Theoretical study on the translocation of partially charged polymers through nanopore

The translocation time τ of partially charged polymers through a neutral nanopore is calculated using Fokker–Planck equation with adsorbing–adsorbing boundary conditions. For the polymer with one charged monomer, we find that τ is dependent on the position of the charged monomer and on the magnitude of the driving force f inside the nanopore. When the charge is located at the front half of the polymer chain, τ is larger than that of neutral polymer and increases with f. When the charge is located at the back half, it is smaller than that of the neutral polymer and decreases with increasing f. We have also studied the behavior of a symmetrical polymer with two like charges located symmetrically in the chain and that of an asymmetrical polymer with two unlike charges. Moreover, we have calculated the translocation time for a general condition of polymer with two randomly distributed charges. All results show that τ is dependent on the positions of charges in the polymer chain and on the magnitude of the driving force. The results can be explained qualitatively by the free‐energy landscape of polymer translocation. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1017–1025     

Rapid Screening of Drug Absorption Potential Using the Immobilized Artificial Membrane Phosphatidylcholine Column and Molar Volume

The immobilized artificial membrane phosphatidylcholine (IAMPC) chromatography was evaluated for the predictability of oral absorption potential of 40 structurally unrelated drugs. The chromatographic capacity factors (k_IAM) were determined as a function the pH and composition of the mobile phase, and were corrected for the molar volume of the solutes (k_IAM/MWⁿ). The correlation between k_IAM/MWⁿ and the human fraction of intestinal absorption (F_a) was highest when measured at 20% acetonitrile (pH 5.5) with the power function n = 2.5. The best-fit equation for the sigmoid relationship between k_IAM/MWⁿ and F_a was obtained: F_a (%) = 94.3 × {1-exp[-17.9 × (k_IAM/MW^2.5) × 10⁶]}^2.1 (r = 0.925). This in vitro prediction method may be useful in a rapid screening of drug candidates with high oral absorption potential in humans.     

Molecular Dynamics Simulations of Polymer Translocations

Summary: Molecular dynamics simulation studies of the translocation of charged homopolymers of length, N, driven by an electric potential gradient through a channel have been performed. We find that the translocation time, τ, displays an inverse power dependence on the temperature of the simulation τ ∼ (T − T₀)^−7/4, which is in very good agreement with experimental results. In addition, the dependence of τ on the driving field strength and the velocity of translocation on the polymer length N have also been obtained. The results suggest that such minimalist models are useful in modelling biological processes and that the molecular dynamics method is a suitable approach for carrying out these simulations.

Snapshot of the polymer during the simulation.     

Diffusion rate of polyethylene glycol into cell walls of red pine following vacuum impregnation

Rates of penetration of polyethylene glycol (PEG) molecular weight (MW) 1,000, 2,000, and 4,000 from 30% aqueous solutions into hydrated cell walls of red pine samples following vacuum impregnation were estimated by examining retained swelling of the samples after different post-treatment conditioning times. To model PEG diffusion into wood cell walls, a hollow cylinder diffusion model was developed and diffusion coefficients were estimated and compared to those determined with a plane membrane diffusion model. The models gave similar results. The diffusion coefficient of PEG MW 1,000 at room temperature was estimated to be in the order of 10⁻¹³ m²/s, while the penetration rates of both PEG 2,000 and 4,000 were about an order lower. These findings indicate that treatments of wood by PEG can be significantly shorter than present practices of soaking green samples in solution if the samples are vacuum/pressure impregnated with PEG solution.     

Synthesis of multidentate functional monomer for ion imprinting

In this work, N,N,N‐tri(2‐carboxyethyl)‐3‐(2‐aminoethylamino)propyl‐trimethoxysilane was prepared as a multidentate functional monomer. The 3D model of the monomer coordinating with Cu²⁺ indicated that the monomer is able to provide five ligating atoms like ethylenediaminetetraacetic acid‐Cu²⁺ to complex with Cu²⁺. When Cu²⁺ was used as a template ion, the synthesis conditions of Cu²⁺‐imprinted polymers were optimized upon orthogonal design. It is interesting to find that Cu²⁺‐imprinted polymer offers a selectivity coefficient of 192.2 when the molar ratio of Cu²⁺ to monomer was exactly 1:1. That means there is no excess ligating atom in the ion‐imprinted polymer and therefore, the nonspecific adsorption could be avoided. Benefiting from the excellent selectivity of Cu²⁺‐imprinted polymer, even if the concentration of Zn²⁺ was 25 times that of Cu²⁺, Cu²⁺‐imprinted polymer still affords a high selectivity coefficient. Finally, the optimal synthesis conditions for Cu²⁺‐imprinted polymer, except the pH, were adopted to prepare Ni²⁺‐imprinted polymer, and Ni²⁺‐imprinted polymer also offered satisfying selectivity to Ni²⁺. That implies this multidentate monomer is adaptable in ion imprinting and, the optimal synthesis conditions of Cu²⁺‐imprinted polymer except pH are likely suitable for the imprinting of other ions besides Cu²⁺.     

Synthesis of nano-sized arsenic-imprinted polymer and its use as As selective ionophore in a potentiometric membrane electrode: Part 1

In this study, a new strategy was proposed for the preparation of As (III)-imprinted polymer by using arsenic (methacrylate)₃ as template. Precipitation polymerization was utilized to synthesize nano-sized As (III)-imprinted polymer. Methacrylic acid and ethylene glycol dimethacrylate were used as the functional monomer and cross-linking agent, respectively. In order to assembly functional monomers around As (III) ion, sodium arsenite and methacrylic acid were heated in the presence of hydroquinone, leading to arsenic (methacrylate)₃. The nano-sized As (III) selective polymer was characterized by FT-IR and scanning electron microscopy techniques (SEM). It was demonstrated that arsenic was recognized as As³⁺ by the selective cavities of the synthesized IIP. Based on the prepared polymer, the first arsenic cation selective membrane electrode was introduced. Membrane electrode was constructed by dispersion of As (III)-imprinted polymer nanoparticles in poly(vinyl chloride), plasticized with di-nonylphthalate. The IIP-modified electrode exhibited a Nernstian response (20.4 ± 0.5 mV decade⁻¹) to arsenic ion over a wide concentration range (7.0 × 10⁻⁷ to 1.0 × 10⁻¹ mol L⁻¹) with a lower detection limit of 5.0 × 10⁻⁷ mol L⁻¹. Unlike this, the non-imprinted polymer (NIP)-based membrane electrode was not sensitive to arsenic in aqueous solution. The selectivity of the developed sensor to As (III) was shown to be satisfactory. The sensor was used for arsenic determination in some real samples.     

Effects of Electrostatic Interactions on the Translocation of Polymers Through a Narrow Pore Under Different Solvent Conditions: A Dissipative Particle Dynamics Simulation Study

Polymer translocation through a narrow pore is investigated using a particle‐based dissipative particle dynamics (DPD) method. A rigid core is included in each particle to avoid particle interpenetration problems based on the original DPD method. Electrostatic interactions of charged particles are simply represented via screened Coulombic interactions. The average translocation time τ versus polymer length N satisfies the scaling law τ ∼ N^β. The scaling exponent β depends on solvent quality. The results demonstrate that solvent quality exerts a considerable influence on the dynamics of translocation of polymers. The findings may help facilitate understanding of the dynamic behaviors of various polymer and DNA molecules during translocation processes.

     

Preparation and pore-size control of hydrophilic monodispersed polymer microspheres for size-exclusive separation of biomolecules by the SPG membrane emulsification technique

This paper describes an experiment directed toward the preparation of monodispersed porous polymer microspheres with a diameter of ca. 50 m, which is applicable to the chromatographic separation of biomolecules such as proteins and peptides by size exclusion. Fairly monodispersed polymer microspheres were successfully prepared by suspension copolymerization of polyethylene glycol monomethacrylate and ethylene glycol dimethacrylate as monomer and cross-linker, respectively. Monodispersed O/W emulsion was prepared by the SPG membrane emulsification technique, and was used in the subsequent droplet-swelling process in which monodispersed seed droplets were swollen by adsorbing the secondary emulsion droplets. The effects of the organic diluent in suspension polymerization and comonomer on the porous structure of the polymer microspheres were investigated by scanning electron microscopy and mercury-intrusion porosimetry, and the separation performances of polystyrene, polyethylene glycol, and various biomolecules by size-exclusion chromatography. As a result, it was evident that benzene, 1-butanol, and butyl acetate worked as nonsolvents for the polymer prepared in this study, and that polymer microspheres prepared with these solvents had larger pores. Size-exclusion chromatography revealed that the exclusive limiting molecular weight was 1.9×10⁵ when polystyrene was used as a standard polymer, and 3.5×10⁴ when polyethylene glycol was used as a standard polymer. Furthermore, we confirmed that the monodispersed polymer microspheres with defined pores clearly separated the six representative kinds of biomolecules with molecular weights ranging from 75 to 6.4×10⁵.     

Swelling behavior of the filling-type membrane

A model that can express the swelling of the filling-type membrane was developed by modifying a model that was developed for a crystalline polymer. The filling-type membrane is composed of two different polymers. One is porous substrate and another is a polymer that filled pores of the substrate. The filling technique can effectively suppress polymer swelling due to the substrate matrix. The model needs two parameters: one is a unit ratio of tie segments in the substrate to the filling polymer, f, which can express a mechanical strength of the substrate, and another is the Flory interaction parameter, χ, between the filling polymer and a solvent that expresses a mixing energy. A porous high-density polyethylene film was used as a porous substrate, and plasma-graft filling polymerization technique could make the filling-type membrane. Methylacrylate was used as a grafting monomer that filled the pores of substrate. A swelling behavior of the filling-type membrane and pure poly(methylacrylate) were measured by the vapor sorption method at different solvent activities. The model was in good agreement with experimental results for the filling-type membrane. Using the model, swelling of the filling-type polymer was compared with a crosslinked polymer, which can be expressed by Flory and Rehner model. The comparison showed that the filling technique is a good way to suppress polymer swelling, and a high crosslinking density is needed to obtain the same level of swelling suppression effect the filling type membrane showed. © 1997 John Wiley & Sons, Inc.     

A soluble and multichromic conducting polythiophene derivative

A new soluble polythiophene derivative was synthesized by both chemical and electrochemical oxidative polymerization of 1-4-nitrophenyl-2,5-di(2-thienyl)-1H-pyrrole (SNSNO₂). Chemical method produces a polymer which is completely soluble in organic solvents. The structures of both the monomer and the soluble polymer were elucidated by ¹H and ¹³C-NMR and FTIR. The average molecular weight has been determined by GPC to be Mn = 6.3 × 10³ for the chemically synthesized polymer. P(SNSNO₂) was also synthesized via potentiostatic electrochemical polymerization. Characterizations of the resulting polymer were performed by cyclic voltammetry CV, FTIR and UV-Vis spectroscopy. Four-probe technique was used to measure the conductivities of the samples. Moreover, the spectroelectrochemical and electrochromic properties of the polymer film were investigated. In addition, dual type polymer electrochromic devices ECDs based on P(SNSNO₂) with poly3,4-ethylenedioxythiophene (PEDOT) were constructed. Spectroelectrochemistry, electrochromic switching and open circuit stability of the devices were studied. They were found to have good switching times, reasonable contrasts and optical memories.     

SYNTHESES OF THE SOLUBLE,HIGH MOLECULAR WEIGHT AND LADDERLIKE POLYPH ENYLSILSESQUIOXAN E AND COPOLYMETHYLPHENYLSILSESQUIOXANES BY PREAMMINOLYSIS METHOD

Soluble, high molecular weight (MW) and ladderlike polyphenylsilsesquioxane (LPPSQ) and its copolymers, ladderlike random and block copolymethyiphenylsilsesquioxanes(LR-PMPSQ and LB-PMPSQ)have been prepared by preamminolysis, hydrolysis and polycondensation reactions. The preparation method can be carried out easily at the temperature below 95℃with high yield of 95 %, instead of the conventional way by using high-boiling solvent and any reaction activator or by precipitation with methanol. Three kinds of ladderlike polymers have been characterized. The MW's of the polymers reached to 10~6 without noticeable gelling. The scheme for synthetic route has been proposed.     

Potentiometric sensors for Ag+ based on poly(3-octylthiophene) (POT)

Potentiometric ion sensors were prepared from the conjugated polymer poly(3-octylthiopene) (POT). The influence of additional membrane components, including silver 7,8,9,10,11,12-hexabromocarborane (AgCB₁₁H₆Br₆) and potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (KTpFPB) as lipophilic salts, and [2.2.2]p,p,p-cyclophane as silver ionophore, was studied. The membrane components were dissolved in chloroform and membranes were prepared by solution casting on glassy carbon disk electrodes. For comparison, POT-based potentiometric sensors were also prepared by galvanostatic electrosynthesis of POT from the 3-octylthiophene monomer. All the POT-based ion sensors fabricated by solution casting show Nernstian or slightly sub-Nernstian response to Ag⁺, even those based only on POT without any additional membrane components. The potentiometric response of electrochemically polymerized POT depends on the film thickness and the doping anion incorporated in the conducting polymer during polymerization. It is of particular importance that chemically synthesized undoped POT (without any additives) shows a sensitive and selective potentiometric response to Ag⁺ ions although UV-vis results show that POT remains in its undoped form, i.e., POT is not oxidized by Ag⁺. This indicates that undoped POT can exhibit good sensitivity and selectivity to Ag⁺ also in the absence of metallic silver in the polymer film. In this case, the potentiometric response is related to interactions between Ag⁺ and the conjugated polymer backbone. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, 13–16, 2005     

An optical sensor for the determination of digoxin in serum samples based on a molecularly imprinted polymer membrane

This paper reports the synthesis and testing of a molecularly imprinted polymer membrane for digoxin analysis. Digoxin-specific bulk polymer was obtained by the UV initiated co-polymerisation of methacrylic acid and ethylene glycol dimethacrylate in acetonitrile as porogen. After extracting the template analyte, the ground polymer particles were mixed with plasticizer polyvinyl chloride to form a MIP membrane. A reference polymer membrane was prepared from the same mixture of monomers but with no template. The resultant membrane morphologies were examined by scanning electron microscopy. The imprinted membrane was tested as the recognition element in a digoxin-sensitive fluorescence sensor; sensor response was measured using standard solutions of digoxin at concentrations of up to 4 × 10⁻³ mg L⁻¹. The detection limit was 3.17 × 10⁻⁵ mg L⁻¹. Within- and between-day relative standard deviations RSD (n = 5) were in the range 4.5-5.5% and 5.5-6.5% respectively for 0 and 1 × 10⁻³ mg L⁻¹ digoxin concentrations. A selectivity study showed that compounds of similar structure to digoxin did not significantly interfere with detection for interferent concentrations at 10, 30 and 100 times higher than the digoxin concentration. This simply manufactured MIP membrane showed good recognition characteristics, a high affinity for digoxin, and provided satisfactory results in analyses of this analyte in human serum.     

Solid contact ion sensor with conducting polymer layer copolymerized with the ion-selective membrane for determination of calcium in blood serum

A new solid contact ion selective electrode with intermediate conducting polymer (CP) layer formed by electropolymerization on a gold electrode of a bifunctional monomer, n-phenyl-ethylenediamine-methacrylamide (NPEDMA), which contains a methacrylamide group attached to aniline, is presented. The conducting polymer was studied by means of optical spectroscopy, cyclic voltammetry and potentiometric measurements. Ca²⁺-ion-selective membrane based on acrylated urethane polymer was shown to co-polymerize with the CP forming highly adhesive boundary that prevents formation of water layers between the CP and membrane, thus enhancing the stability and life-time of the sensor. The designed ion-selective electrode was successfully used for determination of total calcium ion concentration in blood serum samples.     

Albumin molecularly imprinted polymer with high template affinity — Prepared by systematic optimization in mixed organic/aqueous media

An approach using systematic optimization for the formation of an albumin molecularly imprinted polymer (MIP), able to separate albumin from proteins in solution, has been prepared by imprinting albumin using a copolymer comprising 3-dimethylaminopropyl methacrylate and tetraethylene glycol dimethacrylate in a mole ratio of 1 to 8. Cytochrome c, lysozyme and myoglobin were used in competitive re-binding experiments to compete with the polymer's native template with all protein species present at 0.0004 g mL^− 1. The effects of: monomer to crosslinker mole ratio, polymerization temperature and time were investigated. It was found that the addition of water 6.04%, into the pre-polymerization albumin-monomer complex enhanced the adsorption capacity and selectivity of the resulting MIP from 2.18 × 10^− 3 to 6.02 × 10^− 3 g g-MIP^− 1 and 83.5% to 98.7%, respectively. These results also showed that the MIP possessed high selectivity and adsorption capacity with respect to albumin in comparison with interfering species also present in solution. Polymerization temperature, time and the water content of the pre-polymerization mixture were all shown to have significant effects on the resulting albumin-MIP's performance. However, their influence on the polymer's affinity for the potentially interfering species was negligible. Additionally, higher polymerization temperatures (> 38 °C) and extended polymerization times (> 60 h) increased monomer conversion as determined by HPLC, but decreased the selectivity and adsorption capacity of the MIP. An optimized MIP, with very high selectivity and 6.37 × 10^− 3 g g-MIP^− 1 template re-adsorption capacity was obtained using the following polymerization conditions: 0.125 mole ratio of monomer to crosslinker, 6.04 wt.% water content with respect to the mass of the monomer complex, 60 h polymerization time at 38 °C, and with 0.47% albumin in the pre-polymerization monomer complex. Finally, the functions of polymerization temperature, time and the significance of the water content in the albumin-monomer complex are also discussed.     

Topologically entangled polymers

Summary The statistical mechanics of a ring polymer confined to a plane and entangled with many randomly placed thin rods perpendicular to the plane are considered. The entanglements are characterized by the Gauss linking number. If the statistics of the random distribution of the rods is given by only the second cumulant then it is shown that the resulting entanglement problem can be solved formally exactly. For this special case the exact solution becomes possible because the problem can be reduced to one involving the winding of the polymer around one infinitely thin rod. The exact solution can be obtained for both the annealed and the quenched random distribution of obstacles. The entanglement of the ring polymer around the obstacles leads to a repulsive topological potential which is an effective interaction between the polymer and the rods. The origin of this potential is solely due to the constraint that the winding number be conserved. It is shown that forR ²/Lll (R is the location of the polymer segment,L is the total length of the polymer, andl is the length of the monomer) the topological potential for the annealed random case goes asN ln ln(Ll/R ²) whereN is the number of obstacles whereas for the quenched random case the potential is given byC lnLl/R ², whereC is a numerical constant that depends onN.     

Response Characteristics of a Glucose Electrode with a Sensing Membrane Prepared by Plasma Polymerization

A glucose electrode was composed of a dissolved oxygen electrode and an immobilized glucose oxidase membrane prepared by plasma polymerization of propargyl alcohol as a monomer. Fairly good precision of the electrode response to sample solutions was obtained by measurements using the steady-state method or the reaction rate method. Activity of the glucose oxidase immobilized within the membrane and mounted on the electrode lasted for 50 consecutive measurements over 5 days, and, if the membrane was stored in a buffer solution of pH 7.0 at a temperature of 0°C, the activity was preserved for more than 2 months. Such immobilization of the glucose oxidase with the plasma polymer effectively suppressed interference from Cu²⁺ions, which would seriously interrupt oxidation of the glucose in homogeneous solutions, in the sample solutions.     

Synthesis and Properties of pH-Responsive Polymers with Cadaverine Side Groups

A water-soluble monomer N¹-(4-vinylbenzyl)-pentane-1,5-diamine dihydrochloride (VBPDA) with cadaverine (1,5-pentanediamine) group was synthesized. pH-responsive polymer with cadaverine group was obtained by free radical polymerization of VBPDA using 4,4-azobis(4-cyanovaleric acid) (ACVA) as the initiator. The structure and molecular weight of the polymer were characterized by FTIR, ¹H-NMR and GPC-MALLS. Aggregation behavior of the polymer in aqueous solution was investigated by dynamic light scattering (DLS), UV-Vis and fluorescence measurements. The experimental results show that the fluorescence intensity of the aggregates decreases and the size of the aggregates increases with increasing pH due to the continuous dehydration of the cadaverine side groups.     

单链高分子在纳米孔隙中的跨膜输运问题

针对单链高分子通过薄膜上纳米孔隙的输运这一现象分别首次实验和理论方面介绍了现今的研究进展情况.文中以理论和实验上共同关注的单链高分子跨膜输运的平均通过时间问题展开论述.具体地,作者考察了薄膜的厚度、薄膜的曲率、膜两侧的溶剂性质、单链高分子聚集态的变化以及链间相互作用等因素对输运过程的影响,并讨论了与这些因素相对应的实际应用.同时,分别对几个研究组的实验结果、解析以及模拟的理论结果进行了分析比较,旨在促进这一现象在相关领域的研究.     

Dual Intramolecular Electron Transfer for In Situ Coreactant‐Embedded Electrochemiluminescence Microimaging of Membrane Protein

The demand for transporting coreactant to emitter and short lifetime of the radicals in electrochemiluminescence (ECL) emission inhibit greatly its application in cytosensing and microscopic imaging. Herein we designed a dual intramolecular electron transfer strategy and tertiary amine conjugated polymer dots (TEA‐Pdots) to develop a coreactant‐embedded ECL mechanism and microimaging system. The TEA‐Pdots could produce ECL emission at +1.2 V without need of coreactant in test solution. The superstructure and intramolecular electron transfer led to unprecedented ECL strength, which was 132 and 45 times stronger than those from the mixture of Pdots with TEA at equivalent and 62.5 times higher amounts, respectively. The ECL efficiency was even higher than that of typical [Ru(bpy)₃]²⁺ system. Therefore, this strategy and coreactant‐embedded ECL system could be used for in situ ECL microimaging of membrane protein on single living cells without additional permeable treatment for transporting coreactant. The feasibility and validity were demonstrated by evaluating the specific protein expression on cell surface. This work opens new avenues for ECL applications in single cell analysis and dynamic study of biological events.