimes and find that the rheological quantities, namely, viscosity, first and second normal stress differences, are independent of architecture. In contrast, the polymer deformation shows an apparent dependence on architecture in the nonlinear regime. These findings shall shed significant light on the nature of rheological behaviors of unentangled melts.

Topological constraints of network chains in telechelic associative polymer gels.

We present an analysis of topological constraints of network chains, in particular entanglements, in ABA telechelic associative polymer gels generated by Brownian dynamics technique with a B selective solvent. We find two fundamental types of entanglements formed by bridge chains: first, two or more bridge chains linking different micelles impose topological constraints on each other because they cannot cross, denoted as type-I entanglement; second, two or more bridge chains linking a pair of micelles are twisted together, denoted as type-II entanglement. More complex constraints are composed of both types. There is no difference between type-I and type-II entanglements in polymer melts, but in gels, only type-I entanglement provides extra junctions that can significantly affect the modulus. The dependences of entanglement on chain length and concentration are investigated. The simulations reveal that even at low concentrations where only parts of long chains are entangled, they can provide a considerable number of junctions.

Temperature-Dependent Immobilization of a Tungsten Peroxo Complex That Catalyzes the Hydroxymethoxylation of Olefins.

A tungsten peroxo complex stabilized by the bidentate picolinato ligand has been synthesized and then immobilized successfully on imidazole-functionalized silica. The immobilized tungsten-based catalyst was employed as an efficient catalyst for the one-pot synthesis of ß-alkoxy alcohols from olefins and methanol with H2 O2 . Regarding the catalyst evaluation and the results of characterization by the various methods, it was demonstrated that the immobilization of tungsten peroxo complex was highly temperature-dependent. The tungsten peroxo complex can dissociate and diffuse into the liquid phase at reaction temperature, resulting in a homogeneous reaction. Nevertheless, the catalytically active species was anchored on the imidazole-functionalized silica by hydrogen bonding as the temperature was lowered to 0 °C after the reaction, which thus offered a highly effective approach for recycling the catalyst for consecutive cycles. In addition, various olefins can be converted to the corresponding ß-alkoxy alcohols with good conversion and selectivity under relative mild conditions by H2 O2 .

Shear thinning behavior of linear polymer melts under shear flow via nonequilibrium molecular dynamics.

The properties of both untangled and entangled linear polymer melts under shear flow are studied by nonequilibrium molecular dynamics simulations. The results reveal that the dependence of shear viscosity η on shear rate γ, expressed by n ~ γ(-n), exhibits three distinct regimes. The first is the well-known Newtonian regime, namely, η independent of shear rate at small shear rates γ < τ0(-1) (where τ0 is the longest polymer relaxation time at equilibrium). In the non-Newtonian regime (γ > τ0(-1)) the shear dependence of viscosity exhibits a crossover at a critical shear rate γc dividing this regime into two different regimes, shear thinning regime I (ST-I) and II (ST-II), respectively. In the ST-I regime (τ0(-1) < γ < γc), the exponent n increases with increasing chain length N, while in the ST-II regime (γ > γc) a universal power law n ~ γ(-0.37) is found for considered chain lengths. Furthermore, the longer the polymer chain is, the smaller the shear viscosity for a given shear rate in the ST-II regime. The simulation also shows that a characteristic chain length, below which γc will be equal to τ0(-1), lies in the interval 30 < N < 50. For all considered chain lengths in the ST-II regime, we also find that the first and second normal stress differences N1 and N2 follow power laws of N1 ~ γ(2/3) and N2 ~ γ(0.82), respectively; the orientation resistance parameter mG follows the relation mG ~ γ(0.75) and the tumbling frequency ftb follows ftb ~ γ(0.75). These results imply that the effects of entanglement on the shear dependences of these properties may be negligible in the ST-II regime. These findings may shed some light on the nature of shear thinning in flexible linear polymer melts.

Traditional chinese medicine in cancer care: a review of case series published in the chinese literature.

Traditional Chinese medicine (TCM) has been widely used in cancer in China. Case series report a series of cases exposed to a certain intervention. To understand the current situation of case series of TCM for cancer, we performed this review. We included case series of cancer patients treated with TCM therapy. Electronic searches were conducted in four main Chinese databases until February 2011. A total of 1,217 reports of case series (92,945 patients) were included. The top five types of cancer were lung cancer, liver cancer, stomach cancer, leukemia, and esophageal cancer. Leukopenia and hiccup treated by TCM were the most common adverse reactions after surgery or induced by chemo/radiotherapy. More than half of the patients were treated with TCM therapies alone. The application of herbal medicines especially formula based on syndrome differentiation was highly prevalent, and the typical administration route was oral usage. 1,182 reports were published in a structured format. The quantity of TCM case series for cancer treatment is substantial. Further studies should focus on the most common types of cancer and the most frequently applied TCM therapies. We presented a recommendation from the methodological point of view for the format of reporting.

Monte Carlo simulation of self-assembly of symmetric ABC three-arm star copolymers under cylindrical confinement.

Self-assembly of symmetric ABC three-arm star copolymers confined in cylindrical nanopores is investigated by means of a lattice Monte Carlo simulation method. The dependence of morphologies on the degree of confinement and preference of pore surface is studied systematically. For the symmetric ABC three-arm star copolymers which form polygonal cylinder structures with periodic spacing L(0) in bulk, various novel structures are observed inside the nanopores. In the nanopores with a neutral surface, we find a minimum diameter value (D(min) ≈ L(0)) under which helical arranged droplets are formed; otherwise, parallel polygonal cylinder structures are identified. By adjusting the preference between component A and the pore surfaces, a number of novel structures such as A cylinder + BC single-strand helix and complex multilayer double helices are identified. Additionally, the confinement-induced morphology transition is interpreted by the frustration parameter D/L(0).