Green Synthesized Liquid-like Dynamic Polymer Chains with Decreased Nonspecific Adhesivity for High-Purity Capture of Circulating Tumor Cells

The capture of circulating tumor cells(CTCs)is of great significance in reducing cancer mortality and complications.However,the nonspecific binding of proteins and white blood cells(WBCs)weakens the targeting capabilities of the capture surfaces,which critically hampers the efficiency and purity of the captured CTCs.Herein,we propose a liquid-like interface design strategy that consists of liquid-like polymer chains and anti-EpCAM modification processes for high-purity and high-efficiency capture of CTCs.The dynamic flexible feature of the liquid-like chains endows the modified surfaces with excellent antiadhesion property for proteins and blood cells.The liquid-like surfaces can capture the target CTCs and show high cell viability due to the environmentfriendly surface modification processes.When liquid-like surface designs were introduced in the deterministic lateral displacement(DLD)-patterned microfluidic chip,the nonspecific adhesion rate of WBCs was reduced by more than fivefold compared to that in the DLD chip without liquid-like interface design,while maintaining comparable capture efficiency.Overall,this strategy provides a novel perspective on surface design for achieving high purity and efficient capture of CTCs.

A Novel Dynamic Polymer Synthesis via Chlorinated Solvent Quenched Depolymerization

Dynamic polymers with both physical interactions and dynamic covalent bonds exhibit superior performance,but achieving such dry polymers in an effi-cient manner remains a challenge.Herein,we report a novel organic solvent quenched polymer synthesis using the natural molecule thioctic acid(TA),which has both a dynamic disulfide bond and carboxylic acid.The effects of the solvent type and concentration along with reaction times on the proposed reaction were thoroughly explored for polymer synthesis.Solid-state proton nuclear magnetic resonance(1 H NMR)and first-principles simulations were carried out to investigate the reaction mechanism.They show that the chlorinated solvent can efficiently stabilize and mediate the depolymerization of poly(TA),which is more kinetically favorable upon lowering the temperature.Attributed to the numerous dynamic covalent disulfide bonds and noncovalent hydrogen bonds,the obtained poly(TA)shows high extensibility,self-healing,and reprocessable properties.It can also be employed as an efficient adhesive even on a Teflon surface and 3D printed using the fused deposition modeling technique.This new polymer synthesis approach of using organic solvents as catalysts along with the unique reaction mechanism provides a new pathway for efficient polymer synthesis,especially for multifunctional dynamic polymers.

Dynamic polymeric materials based on reversible B–O bonds with dative boron–nitrogen coordination

To minimize the environmental pollution caused by polymeric waste,materials based dynamic chemistry have attracted extensive attention around the world.Various dynamic covalent bonds or noncovalent interactions have been employed to design multifunctional polymers with recyclability,reprocessablility,and sustainability.Among them,polymers based on reversible boron–oxygen(B–O)bonds have been widely investigated because of their unique properties.Particularly,lots of scientists have demonstrated that the combination with boron–nitrogen(B–N)coordination can effectively accelerate the dynamicity as well as enhance the stability of B–O bonds.Therefore,numerous polymers containing dynamic B–O bonds with dative B–N coordination have been designed and synthesized in recent years.These polymers exhibit excellent versatility and great potential for diverse applications such as biosensors,battery electrolytes,and artificial skins.This review provides an overview of the comprehensive influence of dynamic B–N coordination chemistry on B–O bonds in organoboron species and highlights the developments in the area of constructing boron‐containing polymeric materials with this interesting linkage.The design guidelines,existing challenges,and future perspectives in this burgeoning field are discussed and proposed.

Physical Diffusion and Electron-transfer Dynamics of Electroactive Solutes in Polymer Electrolytes Ⅲ. Effect of the Polymer Solvents

The diffusion coefficients(Dapp) and the heterogeneous electron transfer rate constants(ks)for ferrocene in several polymer solvents were determined by using steady-stae voltammetry. Thetemperature dependence of the two parameters indicates Arrhenius behavior. The polymer solventeffects on diffusion and electron transfer dynamics of ferrocene were discussed

Ring-Polymer Molecular Dynamics Studies of Thermal Rate Coefficients for Reaction F+H2O→HF+OH

The prototype tetra-atomic reaction F+H2O→HF+OH plays a significant role in both atmospheric and astronomical chemistry.In this work,thermal rate coefficients of this reaction are determined with the ring polymer molecular dynamics(RPMD)method on a full-dimensional potential energy surface(PES).This PES is the most accurate one for the title reaction,as demonstrated by the correct barrier height and reaction energy,compared to the benchmark calculations by the focal point analysis and the high accuracy extrapolated ab initio thermochemistry methods.The RPMD rate coefficients are in excellent agreement with those calculated by the semiclassical transition state theory and a two-dimensional master equation technique,and some experimental measurements.As has been found in many RPMD applications,quantum effects,including tunneling and zero-point energy effects,can be efficiently and effectively captured by the RPMD method.In addition,the convergence of the results with respect to the number of beads is rapid,which is also consistent with previous RPMD applications.

Ring Polymer Molecular Dynamics of the C(^(1)D)+H_(2) Reaction on the Most Recent Potential Energy Surfaces

Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.

Physical Diffusion and Electron-transfer Dynamics of Electroactive Solutes in Polymer Electrolytes Ⅰ. Effect of the Nature of Electroactive Solutes

The diffusion coefficients(Dapp) and the heterogeneous electron-transfer rate constants(ks)for ferrocene and its seven derivatives in MPEG/LiClO4 electrolyte were determined by using steadystate voltammetry. The two parameters increase with increasing temperature, indicating Arrhenius behavior. The effects of the nature of electroactive solute molecules on Dapp, ks, and the half-wave potentials(E1/2) are discussed.

Physical Diffusion and Electron-transfer Dynamics of Electroactive Solutes in Polymer Electrolytes Ⅱ. Effect of the Ionic Size of Supporting Electrolytes

The ditheion coefficients(Dapp) and the heterogeneous electron-transfer rate constan(ks)for ferrocene in MPEG/salt electrolytes were determined by using Steady-stae voltammetry. The temperature dependence of the two parameters obeys the Arrhenius equstion. The effect of the ionic size of sir supporting electrolytes on diffusion and electron transfer dynamics of fermcene was discussed

MOLECULAR DYNAMICS SIMULATION ON VIERATIONAL SPECTROSCOPIC FEATURES OF HYDROGEN BONDS IN CRYSTALLINE POLYMERS

Introduction The molecular dynamics simulation technique has recently proved to be a suitable alternative approachfor simulation of vibrational spectroscopy. In this study, molecular dynamics was utilized to understandlow frequency vibrations in highly ordered poly(ρ-phenylene terephthalmide) (PPTA). A key structuralfeature of this polymer is the presence of hydrogen bonds. There is little question that this strong localized

Enhancing hydrolytic stability of dynamic imine bonds and polymers in acidic media with internal protecting groups

Imine bonds are among the most explored building motifs in dynamic chemistry,polymers,and materials,and yet,their acid-resistance remains a longstanding issue.Herein we demonstrate a concept of internal protecting groups for improving the kinetic stability of dynamic imine bonds and polymers.Systematic examination of structure-reactivity relationship of a series of aldehydes/imines bearing a neighboring carboxyl allowed uncovering of required structural features for dynamically masking imine bonds with cyclic structures.Mechanistic studies indicated that noncovalent interactions along with sterics control the ringchain equilibrium and the stability of imine bonds.The incorporation of internal protecting groups into imine polymers further enabled their controlled stability in acidic media.Moreover,a combination of dynamic covalent network and coordination supramolecular network provided a facile means for the modulation of luminescent and mechanical properties of polymers.The strategies and results reported should be beneficial to molecular assemblies,dynamic polymers,biological delivery,and intelligent materials.

Dynamic Sulfur-Rich Polymers from Elemental Sulfur and Epoxides

Sulfur-containing dynamic polymers had attracted significant attention due to their unique chemical structures with high reversibility.Utilizating sulfur, an inexpensive industrial waste product, to synthesize dynamic polysulfide polymers through reverse vulcanization has been a notable approach. However, this method required high temperatures and resulted in the release of unpleasant oders. In this study, we presented a robust method for the preparation of sulfur-rich polymers with dynamic polysulfide bonds from elemental sulfur and inexpensive epoxide monomers via a one-pot strategy at the mild room temperature. Different types of polysulfide molecules and polymers were synthesized by reacting various epoxide compounds with sulfur, along with the investigation of their structures and dynamic behaviors. It was noteworthy that the obatined polymers prepared from m-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline and elemental sulfur exhibit multiple dynamic behaviors, including polysulfide metathesis and polysulfide-thiol exchange, enabling their rapid stress relaxation, self-healing, reprocessing and degradable properties of the cross-linked polymer. More importantly, the hydroxyl groups at the side chains from epoxide ring opening exhibited potential transesterification. This work provided a facile strategy for designing dynamic sulfur-rich polymers via a mild synthesis route.

Bifurcation control and eigenstructure assignment in continuous solution polymerization of vinyl acetate

The major difficulty in achieving good performance of industrial polymerization reactors lies in the lack of understanding of their nonlinear dynamics and the lack of well-developed techniques for the control of nonlinear processes, which are usually accompanied with bifurcation phenomenon. This work aims at investigating the nonlinear behavior of the parameterized nonlinear system of vinyl acetate polymerization and further modifying the bifurcation characteristics of this process via a washout filter-aid controller, with all the original steady state equilibria preserved. Advantages and possible extensions of the proposed methodology are discussed to provide scientific guide for further controller design and operation improvement.

The New Methods for Characterization of Molecular Weight of Supramolecular Polymers

Supramolecular polymers,as a type of dynamic polymers,are subordinate to the interdisciplinary field of polymer chemistry and supramolecular chemistry,whose development has greatly promoted the prosperity of new materials.Notably,molecular weight is one of the most important parameters of supramolecular polymers,which affects the physical/chemical properties and processing applications of materials.Developing new methods for characterizing the molecular weight of supramolecular polymers is crucial for advancing the development of supramolecular polymers.In this review,we elaborate and summarize three strategies for characterizing the molecular weight of supramolecular polymers that recently reported by our research group according to the characteristics of supramolecular polymers,including(1)the molecular weight distinction corresponding to variable fluorescence colors,(2)matching different molecular weights with different fluorescence lifetime,(3)transforming supramolecular polymers into mechanically interlocked polymers or covalent polymers.Besides,we also discuss the limitations of current methods for characterizing supramolecular polymers.We hope that this review can promote the development of supramolecular polymers and significantly inspire to exploit new methods to characterizing molecular weight of supramolecular polymers.

Static Threshold Pressure Gradient Characteristics of Liquid Influenced by Boundary Wettability

We propose an experimental setup to measure the threshold pressure gradient （TPG） of microchannels with different wettability surfaces by the static method in microchannels with diameters from 20 μm to 320 μm, and compare the TPG of microchannels with adsorption of cetyl trimethyl ammonium bromide （CTAB） with that without CTAB adsorption. The results show the existence of TPG in microchannels. The TPG of microchannels increases with decreasing hydrodynamic diameter, and the relation between TPG and diameter is in agreement with the single-log normalization. The TPG of a microchannel with CTAB adsorption decreases obviously as compared with the microchannel without CTAB adsorption. The TPG of microchannels with different wettabilities of boundary surface are different, and the resistance of liquid flow can be reduced by changing the wettability of boundary surfaces.

Thin Film Flow of a Second Grade Fluid over a Stretching/Shrinking Sheet with Variable Temperature-Dependent Viscosity

Effects of variable viscosity on the flow and heat transfer in a thin film on a horizontal porous stretching sheet are analyzed. The steady boundary layer equations for momentum and thermal energy are simplified by using similarity transformations. The resulted and coupled nonlinear differential equations are solved by Homotopy analysis method. The results are presented graphically to interpret various physical parameters appearing in the problem.

Statistics of Polymer Capture by a Nanopore:A Brownian Dynamics Simulation Study

We investigate the statistics of polymer capture by a nanopore using Brownian dynamics simulations. It is found that when the velocity flux is greater than a critical velocity flux, the capture picture is a random selection process, otherwise it tends to a statistical process governed by energetic considerations. In addition, the chain ends capture probability decreases as the chain length increases and satisfies a power-law scaling of P0（N）-N^-0.8.

Using Gamma-Radiation for Drug Releasing from MWNT Vehicle

A drug delivery system via multi-walled carbon nanotube （MWNT） vehicle was synthesized in aqueous solution. MWNTs were first noncovalently functionalized with chitosan oligomers （CS） with a molecule weight of 4000-6000, making MWNTs water-soluble, and then a cancer ancillary drug tea polyphenols （TP） was conjugated mainly via the hydrogen bond between CS and TP molecules, making MWNTs efficient vehicle for drug delivering. The release of drug molecules can be realized by pH variation and γ-radiation, leading to new methods for controlling drug release from carbon nanotubes carrier. Due to the high penetrability of γ-rays, γ-radiation shows up new opportunities in controlled drug release, possibly facilitating the future cancer treatment in vivo.

Can Heavier Liquid Float on Top of a Lighter One？

We report on a first observation of a floating- spherical Hg （density 13g/cm3） drop on top of a glycerin （density 1.26g/cm3） drop, the latter is hemispherical and about four times larger in volume. This observation is clearly against nature＇s gravity law and has never been reported before. Here we present spectacular high resolution photos that clearly demonstrate this remarkable floating phenomenon. Using milli-Q water, the Hg drop would stay down adhered at the triple line. Instead, the coincidental use of tap water displays the same phenomenon. Increasing the volume of the supporting liquid to a certain value causes the Hg drop to sink. A 5-M NaCl aqueous solution is found enough to show the same floating phenomenon. This floating mercury as a phenomenon is puzzling. On this length scale it seems that surface tension and curvature dominate over gravity.

Analysis of Rheological Behavior of Some Aqueous PEO Gels under Thermal Treatment

Evolution of viscosity of some aqueous poly （ethylene oxide） gels is observed as functions of polymeric concentration and temperature for samples subjected to thermal shock. The experimental data are analyzed following an appropriate algorithm, and reveal the transient effect from Newtonian to non-Newtonian flow as a function of the polymeric concentration.

Positioning a fluorescent probe at the core of a glassy star polymer for detection of local dynamics

Accessing local dynamics within a single macromolecule is the key to understand the physical origin of the viscoelasticity and especially the glass transition. In order to extract specific information on the dynamics of the branch point of a star polymer around its glass transition temperature, four-arm star poly （n-butyl methacrylate） with a fluorescent core was synthesized using perylene diimide as initiator and polymerization conducted via atom transfer radical polymerization. The process is found to be effective in positioning the fluorophore at the branch point with the fluorophore intact, which allows the successful application of single molecule fluorescence defocus imaging in examining the local site- sensitive dynamics. The power spectra of rotation trajectories, the population of rotating fluorophores as well as the distribution of angular displacement were used to revel the difference in local dynamics between branch point and the arm＇s end. It is discovered that the local dynamics at the core of the star polymer is much less activated than that at the arm＇s end. The results demonstrate the strong effect dues to the topological constrain at the branch point and the more free space at the arm＇s end.