Influence of the roughness, topography, and physicochemical properties of chemically modified surfaces on the heterogeneous nucleation of protein crystals

In this study, the influence of some factors on the heterogeneous nucleation of hen egg-white lysozyme (E.C. 3.2.1.17) on a series of chemically modified surfaces has been investigated. Microbatch crystallization experiments were conducted on the microscope glass slides that were treated with poly-L-glutamic acid (PLG), poly(2-hydroxyethyl methacrylate) (P2HEMA), poly(methyl methacrylate) (PMMA), poly(4-vinyl pyridine) (P4VP), and (3-aminopropyl)triethoxysilane (APTES). An optical microscope with a heating/cooling stage was employed to measure the induction time of heterogeneous nucleation. The surface topography and roughness were characterized by atomic force microscopy. Contact angles for crystallization solution on the investigated surfaces were measured by a contact angle meter. From the theoretical analysis, the energetic barrier to heterogeneous nucleation was found to increase at higher contact angles and to decrease at higher roughness. Experimentally, a qualitative increase of the induction time of the heterogeneous nucleation on P2HEMA, APTES, and PMMA surfaces with the contact angle was observed. Such surfaces as P2HEMA, PLG, and APTES, which were of higher roughness, were shown to promote the heterogeneous nucleation. In addition, the surface with specific topography is expected to increase the possibility of the formation of a critical nucleus. Finally, the P4VP surface appeared to suppress the heterogeneous nucleation as a result of the electrostatic interaction between the lysozyme and P4VP molecules.     

Membrane thickness and preparation temperature as key parameters for controlling the macrovoid structure of chiral activated membranes (CAM)

A macrovoid structure is formed in polysulfone (PSf) polymeric membranes prepared by the immersion technique using N-dimethylformamide (DMF)/water as a solvent/non-solvent pair. It is actually important controlling the macrovoid formation process, because macrovoids can cause unwanted mechanical failure during high-pressure applications. In order to control the formation of these structures, the influence of different parameters like membrane thickness, solvent additives (isopropyl myristate, IPM or N-hexadecyl-l-hydroxypriline, HHP), temperature of the coagulation bath, and solvent/non-solvent pair has been studied for chiral activated membranes. With the same purpose, corresponding membranes where physically characterized by scanning electron microscopy (SEM) measurements of their cross-section images. Those SEM images have been treated by the software IFME^®, which provides the parameters of asymmetry and irregularity of the membranes. The surface of the membranes has been analyzed by atomic force microscopy (AFM) and brightness analysis in order to calculate their roughness. A comparison of the same PSf membranes, but prepared by evaporation precipitation, or by using chloroform/methanol as solvent/non-solvent pair during the immersion precipitation step, has been also checked. That paper helps us to understand and predict which will be the best conditions to prepare the optimum membranes.     

Hyperbolic Spirals as Surface Structures in Thin Layers

When thin layers of 4-chloro-3-methylphenol and a copolymer of methyl(methacrylate) and maleic acid dissolved in acetone are dried by solvent evaporation, various surface structures appear. Besides linear surface deformations that can ramify like fractals, spirals of the hyperbolic type have been found. The surface structures are due to crystallization processes and flows caused by surface tension differences. The spirals are surface elevations with grooves on both sides as shown by surface profile measurements by means of a microscope interferometer. The addition of surfactants reduces the structure formation. A large surfactant concentration prevents the structure formation. Copyright 2001 Academic Press.     

Enthalpy-entropy compensation of ionic liquid-type Gemini imidazolium surfactants in aqueous solutions: a free energy perturbation study

Hierarchical nanocrystalline ZSM-5 zeolite (NZ5) was synthesized at 100 °C under atmospheric pressure using methylamine as a mineralizing agent. The crystallization process of NZ5 was characterized by dynamic light scattering (DLS), X-ray diffraction (XRD), and infrared spectroscopy (FTIR). The results of contrastive experiments showed that evaporation of the solvent promoted the aggregation of primary particles, and the addition of methylamine accelerated the crystallization process. The NZ5 aggregate consisted of 20 nm individual particles, as shown in scanning electron microscope (SEM). The lattice fringes in the transmission electron microscope (TEM) images and the XRD results indicated that individual particles of NZ5 were highly crystalline. N(2) adsorption-desorption isotherms showed that NZ5 had high BET surface areas with mesopores having a mean diameter of about 9 nm. NZ5 exhibited a long lifetime, a stable and high yield of liquid hydrocarbons, and a high anti-coking performance in methanol-to-hydrocarbons reaction. Catalytic testing and TGA results showed that the lifetime of NZ5 was about ten times longer than that of micro-sized ZSM-5 zeolite (MZ5), and the average coking rate with NZ5 was one fifth over that of MZ5.     

Surface roughness in dynamically crystallized isotactic polypropylene films

The relationship between the dynamic crystallization conditions and surface topography of iso‐polypropylene (i‐PP) films was examined with fractal geometry. When i‐PP was crystallized from a melt at cooling rates in the range between 1 and 100 °C/min, the generated surface topography presented self‐affine behavior at least in the scale range from 0.1 to 100 μm. Moreover, the calculated roughness exponent of these surfaces increased with the cooling rate used to crystallize the samples, which meant a smoother surface at higher crystallization rates. This behavior could be qualitatively explained in terms of the temperature effect on the nucleus stability, the molecular mobility, and the surface tension. In addition, the morphology of quenched samples was analyzed, and different hypotheses were proposed to explain the unusual observed behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 646–655, 2004     

Probing structural changes of spin-coated polystyrene film after swelling and precipitation by synchrotron GIUSAXS and AFM

Polystyrene film of about 50 nm in thickness on silicon wafer was obtained by spin-coating in tetrahydrofuran solution. The film exhibits a rough surface as shown by atomic force microscopy images and ellipsometry data. Furthermore, such surface roughness produced a characteristic lateral correlation peak in an “out-ofplane” scan in the synchrotron grazing incidence ultra-small angle X-ray scattering pattern. The film was treated with liquids of solvent and non-solvent sequentially, resulting in a process of swelling and precipitation of the polystyrene film. Such a solvent/non-solvent treatment completely changed the original surface structure of the film. Aggregates of polystyrene of different sizes were observed both in atomic force microscopy and synchrotron grazing incidence ultra-small angle X-ray scattering measurements. The results demonstrate that synchrotron grazing incidence ultra-small angle X-ray scattering is a unique means to investigate large area micro-structural features of thin films supported on smooth surfaces.     

Atomic force microscopy of dense and asymmetric cellulose-based membranes

The surface structures of dense and integrally skinned cellulose acetate (CA) and cellulose acetate butyrate (CAB) membranes, prepared by phase inversion under different casting conditions, are investigated by tapping mode atomic force microscopy (TM AFM). The results obtained show that: (i) The top and bottom surfaces of the dense CA membrane were quite uniform in comparison with the corresponding faces of asymmetric CA and CAB membranes. Despite the casting conditions the active and support layers of the asymmetric membranes display large differences on the roughness parameters. (ii) The asymmetric membranes prepared with an organic system as a non-solvent pore-former (method IV) display smaller nodule aggregates and lower values of the roughness parameters than the ones prepared using an inorganic system as swelling agent (method I). This is more pronounced for the CA membranes than for the CAB membranes. (iii) In the active layer of asymmetric CA membranes casted at longer evaporation times, the measured values of surface roughness parameters tend to decrease. Also, for these CA membranes, as the evaporation time increases the average size of the depression areas observed on the surface decreases.

The laboratory-made CA and CAB membranes display a wide range of nanofiltration and reverse osmosis permeation characteristics. These characteristics are correlated to surface roughness parameters of the active layers.     

Poly(L‐lactide)/C60 nanocomposites: Effects of C60 on crystallization of poly(L‐lactide)

The effects of solvent type and concentration of C₆₀ on the crystallization of poly(L ‐lactide) (PLLA) during solvent evaporation, heating from room temperature, and cooling from the melt were investigated by polarized optical microscopy and differential scanning calorimetry. The addition of C₆₀ enhanced the PLLA crystallization during solvent evaporation, during heating of the melt‐quenched films, and during cooling from the melt of As‐cast films, except for heating and cooling of the PLLA film with 1 wt % of C₆₀ prepared with dichloromethane. In the case of solvent evaporation, the difference in crystallinity between the PLLA films with and without C₆₀ became higher for the solvent with a lower boiling point. In the case of heating of melt‐quenched films, the addition of C₆₀ had a small effect on the crystallinity of PLLA, whereas significantly lowered the peak top and ending temperatures of cold crystallization, except for melt‐quenched PLLA film with 1 wt % of C₆₀ prepared with dichloromethane. The crystallinity of PLLA was determined by the solvent type, rather than by the C₆₀ concentration. In the case of cooling from the melt of As‐cast films, the addition of C₆₀ elevated the crystallinity and cold crystallization temperature values of PLLA films, except for PLLA films prepared with dichloromethane. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2167–2176, 2007     

FORMATION OF FLOWER-LIKE AGGREGATES FROM SELF-ASSEMBLING OF MICELLES WITH PEO SHELLS AND CROSS-LINKED POLYACRYLAMIDE CORES

Amphiphilic block copolymers,poly(ethylene oxide)-b-poly(N-acryloxysuccinimide) (PEO-b-PNAS) with various molecular weights have been successfully synthesized by atom transfer radical polymerization (ATRP) of NAS using functionalized PEO (PEO-Br) as ATRP macroinitiator.The self-assembling of the block copolymers in water,which is a good solvent for PEO and a non-solvent for PNAS.yielded spherical core-shell micelles with PNAS as core and PEO as shell.The cross-linked reaction of oxysuccinimide in PNAS ch...     

Lamellar orientation in thin films of symmetric semicrytalline polystyrene-b-poly(ethylene-co-butene) block copolymers: effects of molar mass, temperature of solvent evaporation, and annealing

Orientation of the lamellar microdomains in thin films of three symmetric polystyrene-b-poly(ethylene-co-butylene) block copolymers (S65E155, S156E358, and S199E452) on mica was investigated via atomic force microscopy (AFM), grazing incidence X-ray diffraction (GIXRD) and X-ray photoelectron spectroscopy (XPS). The results show that lamellar orientation in the SxEy block copolymers greatly depends on the molar mass of the block copolymers, the temperature of solvent evaporation, and annealing. The nascent thin film of the low molar mass block copolymer, S65E155, shows a multilayered structure parallel to the mica surface with the PS block at both polymer/mica and polymer/air interfaces, but the high molar mass block copolymers, S156E358 and S199E452, exhibit a structure with lamellar microdomains perpendicular to the mica surface. When the solvent is evaporated at a lower temperature, the crystallization rate is fast and a two-dimensional spherulite structure with the lamellar microdomains perpendicular to the mica surface is observed. Annealing of all the thin films with lamellar microdomains perpendicular to the mica surface leads to morphological transformation into a multilayered structure parallel to the mica surface. In all SxEy thin films on mica, the stems of PE crystals are always perpendicular to the interface between the lamellar PE and PS microdomains. A mechanism is proposed for the formation of different microdomain orientations in the thin films of semicrystalline block copolymers. When the thin film is prepared from a homogeneous solution, microdomains perpendicular to the substrate surface are formed rapidly for strongly segregated block copolymers or at a lower crystallization temperature and kinetically trapped by the strong segregation strength or solidification of crystallization, while for weakly segregated block copolymers or at slower crystallization rate, the orientation of the microdomains is dominated by surface selectivity.     

Synthesis and Characterization of Poly(ether-block-amide) Membranes

Poly(ether-block-amide) membranes were made via casting a solution on a nonsolvent (water) surface. In this research, effects of different parameters such as ratio of solvent mixture (n-butanol/isopropanol), temperature, composition of coagulation bath (water) and polymer concentration, on quality of the thin film membranes were studied. The mechanism of membrane formation involves solution spreading, solvent–nonsolvent exchange, and partial evaporation of the solvent steps. Solvent- nonsolvent exchange is the main step in membrane formation and determines membrane morphology. However, at higher temperature of polymeric solution greater portion of solvent evaporates. The results showed that type of demixing process (mutual affinity between solvent and nonsolvent) has important role in film formation. Also, addition of solvent to the nonsolvent bath is effective on membrane morphology. The film quality enhances with increasing isopropanol ratio in the solvent mixture. This behavior can be related to increasing of solution surface tension, reduction of interfacial tension between solution and nonsolvent and delayed solvent-nonsolvent demixing. Uniform films were made at a temperature rang of 60–80 °C and a polymer concentration of 4–7 wt%. Morphology of the membranes was investigated with scanning electron micrograph (SEM). Pervaporation of ethyl butyrate/water mixtures was studied using these membranes and high separation performance was achieved. For ethyl butyrate/water mixtures, It was observed that both permeation flux and separation factor increase with increasing ethyl butyrate content in the feed. Increasing temperature in limited range studied resulted in decreasing separation factor and increasing permeation flux.     

二氧化硅胶体晶体组装形貌研究

用原子力显微镜表征了二氧化硅胶体晶体的组装,探讨了二氧化硅微球用自然沉降法、抽滤法、溶剂挥发法组装时的组装行为,同时讨论了不同颗粒表面电位、不同溶剂介质及不同温度对其组装结果的影响。结果表明,颗粒表面电位是影响二氧化硅胶体晶体有序组装的重要因素之一。文中总结了最优的介质组成和温度条件,指出溶剂挥发法是较优的二氧化硅胶体晶体组装方法,其方法操作简单、周期短、得到的胶态晶体质量高,能在较大面积内高度有序。     

Crystallization of calcium sulfate on polymeric surfaces

Surface crystallization of calcium sulfate dihydrate (gypsum) on a series of polymeric surfaces was studied using a quartz microbalance system. Polyelectrolyte multilayer films (positively and negatively charged surfaces) were formed on the quartz crystal microbalance (QCM) sensors utilizing a layer-by-layer spin-assembly method. The kinetics of gypsum surface crystallization was quantified in terms of the evolution of gypsum mineral scale on the different surfaces. For comparison mineral scaling was also evaluated on silica and polyamide surfaces. For surfaces of the same charge polarity (+/-), the mass density of gypsum scale was lower (PSS相似文献   

A facile method for preparing sticky, hydrophobic polymer surfaces

Textured surfaces consisting of nanometer- to micrometer-sized lightly sulfonated polystyrene ionomer (SPS) particles were prepared by rapid evaporation of the solvent from a dilute polymer solution-cast onto silica. The particle textured ionomer surfaces were prepared by either spin-coating or solution-casting ionomer solutions at controlled evaporation rates. The effects of the solvent used to spin-coat the film, the molecular weight of the ionomer, and the rate of solvent evaporation on the surface morphology of cast films were investigated. The surface morphologies were consistent with a spinodal decomposition mechanism, where the surface first existed as a percolated-like structure and then ripened into droplets if molecular mobility was retained for sufficient time. The SPS particles or particle aggregates were robust and resisted separation from the surface even after annealing at 120 °C for 1 week. The water contact angles on as-prepared surfaces were relatively low, ～90°, due to the polar groups in the ionomer, but when the surface was modified by chemical vapor deposition of 1H,1H,2H,2H-perfluorooctyltrichlorosilane, the surface contact angles increased to ～109° on smooth surfaces and up to ～140° on the textured surfaces. Although the surfaces were hydrophobic, the contact angle hysteresis was relatively high and water droplets stuck to these surfaces even when the surface was turned upside down.     

Fabrication study of polysulfone hollow-fiber microfiltration membranes: Optimal dope viscosity for nucleation and growth

Fabrication of polysulfone hollow-fiber microfiltration membranes through non-solvent induced phase separation (NIPS) by dry–wet spinning was studied. For all sample preparations, we used N-methylpyrrolidone (NMP) as solvent, polyethylene glycol (PEG) as additive, aqueous NMP solution as bore liquid, and water as coagulation bath. Particular focus was placed on the influence of PEG molecular weight (Mw) on membrane structure. Characterization of the obtained membranes was performed by measuring pure water permeate flux, tensile strength, and tensile elongation at break, and by analyzing scanning electron microscope (SEM) images of hollow-fiber cross-sections, outer surfaces, and inner surfaces.     

Diffusion phenomena in ternary systems polymer-nonsolvent-solvent

Diffusion in a boundary between a polymer+solvent solution and non-solvent was treated by accounting for the presence of the four diffusion coefficients that describe the isothermal transport process in a three component system. Diffusion equations were integrated assuming a concentration dependence of diffusion coefficients that account for the thermodynamic conditions on the cross diffusion terms of Eq. (1). The presence of non-zero cross terms promotes an incongruent diffusion of polymer whose concentration increases at the boundary between the polymer+solvent solution and the non-solvent. Although our model describes diffusion in the range of homogeneous solution, this incongruent polymer diffusion is a process similar to that promoted by the solvent evaporation from the polymer+solvent film that some authors suggested as an intermediate step before the film immersion into the coagulation bath to obtain good asymmetric membranes.     

FTIR imaging coupled with multivariate analysis for study of initial diffusion of different solvents in cellulose acetate butyrate films

Fourier transform infrared (FTIR) spectroscopic imaging was used to study the initial diffusion of different solvents in cellulose acetate butyrate (CAB) films containing different amounts of acetyl and butyryl substituents. Different solvents and solvent/non-solvent mixtures were also studied. The FTIR imaging system allowed acquisition of sequential images of the CAB films as solvent penetration proceeded without disturbing the system. The interface between the non-swollen polymer and the initial swelling front could be identified using multivariate data analysis tools. For a series of ketone solvents the initial diffusion coefficients and diffusion rates could be quantified and were found to be related to the polar and hydrogen interaction parameters in the Hansen solubility parameters of the solvents. For the solvent/non-solvent system the initial diffusion rate decreased less than linearly with the weight-percent of non-solvent present in the solution, which probably was due to the swelling characteristic of the non-solvent. For a given solvent, increasing the butyryl content of the CAB increased the initial diffusion rate. Increasing the butyryl content from 17 wt.% butyryl to 37 wt.% butyryl produced a considerably larger increase in initial diffusion rate compared to an increase in butyryl content from 37 wt.% to 50 wt.% butyryl.     

热处理对聚偏氟乙烯-酰胺类溶剂所制薄膜结晶行为的影响

使用红外光谱和偏光显微镜对PVDF(聚偏氟乙烯)-DMF(N,N-二甲基甲酰胺)和PVDF-DMAc(N,N-二甲基乙酰胺)体系结晶行为的研究表明,PVDF薄膜的结晶受制备溶剂,后期热处理温度和膜厚度等因素的影响;升高温度,β相含量减小;当温度低于90℃时,PVDF-DMF体系的F(β)值较DMAc体系大,在90~160℃之间则相反,且两种体系的F(β)值分别在约90℃和80℃发生“突变”;同时,结晶还明显受到薄膜厚度的影响,厚度大,结晶较完善.     

High throughput study of phase inversion parameters for polyimide-based SRNF membranes

High throughput (HT) techniques were applied for the first time for a detailed study of parameters involved in a phase inversion process. The synthesis of integrally skinned asymmetric polyimide (Matrimid^®) membranes was investigated. In spite of being one of the most important materials of reference in solvent resistant nanofiltration (SRNF), a detailed study of the phase inversion parameters for this system is still missing. Phase inversion parameters were selected both on the level of the composition of the casting solution (polymer concentration, solvent type, co-solvent/solvent weight ratio, non-solvent content) as on the level of the post-casting (evaporation time) and immersion (composition coagulation medium) conditions. The study of this extensive parameter space was conducted in a HT-fashion, in which the entire membrane preparation and testing process was miniaturized, parallellized and automated. Thanks to the availability of reliable HT techniques at all levels (i.e. preparation of polymer solutions, membrane casting and membrane testing), 145 membranes were prepared and tested (in triplicate) in the separation of the dye rose Bengal from 2-propanol within a time frame of a few months, meaning a dramatic improvement in time- and cost-efficiency. An attempt was made to link the SRNF performances of the prepared membranes and their SEM-observed morphologies more fundamentally to the phase inversion parameters through the use of Hansen solubility parameters and viscosity measurements.     

Amination of surfaces via self-assembly of dopamine

Catechols can strongly bind to a variety of substrates so as to functionalize the target surfaces by forming self-assembled monolayer. However, catecholic amine might self-oxidize and polymerize at high pH since the amine is susceptible to nucleophilic addition reaction that results in polymerized oligomers on surfaces. Therefore, the availability of amines for further derivation reaction would be restricted to a large extent. Herein, by controlling pH values to avoid self-oxidative polymerization, dopamine (DA) forms thin and surface-adherent monolayers onto a wide range of inorganic and organic materials, including mica, silica, and Au surface, allowing amination of the surfaces that resemble commercially used aminosilanization. The self-assembly process was traced by surface topography and elemental composition analysis using atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS), and electrochemical characterization (electrochemical impedance spectroscopy and cyclic voltammetry measurements). Then, the aminated surfaces were used for secondary derivation reactions to create a variety of ad-layers, including patterned streptavidin through specific binding interaction with biotin and ferrocene surface via amidation reaction. The surface and interface properties of the obtained surfaces were tested by electrochemical measurements.