Critical dynamics of the sol-gel transition studied using particle-tracking microrheology.

The formation of tetra-PEG gels, a model network with a well-defined structure, was investigated using particle-tracking microrheology. The dynamic scaling and critical relaxation exponents in the sol-gel transition were determined by applying the time-cure superposition method. Some values of the exponents differed from those of the Rouse model theory.

Protein Preferential Solvation in (Sucralose + Water) Mixtures.

Addition of sugars such as sucrose to aqueous protein solutions generally stabilizes proteins against thermal denaturation by preferential exclusion of sugars from proteins (preferential hydration of proteins). In this study, we investigated the effect of sucralose, a chlorinated sucrose derivative, on protein stability and preferential solvation. Circular dichroism and small-angle X-ray scattering measurements showed that sucrose increased the denaturation temperature of myoglobin and was preferentially excluded from the protein, whereas sucralose decreased the denaturation temperature of myoglobin and was preferentially adsorbed to the protein.

Anion specific conformational change in aqueous gellan gum solutions.

I NMR is applied to investigate the motional state and the selective interaction of I ions in tetramethylammonium form of gellan gum (TMA gellan), together with monitoring the conformational change by the optical rotation measurement. The experimental results indicate that I ion promotes the conformational transition, and there exists the preferential affinity of I ion for the ordered conformation of TMA gellan.

Editorial on Special Issue "New Era in the Volume Phase Transition of Gels".

The Special Issue of gels titled "Advancements in Gel Science" has been published from MDPI in 2019 [...

Formation of Multi-Channel Collagen Gels Investigated Using Particle Tracking Microrheology.

Collagen is one of the most common materials used to form scaffolds for tissue engineering applications. The multi-channel collagen gel (MCCG) obtained by the dialysis of an acidic collagen solution in a neutral buffer solution has a unique structure, with many capillaries of diameters several tens to a few hundred micrometers, and could be a potential candidate as a biomimetic scaffold for three-dimensional tissue engineering. In the present study, the formation of MCCG was investigated by rheological measurements based on a particle tracking method (particle tracking microrheology, PTM).

Necklace-like microstructure in shallow-quenched aqueous solutions of poly(n-isopropylacrylamide), detected by advanced small-angle neutron scattering methods.

The microstructure of aqueous poly(N-isopropyl acrylamide) (PNIPA) gel and solution was investigated by small-angle neutron scattering (SANS) in the vicinity of the gel volume phase transition at T (= 34 °C). The SANS technique was reinforced by refractive neutron lenses and perfect single crystals in order to get access to μm length scales. At 31 °C SANS shows Ornstein-Zernike (OZ) type scattering in the swollen gel which at 32 °C starts to deviate from the OZ-formalism, exhibiting excess scattering and at the wave number q≅ 5 × 10Å a crossover to Porod's asymptotic q power law.

Stretching PEO-PPO Type of Star Block Copolymer Gels: Rheology and Small-Angle Scattering.

Cross-linked Tetronic star block copolymer gels, based on poly(ethylene oxide) and poly(propylene oxide), behave quite regular with respect to mechanical properties, but exhibits unusual absence of structural response to strain. The elastic response is linear up to more than 100% strain, with a steady-state modulus of the order of 0.01 MPa after an initial stress relaxation.

Structural Study of Four-Armed Amphiphilic Star-Block Copolymers: Pristine and End-Linked Tetronic T1307.

We present a comparative structural study of 30 wt % aqueous suspensions of two related systems based on 4-arm PEO-PPO type of macromolecules (Tetronic T1307, BASF) with the PPO block near the star center. One system concerns the pristine 4-arm PEO-PPO star block copolymer T1307. The second system is a 1:1 blend consisting of, respectively, tetra-amine (TAT) and tetra--hydroxysuccinimide (TNT) terminated T1307.

Nonsolvents-induced swelling of poly(methyl methacrylate) nanoparticles.

Polymer nanoparticles have been used in a wide variety of applications. In most of these applications, they are generally dispersed in a non-solvent. However, the effect of the non-solvent on the structure, physical properties and function of the nanoparticles has not yet ever taken into account.

Liquid crystalline inorganic nanosheets for facile synthesis of polymer hydrogels with anisotropies in structure, optical property, swelling/deswelling, and ion transport/fixation.

Macroscopically anisotropic hydrogels were synthesized by hybridization of poly(N-isopropylacrylamide) with liquid crystalline inorganic nanosheets; their anisotropies in the structure and properties are demonstrated.

Salt effect on microscopic structure and stability of colloidal complex obtained from neutral/polyelectrolyte block copolymer and oppositely charged surfactant.

The salt effect on complex formation of poly(acrylamide)-block-poly(acrylic acid) (PAM-b-PAA) and dodecyltrimethylammonium bromide (DTAB) at different NaBr concentrations, C(NaBr), was investigated by laser light scattering (LLS) and small angle neutron scattering (SANS). LLS and SANS clearly indicates that the aqueous solution of PAM-b-PAA and DTAB associate into colloidal complexes. For low surfactant-to-polymer charge ratio Z lower than the critical value Z(C), the colloidal complexes are single DTAB micelles dressed by a few PAM-b-PAA.

Visible light-induced water oxidation catalyzed by molybdenum-based polyoxometalates with mono- and dicobalt(III) cores as oxygen-evolving centers.

The Mo-based polyoxometalates containing mono- and dicobalt(III) catalyst cores, [CoMo(6)O(24)H(6)](3-) and [Co(2)Mo(10)O(38)H(4)](6-), were found to serve as O(2)-evolving catalysts in a system consisting of tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)) and sodium persulfate (S(2)O) in an aqueous borate buffer solution at pH 8.0. Kinetics of O(2) evolution reveals that the higher cobalt nuclearity is not necessary to attain the highly active nature of the catalyst.

Design of an injectable in situ gelation biomaterials for vitreous substitute.

To adapt the physical properties of living materials to their biological function, nature developed various types of polymers with outstanding physical behavior. One example is the vitreous body, which is important intraocular elements not only because of its optical and mechanical performances, but also due to its important role in the pathogenesis and treatment of conditions affecting adjacent tissues and eventually the whole eye. Here, we report a novel biocompatible material for injectable vitreous substitute, composed of thermosensitive amphiphilic polymer, which is capable of forming a transparent gel in the vitreous cavity.

Changing the volume of a giant macrocycle: the swelling of the macrocycle with organic solvents.

The novel tetrahedral macrocycles 1a-1c have been synthesized. Macrocycles 1a and 1c were revealed to have the property to increase in volume in solution by complexation between the macrocycle and the solvent molecules.

Stereoregulation of thermoresponsive polymer brushes by surface-initiated living radical polymerization and the effect of tacticity on surface wettability.

In this study, stereocontrolled poly(N-isopropylacrylamide) (PIPAAm) brushes were grafted from surfaces by atom transfer radical polymerization (ATRP) in the presence of a Lewis acid, and the effect of PIPAAm brush tacticity on the thermoresponsive wettabiliy was investigated. PIPAAm grafted by ATRP in the presence of Y(OTf)(3) showed high isotacticity, while the control brush polymerized in the absence of Y(OTf)(3) was clearly atactic. The isotacticity and molecular weight of PIPAAm brushes were controlled by polymerization conditions.

Photochemical and thermal hydrogen production from water catalyzed by carboxylate-bridged dirhodium(II) complexes.

A series of dinuclear Rh(II) complexes, [Rh(2)(μ-OAc)(4)(H(2)O)(2)] (HOAc = acetic acid) (1), [Rh(2)(μ-gly)(4)(H(2)O)(2)] (Hgly = glycolic acid) (2), [Rh(2)(μ-CF(3)CO(2))(4)(acetone)(2)] (3), and [Rh(2)(bpy)(2)(μ-OAc)(2)(OAc)(2)] (4), were found to serve as H(2)-evolving catalysts in a three-component system consisting of tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)), methylviologen (MV(2+)), and ethylenediaminetetraacetic acid disodium salt (EDTA). It was also confirmed that thermal reduction of water into H(2) by MV(+)˙, in situ generated by the bulk electrolysis of MV(2+), is effectively promoted by 1 as a H(2)-evolving catalyst. The absorption spectra of the photolysis solution during the photocatalysis were monitored up to 6 h to reveal that the formation of photochemical or thermal byproducts of MV(+)˙ is dramatically retarded in the presence of the Rh(II)(2) catalysts, for the H(2) formation rather than the decomposition of MV(+)˙ becomes predominant in the presence of the Rh(II)(2) catalysts.

Preparation of thermo-responsive polymer brushes on hydrophilic polymeric beads by surface-initiated atom transfer radical polymerization for a highly resolutive separation of peptides.

Poly(N-isopropylacrylamide-co-N-tert-butylacrylamide) [P(IPAAm-co-tBAAm)] brushes were prepared on poly(hydroxy methacrylate) (PHMA) [hydrolyzed poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate)] beads having large pores by surface-initiated atom transfer radical polymerization (ATRP) and applied to the stationary phases of thermo-responsive chromatography. Optimized amount of copolymer brushes grafted PHMA beads were able to separate peptides and proteins with narrow peaks and a high resolution. The beads were found to have a specific surface area of 43.

Effective separation of peptides using highly dense thermo-responsive polymer brush-grafted porous polystyrene beads.

For the development of well-defined highly dense thermo-responsive polymer grafted surface as an improved stationary phase for thermo-responsive chromatography, poly(N-isopropylacrylamide) (PIPAAm) brush-grafted porous polystyrene beads were prepared by surface-initiated atom transfer radical polymerization (ATRP). The PIPAAm grafted region of polystyrene beads was adjusted by the addition of isooctane as a poor solvent for polystyrene upon the reaction of ATRP initiator immobilization. Using a thermo-responsive HPLC column containing the prepared beads with PIPAAm brush grafted on the inside pores nearby the outer surfaces, angiotensin subtypes were effectively separated with aqueous mobile phase, because the densely grafted PIPAAm on nearby the outer surface effectively interacted with the peptides hydrophobically.

Thermoresponsive polymer brush surfaces with hydrophobic groups for all-aqueous chromatography.

For developing thermoresponsive chromatographic matrices with a strong hydrophobicity, poly(N-isopropylacrylamide-co-n-butyl methacrylate) (poly(IPAAm-co-BMA)) brush grafted silica beads were prepared through a surface-initiated atom transfer radical polymerization (ATRP) with a CuCl/CuCl(2)/Me(6)TREN catalytic system in 2-propanol at 25 degrees C for 16 h. The prepared beads were characterized by chromatographic analysis. Chromatograms of the benzoic-acid family and phenol as model analytes were obtained with high-resolution peaks because of their strong hydrophobic interactions to the densely grafted hydrophobized copolymers on the beads.

Thermo-responsive polymer brush-grafted porous polystyrene beads for all-aqueous chromatography.

Poly(N-isopropylacrylamide) (PIPAAm) brush-grafted porous polystyrene beads with variable grafted polymer densities were prepared using surface-initiated atom transfer radical polymerization (ATRP) for applications in thermo-responsive chromatography. Utilization of these grafted beads as a stationary phase in aqueous chromatographic analysis of insulin provides a graft density-dependent analyte retention behavior. The separations calibration curve on PIPAAm-grafted polystyrene was obtained using pullulan standards and exhibited inflection points attributed to analyte diffusion into bead pores and partitioning into grafted PIPAAm brush surfaces.

Anisotropic swelling behavior of the cornea.

The phase equilibrium property and structural and dynamical properties of pig cornea were studied by macroscopic observation of swelling behavior, dynamic light scattering (DLS), and small-angle X-ray scattering (SAXS) under various conditions. It was found that the corneal gel collapses into a compact state isotropically or anisotropically depending on the external conditions. The corneal gel collapses uniformly into a compact state at a temperature above 55 degrees C because of the denaturation of collagen, whereas it collapses along an axis parallel to the optic axis with increasing NaCl concentration.

Preparation of thermoresponsive anionic copolymer brush surfaces for separating basic biomolecules.

Poly(N-isopropylacrylamide-co-acrylic acid-co-N-tert-butylacrylamide) (poly(IPAAm-co-AAc-co-tBAAm) brush grafted silica beads were prepared through a surface-initiated atom transfer radical polymerization (ATRP) with CuCl/CuCl(2)/Me(6)TREN catalytic system in 2-propanol at 25 degrees C for 4 h. The prepared beads were characterized by chromatographic analysis. Basic analytes, catecholamine derivatives, and angiotensin peptides could be separated by a short column length containing the beads because of its high densely grafted copolymer structure.

Influence of graft interface polarity on hydration/dehydration of grafted thermoresponsive polymer brushes and steroid separation using all-aqueous chromatography.

We have prepared poly( N-isopropylacrylamide) (PIPAAm) brush-grafted surfaces with varied temperature-responsive hydrophobic properties through surface-initiated atom transfer radical polymerization (ATRP). These temperature-responsive surfaces were characterized by chromatographic analysis using modified silica beads as a chromatographic stationary phase in aqueous mobile phase. Mixed silane self-assembled monolayers (SAMs) comprising ATRP initiator and silanes with various terminal functional groups were formed on the silica bead surfaces.

Dimensions of a free linear polymer and polymer immobilized on silica nanoparticles of a zwitterionic polymer in aqueous solutions with various ionic strengths.

The dimensions and intermolecular interactions of a surface-grafted and unbound free polyampholyte, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), were estimated in aqueous solutions with various ionic strengths. Free linear PMPC was synthesized by atom-transfer radical polymerization (ATRP), and static light scattering (SLS) and dynamic light scattering (DLS) were carried out for the PMPC solutions with various concentrations of NaCl, c s. The hydrodynamic radius R H and the second virial coefficient A 2 of PMPC were independent of c s (0-0.