Absolute rate of turbulent coagulation from turbidity measurement

Turbidity method has been applied to assess colloid stability. While the method is simple and easy, it is not straightforward in evaluating absolute coagulation rates of colloidal particles. That is, the method requires the evaluation of the extinction cross section of doublets. Recently, the turbidity measurement has been successfully utilized to evaluate the absolute Brownian coagulation rate constant with the T-matrix method, which calculates the extinction cross section of doublets at arbitral size range. The present work was performed to extend the applicability of the method to turbulent coagulation. To this end, we measured the turbidity change of coagulating latex suspensions in a turbulent flow. The measurement was performed as a function of particle size. From the turbidity vs. time relationship, we evaluated turbulent coagulation rate constant using the T-matrix method. Obtained values of the constants agreed well with theoretical ones, demonstrating the usefulness of turbidity method for turbulent coagulation.     

Diffusion-viscometric analysis and conformational characteristics of sodium polystyrenesulfonate molecules

Samples of sodium polystyrenesulfonate of molecular weights varying in a 20-fold range were synthesized. The hydrodynamic behavior of the samples was studied in a 0.2 M NaCl solution in which the initial polyelectrolyte effects are suppressed. Relationships between the molecular weight and the translational friction coefficient and intrinsic viscosity were obtained. The theory describing the hydrodynamic behavior of wormlike chains with taking into account both the percolation effects and the excluded-volume effects was applied to estimation of the length of the statistical segment and the cross section of the sodium polystyrenesulfonate molecules in 0.2 M NaCl solution.     

Simple cross-section model for elementary reactions

A simple reaction cross-section model has been obtained. It consists of hard spheres where the mass of the products has been introduced via angular momentum conservation. For exothermic reactions the cross section shows a maximum, providing that a threshold energy is present. The model has been applied to the alkali-atom—alkyl-oxide reactions, giving a simple understanding of the systematic trend of the cross section and the energy dependence of its maximum.     

Quantum chemical studies of three-photon absorption of some stilbenoid chromophores

Three-photon absorption of a series of donor-acceptor trans-stilbene derivatives is studied by means of density functional theory applied to the third-order response function and its residues. The results obtained by using different functionals are compared with experimental data for similar systems obtained from the literature. With a Coulomb attenuated, asymptotically corrected functional, the excitation energy to the first resonance state is much improved. Comparison with experiment indicates that this is the case for the three-photon cross section as well. In particular, the overestimation of the cross sections and underestimation of excitation energies offered by the density functional theory using common density functionals is corrected for. It is argued that a reliable theory for three-photon absorption in charge transfer and other chromophore systems thereby has been obtained. Further elaboration of the theory and its experimental comparison call for explicit inclusion of solvent polarization and pulse propagation effects.     

Colloidal behavior of nanoemulsions: Interactions,structure, and rheology

Nanoemulsions exhibit unique behavior due to their nanoscopic dimensions, including remarkable droplet stability, interactions, and rheology. These properties are significantly enhanced by nanoscopic droplet size, as well as the selection of surfactant and other molecular species in solution. Electrostatic and polymer-induced interdroplet interactions are particularly powerful tools for fine-tuning the interdroplet interactions, and have led to stimuli-responsive nanoemulsion systems that provide deep insight into their unique properties. As such, nanoemulsions have emerged as powerful model systems for studying a number of colloidal phenomena including suspension rheology, repulsive and attractive colloidal glasses, aggregation processes, colloidal gelation and phase instability, and associative network formation in polymer–colloid mixtures. This review summarizes recent advances in understanding the colloidal behavior of nanoemulsions, and provides a unifying framework for understanding the various complex states that emerge, as well as perspective on emerging challenges and opportunities that will advance the use of nanoemulsions in both fundamental colloid science and technological applications.     

Chemically encapsulated structural elements for probing the mechanical responses of biologically inspired systems

A living cell has a crowded environment with a dense distribution of molecules that requires structured organization for its efficient functioning. One component of this structure, the actin cytoskeleton, is essential for providing mechanical support and facilitating many response activities, including the contraction of muscle cells and chemotaxis. Whereas many investigations have provided insight into the mechanical response from either an in vivo or in vitro perspective, a significant gap exists in determining how the living cell response and the polymer physics response are bridged. The understanding of these systems involves studying their components, including the individual cytoskeletal elements versus the higher-order organism organization in a living cell. Here, we leverage this organization in nature by using a chemistry-based approach to mimic the cytoskeleton in an artificial environment composed of spherically distributed lipid bilayers. This construct bears similarities to the cell membrane. To create a structurally regulated environment, we encapsulate G-actin into giant unilamellar vesicles and then polymerize actin filaments within individual liposomes. We visualize these vesicles with epifluorescence microscopy and confocal microscopy. Atomic force microscopy is then used to probe the mechanical properties of these artificial cells. This polymer cytoskeletal network appears to connect with the lipid bilayer and span the internal space within the liposomes in a manner similar to what is observed in living cells. This work will have implications in a variety of fields, including chemistry, polymer physics, structural biology, and engineering mechanics.     

Collisionally damped ion motion in ICR spectrometry

A Schrödinger equation equivalent to the Langevin equation of ion motion in ICR cells is presented. A wave function for the scattering states has been found as the solution to the equation of ion motion under the influence of electric and magnetic fields perturbed by a scattering potential. Applying the minimized wave packet as a wave function describing coherent states, the scattering amplitudes are determined explicitly. The connection between the collision cross section and the scattering amplitudes is found by making use of the incoming and outgoing particle flux density. The collision cross section found in this way is converted from quantum theory to classical physics. The collision cross section, which plays an essential role in the determination of rate constants can be determined by the aid of ICR experimental data if the contribution of an alternating electric field is taken into account.     

Magnetic field effects on atomic and molecular collisions

The full quantal theory of heavy-particle collisions in the presence of a static magnetic field, B, has been formulated. A new mechanism of magnetic field effect was found which depends on the velocity of the molecular center of mass and plays an important role at high-speed collisions. A power series expansion of the cross section as a function of B was obtained, which can be applied to collisions at weak field. It was also found that the differential cross section can become zero due to the magnetic field when a rovibronic energy level of a molecule is in resonance with another energy level.     

Specific redistribution of cell-penetrating peptides from endosomes to the cytoplasm and nucleus upon laser illumination

Cell-penetrating peptides (CPPs), once postulated to cross cell membranes in a non-endocytic, non-energy-dependent process, have since been found to accumulate in vesicles in live mammalian cells. In this study, we show that it is possible to use laser light from a confocal microscope to cause labeled peptide-conjugated CPPs to redistribute from vesicles into the cytoplasm and nucleus of cells. Following redistribution, the cells are found to be biologically responsive, and they retain morphology for several hours. It was possible to initiate redistribution of both fluorescein- and Alexa633-labeled peptides by selective irradiation of one of the fluorophores. These peptides could potentially be used as tracers to selectively deliver cargo biomolecules into cells by laser illumination using a standard fluorescence confocal microscope.     

On the Origin of Primitive Cells: From Nutrient Intake to Elongation of Encapsulated Nucleotides

Recent major discoveries in membrane biophysics hold the key to a modern understanding of the origin of life on Earth. Membrane bilayer vesicles have been shown to provide a multifaceted microenvironment in which protometabolic reactions could have developed. Cell‐membrane‐like aggregates of amphiphilic molecules capable of retaining encapsulated oligonucleotides have been successfully created in the laboratory. Sophisticated laboratory studies on the origin of life now show that elongation of the DNA primer takes place inside fatty acid vesicles when activated nucleotide nutrients are added to the external medium. These studies demonstrate that cell‐like vesicles can be sufficiently permeable to allow for the intake of charged molecules such as activated nucleotides, which can then take part in copying templates in the protocell interior. In this Review we summarize recent experiments in this area and describe a possible scenario for the origin of primitive cells, with an emphasis on the elongation of encapsulated nucleotides.     

Functionalized polydiacetylene-glycolipid vesicles interacted with Escherichia coli under the TiO2 colloid

The interaction of the conjugated system between functionalized polydiacetylene-glycolipid vesicles and Escherichia coli was investigated under the bactericidal effect of TiO₂ colloid. With various pre-incubation and irradiation time, controllable bacteria quantity in the presence of TiO₂ colloid was obtained in real time. UV–visible and Raman spectra were utilized to monitor and evaluate the structural transition of bacteria-polydiacetylene-glycolipid vesicles conjugated system under the different conditions, which supplied the detailed information of the transform of the polydiacetylene backbone in real time. Thus controllable conjugated bio-interaction between two bio-interfaces was obtained through the introduction of the third factor and monitored in real time. This would be great aid in fundamental understanding more complex interfaces in the biological environment and would be applicable to the biomedical and biophysical fields.     

Dual Photo‐ and pH‐Responsive Supramolecular Nanocarriers Based on Water‐Soluble Pillar[6]arene and Different Azobenzene Derivatives for Intracellular Anticancer Drug Delivery

Two novel types of supramolecular nanocarriers fabricated by the amphiphilic host–guest inclusion complex formed from water‐soluble pillar[6]arene ( WP6 ) and azobenzene derivatives G1 or G2 have been developed, in which G1 is structurally similar to G2 but has an extra phenoxy group in its hydrophobic region. Supramolecular micelles can be initially formed by WP6 with G1 , which gradually transform into layered structures with liquid‐crystalline properties, whereas stable supramolecular vesicles are obtained from WP6 and G2 , which exhibit dual photo‐ and pH‐responsiveness. Notably, the resulting WP6 ? G2 vesicles can efficiently encapsulate anticancer drug mitoxantrone (MTZ) to achieve MTZ‐loaded vesicles, which maintain good stability in a simulated normal physiological environment, whereas in an acid environment similar to that of tumor cells or with external UV irradiation, the encapsulated drug is promptly released. More importantly, cytotoxicity assay indicates that such vesicles have good biocompatibility and the MTZ‐loaded vesicles exhibit comparable anticancer activity to free MTZ, especially with additional UV stimulus, whereas its cytotoxicity for normal cells was remarkably reduced. Flow cytometric analysis further confirms that the cancer cell death caused by MTZ‐loaded vesicles is associated with apoptosis. Therefore, the dual pH‐ and UV‐responsive supramolecular vesicles are a potential platform for controlled release and targeted anticancer drug delivery.     

海藻酸-磷脂微囊复合水凝胶的制备、表征及毒理学分析

采用薄膜分散法合成磷脂微囊,根据胶粒的双电层理论,通过在微囊中加入氯化锰、氯化钙和氯化镁电解质溶液,使微囊处于相对稳定的状态.研究发现加入氯化锰和氯化钙溶液,微囊胶体的粒径没有明显的变化,但加入一定浓度氯化镁溶液,其粒径明显变大.为了进一步增加磷脂微囊稳定性,将氯化锰、氯化钙、氯化镁磷脂微囊胶体分别与海藻酸钠(SA)溶液混合.结果表明,氯化镁与SA几乎不能形成水凝胶,氯化钙与SA形成水凝胶能力强于氯化锰.微囊胶体溶液中的磷脂酰丝氨酸(PS)可以与Ca~(2+)和Mg~(2+)键合形成PS-Ca~(2+)和PS-Mg~(2+),但不能与Mn~(2+)键合形成PS-Mn~(2+).对氯化钙磷脂微囊与海藻酸钠合成的复合水凝胶的形貌、溶胀率及细胞毒性进行了表征,结果表明,氯化钙与SA形成的水凝胶可以捕获胶体中磷脂微囊,且形貌规整,结构稳定,无细胞毒性.     

Functionalized polydiacetylene-glycolipid vesicles interacted with Escherichia coli under the TiO2 colloid

The interaction of the conjugated system between functionalized polydiacetylene-glycolipid vesicles and Escherichia coli was investigated under the bactericidal effect of TiO₂ colloid. With various pre-incubation and irradiation time, controllable bacteria quantity in the presence of TiO₂ colloid was obtained in real time. UV–visible and Raman spectra were utilized to monitor and evaluate the structural transition of bacteria-polydiacetylene-glycolipid vesicles conjugated system under the different conditions, which supplied the detailed information of the transform of the polydiacetylene backbone in real time. Thus controllable conjugated bio-interaction between two bio-interfaces was obtained through the introduction of the third factor and monitored in real time. This would be great aid in fundamental understanding more complex interfaces in the biological environment and would be applicable to the biomedical and biophysical fields.     

A preliminary study on the initial elastic adhesion behavior of leucocytes

By treating the cell body as an elastic colloid and applied with the Hertz contact theory of linear elasticity and the lubrication equation of fluid dynamics, the elastic adhesion behavior of leucocytes in close motion toward a plane surface is investigated. The effect of the Stokes number on the deformation profile of the cell is considered during the adhesion period. From the results of numerical simulation, it is found that under certain conditions (i.e. regardless of the magnitude of F for the cases of ST=1 and 3 and ε0.0055 for ST=10), after exhausting all of the incoming kinetic energy, the cell can rest at an equilibrium separation which is close to the ligand–receptor bond length formed between two interacting surfaces.     

Colloid particle and protein deposition - electrokinetic studies

Recent developments in the electrokinetic determination of particle, polyelectrolyte and protein deposition at solid/electrolyte interfaces, are reviewed. In the first section basic theoretical results are discussed enabling a quantitative interpretation of the streaming current/potential and microelectrophoretic measurements. Experimental results are presented, pertinent to electrokinetic characteristics of simple (homogeneous) surfaces such as mica, silica and various polymeric surfaces used in protein studies. The influence of the ionic strength, background electrolyte composition and pH is discussed, and the effective (electrokientic) charge of these interfaces is evaluated. In the next section, experimental data obtained by streaming potential measurements for colloid particle mono- and bilayers are presented and interpreted successfully in terms of available theoretical approaches. These results, obtained for model systems of monodisperse colloid particles are used as reference data for discussion of more complicated experiments performed for polyelectrolyte and protein covered surfaces. Results are discussed, obtained for cationic polyelectrolytes (PEI, PAH) and fibrinogen adsorbing on mica, interpreted quantitatively in terms of the theoretical approach postulating a heterogeneous 3D charge distribution. The Gouy-Chapman model, based on the continuous charge distribution proved inadequate. Interesting experimental data are also discussed, obtained by electrophoretic methods in the case of protein adsorption on colloid latex particles. In the last section, supplementary results on particle deposition on heterogeneous surfaces produced by controlled protein adsorption are discussed. Quantitative relationships between the amount of adsorbed protein, zeta potential of the interface and the particle coverage are specified. Possibility of evaluating the heterogeneity of protein charge distribution is pointed out. The anomalous deposition of colloid particles on protein molecules bearing the same sign of zeta potential, which contradicts classical DLVO theory, is interpreted in terms of the fluctuation theory. It is concluded that theoretical and experimental results obtained for model colloid systems and flat interfaces can be effectively used for interpretation of protein adsorption phenomena, studied by electrophoresis. In this way the universality of electrokinetic phenomena is underlined.