Polymer translocation through a nanopore in mesoscopic simulations

Dissipative particle dynamics (DPD) simulations are carried out to study the translocation of a single polymer chain through a pore under fluid field. The influences of the field strength E, the chain length N, the solvent quality α_sp, and the pore size h on the translocation time are evaluated. The translocation time τ, which is defined as the time that the chain moves through the pore completely in the direction of the driving force, scales with the field strength E as τ ∼ E^{−0.48±0.01}. We find that the translocation time is proportional to the chain length, which is in agreement with the experimental results and theoretical predictions. Tracing the variation of the square radius of gyration, , and the polymer configuration during translocation, we observe that the chain is elongated when it is passing through the pore, which manifests that the chain is not in equilibrium during the translocation process. We also find that the worse the solvent quality is, the less time it will take to translocate, no matter what the size of the pore is. If the size of the pore is enlarged, the translocation time will be shorter. The information we gain from this study may benefit to the DNA sequencing.     

Translocation of compact polymer chains through a nanopore

We perform dynamical Monte Carlo simulation to study the forced translocation of compact polymer chains in three-dimensional lattices. The chains are driven through a nanopore connecting two infinite channels by an external field. The scaling properties of average translocation time τ and translocation time distribution (TTD) are studied. The effects of contact energy (?_C), electric field strength (E), and nanopore width (L) on the scaling exponent (α) of average translocation time τ ∼ N^α and the TTD are investigated. For the scaling behavior of τ ∼ N^α, we have found that there is no crossover behavior with weak field strength when the nanopore width is one lattice spacing, which is less than average bond length, while crossover behaviors are observed for larger nanopore widths. The scaling exponent α also depends on contact energy ?_C and electric field strength E. For the TTD, it shifts from the Gaussian to a right-skew distribution with the electric field E increasing for short chains; while for long chains, multi-peak distributions are observed. As a primary and simple model, compact polymer chains are extensively used to capture the structure and thermodynamic properties of proteins, therefore we can investigate the protein translocation by simulating compact chain translocation, and this study will be useful for exploring the complex translocation behaviors of proteins.     

Voltage-driven translocation behaviors of IgG molecule through nanopore arrays

Nanopore-based biosensing has attracted more and more interests in the past years, which is also regarded as an emerging field with major impact on bio-analysis and fundamental understanding of nanoscale interactions down to single-molecule level. In this work, the voltage-driven translocation properties of goat antibody to human immunoglobulin G (IgG) are investigated using nanopore arrays in polycarbonate membranes. Obviously, the background ionic currents are modulated by IgG molecules for their physical place-holding effect. However, the detected ionic currents do ‘not’ continuously decrease as conceived; the currents first decrease, then increase, and finally stabilize with increasing IgG concentration. To understand this phenomenon, a simplified model is suggested, and the calculated results contribute to the understanding of the abnormal phenomenon in the actual ionic current changing tendency.     

Crosslinking of PET through solid state functionalization with alkoxysilane derivatives

A new way for crosslinking poly(ethylene terephthalate) (PET) films and fibers is described using solid state functionalization of the PET end groups (alcohol and acid) with two reagents, respectively, 3-isocyanatopropyltriethoxysilane (IPTESI) or/and 3-glycidoxypropyltrimethoxysilane (GOPTMSI). This functionalization is then followed by hydrolysis-condensation reactions of PET-alkoxysilane end groups leading to the PET crosslinking.First of all, the functionalization reactions were investigated on model compounds by ¹H NMR spectroscopy in a range of temperature 80-160 °C. Furthermore, the diffusion of reagents in solid PET, depending on the initial degree of PET crystallinity, was characterized in the same temperature range through the variation of sample mass. On the other hand, this method allowed us to determine the diffusion coefficients and the solubility of the reagents in solid PET at different temperatures and initial crystallinity degrees.End groups functionalized PET films and fibers by alkoxysilane were then crosslinked by immersion of the samples in hot water. The crosslinking density was characterized by measuring the insoluble fraction of PET in good solvent constituted by a mixture of trifluoroacetic acid and dichloromethane (50/50 vol.). An insoluble fraction close to 70% was obtained by the functionalization treatment of amorphous PET film (8% crystallinity) by a mixture of GOPTMSI + IPTESI (50/50 M) at 155 °C for 1 h followed by hydrolysis-condensation reactions at 80 °C for 72 h. Thermomechanical and thermal properties of films and fibers were observed and found to be considerably enhanced in comparison to the untreated samples. The tensile properties of these partially crosslinked samples were maintained up to 320 °C.     

Calcium phosphate bioceramics synthesized from eggshell powders through a solid state reaction

Everyday millions of tons of eggshells are produced as biowaste around the world. Most of this waste is disposed of in landfills without any pretreatment. Eggshells in landfills produce odors and promote microbial growth as they biodegrade. The present invention provides an environmentally beneficial and cost-effective method of producing calcium phosphate bioceramics (hydroxyapatite or tricalcium phosphate) from eggshell waste. In this investigation, heat treatment produced solid state reactions between eggshell powders and dicalcium phosphate dihydrate (CaHPO₄·2H₂O, DCPD) or calcium pyrophosphate (Ca₂P₂O₇). When eggshell powders (CaO) and DCPD were heat treated at 1150 °C for 3 h, only a single hydroxyapatite (HA) phase was found; no diffraction peaks of starting materials and no β-TCP were observed. The XRD patterns of the product fabricated from raw eggshell powders (CaCO₃) and Ca₂P₂O₇ heat treated at 1100 °C for 3 h showed that almost only pure β-TCP remained with a trace amount of HA. The calcium phosphate ceramic synthesized from eggshell powders contains several important trace elements such as Na, Mg and Sr.     

Mechanistic studies of protein refolding facilitated by like-charged polymers

The mechanism of lysozyme refolding facilitated by like-charged polymers was studied using cationic polyelectrolytes of different molecular weights and structures. Lysozyme refolding yield increased with increasing the total charge ratio (R) of the charged polymer to lysozyme in the refolding solution till reaching a plateau at a critical total charge ratio (R_c). The same R_c was observed for different polymers. Similarly, there was a critical minimum polymer molecular weight (M_c) for the facilitated protein refolding, below which the refolding yield decreased. The refolding yield was independent of the charge group structures in polymer. Fluorescence spectroscopy revealed that the polymers had no effect on the protein folding kinetics. Two physical models were proposed to explain the mechanism of the facilitated refolding and the meanings of R_c and M_c. The facilitating effect was attributed to the electrostatic interaction-induced oriented alignment of multiple protein molecules near the polymer chains, which maximizes the electrostatic repulsion between neighboring protein molecules, leading to the inhibition of protein aggregation. The studies provided insight into the mechanism of like-charged polymer-facilitated protein refolding, which would help develop more efficient polymers/particles for facilitated protein refolding applications.     

Modelling effects of current distributions on performance of micro-tubular hollow fibre solid oxide fuel cells

A three-dimensional model, considering mass, momentum, energy and charge conservation, was developed and the equations solved to describe the physico-chemical phenomena occurring within a single, micro-tubular hollow fibre solid oxide fuel cell (HF-SOFC). The model was used to investigate the spatial distributions of potential, current and reactants in a 10 mm long HF-SOFC. The predicted effects of location of current collectors, electrode conductivities, cathode thickness and porosity were analysed to minimise the ranges of current density distributions and maximise performance by judicious design. To decrease the computational load, azimuthal symmetry was assumed to model 50 and 100 mm long reactors in 2-D. With connectors at the same end of the HF-SOFC operating at a cell voltage of 0.5 V and a mean 5 kA m⁻², axial potential drops of ca. 0.14 V in the cathode were predicted, comparable to the cathode activation overpotential. Those potential drops caused average current densities to decrease from ca. 6.5 to ca.1 kA m⁻² as HF-SOFC length increased from 10 to 100 mm, at which much of the length was inactive. Peak power densities were predicted to vary from 3.8 to <2.5 kW m⁻², depending on the location of the current collectors; performance increased with increasing cathode thickness and decreasing porosity.     

Forced translocation of polymer chains through a nanotube: A case of ultrafiltration

Translocation of polymer chains under the application of an external force has been studied through coarse-grained Monte Carlo simulations. The chains are pulled through a nanotube of finite length and diameter and their translocation times measured. The average translocation time, τ follows a scaling relation involving the chain length, N and applied force, F as, τ ∼ N^ν′F^−μ, where ν′ and μ are two different exponents (ν′ = 0.674, and μ = 0.95 ± 0.05). The scaling law is closely similar to the nanopore translocation scaling law reported by Milchev et al. [Ann N Y Acad Sci 2009;1161:95]. Characteristic signatures of the chain escape time have been exhibited by the square of end-to-end distance R², axial radius of gyration R_g−x and other constituent properties. The behavior of the linear polymers under the application of a pulling force has been exploited to gain insights into the ultrafiltration process of unentangled polymers in dilute solution. The generic pulling force-translocation time (F, τ) data obtained through simulation can be matched reasonably well with the hydrodynamic force-critical macroscopic flow time (f_h, Q_c⁻¹) data and also with the hydrodynamic force-reduced critical microscopic flow time (f_h, q_c⁻¹) data obtained in the ultrafiltration experiment on long linear polystyrene chains in cyclohexane, as recently reported by Ge et al. [Macromolecules 2009;42:4400] The simulation technique reported here may be extended to study biomolecular transports occurring in long protein channels, as studied experimentally through current-time or voltage-time traces.     

Voltammetry and spectroelectrochemistry of solid indigo dispersed in carbon paste

Cyclic voltammetry, square wave voltammetry and double potential step UV-vis spectroelectrochemistry were used to study the redox processes of indigo microparticles dispersed in a solid carbon paste electrode. The spectroelectrochemical measurements were performed in a home-made long-path-length thin-layer electrolysis cell. Both the indigo/leucoindigo and indigo/dehydroindigo redox couples underwent reversible 2e⁻/2H⁺ surface-confined reactions. Alkaline electrolytes showed more negative effect on the reduction of indigo to leucoindigo than on its oxidation to dehydroindigo. A new species (probably indolone) was monitored in the re-oxidation of leucoindigo, while isatin was found in the oxidation of indigo at enough positive potential. More detailed electrochemical mechanisms were proposed for the two redox systems, respectively. The present work shows that the microparticle-dispersed carbon paste is an attractive electrode material not only for solid state voltammetry but also for stripping spectroelectrochemistry.     

Ethanol production by solid state fermentation of sweet sorghum using thermotolerant yeast strain

Solid state fermentation of chopped sweet sorghum particles to produce ethanol was studied statically using thermotolerant yeast. The influence of various process parameters, such as yeast cell concentration, particle size and moisture content, on the ethanol yield was investigated. Optimal values of these parameters were 4 × 10⁶ cells/g raw sorghum, Dp = 1.5 mm and 75%, respectively. Addition of reducing agent H₂SO₃ into the fermentation medium provided anaerobic condition, and obtained the maximum ethanol yield of 7.9 g ethanol per 100 g fresh stalks or 0.46 g ethanol/g total sugar, which was 91% of the theoretic yield.     

固相接枝法制备聚丙烯相容剂

通过固相接枝法将甲基丙烯酸缩水甘油酯（GMA）、苯乙烯（St）接枝到聚丙烯（PP）主链上制得聚丙烯相容剂。讨论了界面剂、引发剂、GMA、St、反应时间与反应温度对产物接枝率的影响,结果发现这些实验条件均对聚丙烯相容剂接枝率产生较大的影响,最佳的制备条件为m（PP）：m（GMA）：m（St）：m（BPO）：m（二甲苯）=100：15：15：1：10,反应温度为120℃,反应时间为1h。     

Low-temperature solid state synthesis of Eu-doped Ca2SnO4 ceramics under CO-CO2 atmosphere

High temperature solid state is reported the most common synthesis technique for Ca₂SnO₄ ceramics, nevertheless it requires high thermal treatment temperature and long synthesis time. Our previous studies indicated that Ca₂SnO₄ was much easier to form if SnO₂ and CaCO₃ were roasted under CO-CO₂ atmosphere at relatively low temperatures. In this study, the reaction mechanism between SnO₂ and CaCO₃ under 15 vol% CO/(CO+CO₂) atmosphere and air atmosphere were firstly investigated by using XRD, SEM, XPS, etc. In addition, the Eu-doped Ca₂SnO₄ was synthesized by low-temperature solid state reaction under CO-CO₂ atmosphere. The results indicated that the crystal structure and photoluminescence properties of the products were similar to those of samples synthesized under air atmosphere, whereas the synthetic temperature was reduced by more than 300 °C.     

The influence of activated carbon as an additive in anode materials for low temperature solid oxide fuel cells

The effects of activated carbon (AC) as an additive in multi-oxide nano composite LiNiCuZn–O for application as anode in solid oxide fuel cell (SOFC) is reported. The composite was synthesized using solid state reactions method with varying content of AC in range 0.1%–0.9% for use as anode in the cell. The cell was composed of the synthesized composite as anode, LiNiCuZn–O as cathode and Samaria doped ceria (SDC) as electrolyte. The prepared composites were characterized for morphology and crystal structure by scanning electron microscope (SEM) and x-ray diffraction (XRD) respectively. Furthermore, the crystallite sizes of LiNiCuZn–O and LiNiCuZn–O with AC as an additive have been found in the range from 50 nm to 70 nm. The prepared composite materials were observed porous and the porosity of the sample having 0.5% additive was found highest. The conductivity and power density of the SOFC were studied at temperature of 600 °C. The maximum value of conductivity was found as 4.79 S/cm for the composite containing 0.5% AC as measured by using 4-probe method. The maximum value of power density of the fuel cell with anode comprising of 0.5% AC along with the mentioned cathode and the electrolyte was 455 mW/cm². Therefore, out of the compositions studied, the composite comprising of LiNiCuZn–O with 0.5% AC offered best performance for anode in the cell. This oxide composite is reported as a potential candidate for use as anode in low temperature SOFCs.     

Fracture behavior of solid electrolyte LATP material based on micro-pillar splitting method

The NASICON type solid electrolyte LATP is a promising candidate for all-solid-state Li-ion batteries considering energy density and safety aspects. To ensure the performance and reliability of batteries, crack initiation and propagation within the electrolyte need to be suppressed, which requires knowledge of the fracture characteristics. In the current work, micro-pillar splitting was applied to determine the fracture toughness of LATP material for different grain orientations. The results are compared with data obtained using a conventional Vickers indentation fracture (VIF) approach. The fracture toughness obtained via micro-pillar splitting test is 0.89 ± 0.13 MPa?m^1/2, which is comparable to the VIF result, and grain orientation has no significant effect on the intrinsic fracture toughness. Being a brittle ceramic material, the effect of pre-existing defects on the toughness needs to be considered.     

固相法合成乙酰丙酮镧

以无机镧盐、固体碱、乙酰丙酮(Hacac)为原料,在室温下无溶剂固相研磨合成乙酰丙酮镧。考察了碱的种类,乙酰丙酮的量,NaOH的量,以及研磨时间对产率的影响。采用红外、热重及X射线衍射对目标产物进行了表征,结果与标准谱图基本一致。实验结果表明LaCl3.6H2O 10mmol,Hacac 40mmol,NaOH 30mmol,室温下研磨1 h所得乙酰丙酮镧的产率达97.48%,高出经典液相法8.48个百分点。     

New aspects on the mechanism of the solid state polyamidation of PA 6,6 salt

Hexamethylenediammonium adipate (PA 6,6 salt) was solid state polymerized in the temperature range of 158-190 °C, in a thermogravimetric analysis (TGA) chamber, which simulates a polyamidation reactor. A mechanism based on the role of the volatile component of the salt (i.e. hexamethylenediamine) is found to predominate: the diamine escapes along with polycondensation water, meanwhile this volatilization occurs earlier than the water formation, apparently resulting in an increase of the vacancy defects and of the nucleation sites in the salt crystals. In addition, critical reaction parameters, such as reaction time, temperature, surrounding gas and presence of catalyst in the starting material were investigated, so as to discern the rate-controlling mechanism of the process. Finally, proper SSP kinetics were studied taking into consideration the diamine loss occurred and SSP rate constants were calculated through a suitable rate expression.     

Fluorescein analogues inhibit SecA ATPase: the first sub-micromolar inhibitor of bacterial protein translocation

SecA is a central component of the general secretion system that is essential for bacterial growth and thus an ideal target for antimicrobial agents. A series of fluorescein analogues were first screened against the ATPase activity using the truncated unregulated SecA catalytic domain. Rose bengal (RB) and erythrosin B (EB) were found to be potent inhibitors SecA with IC(50) values of 0.5 μM and 2 μM, respectively. RB and EB inhibit the catalytic SecA ATPase more effectively than the F(1) F(0) -proton ATPase. We used three assays to test the effect of these compounds on full-length SecA ATPase: in solution (intrinsic ATPase), in membrane preparation, and translocation ATPase. RB and EB show the following trend in terms of IC(50) values: translocation ATPase相似文献   

Effect of solid circulation rate on coating efficiency and agglomeration in circulating fluidized bed type coater

Circulating fluidized bed was proposed to be used as a coater, and coating experiments of glass beads with silica powder were performed in a circulating fluidized bed. Glass beads and silica powder were chosen as model particles, because their shape was almost spherical. The respective effects of gas flow rates supplied from a distributor and from an air nozzle for solid circulation, feed rate of powder suspension and particle content in the bed on coating efficiency and agglomeration are mainly discussed. Coating efficiency in circulating fluidized bed coater was correlated well with solid circulation time rather than with gas flow rates or solid circulation rate, while the agglomeration among core particles was mainly governed by solid circulation rate.