PubMed Health⌕ Search

Biomedical subjects

Peter Lindner

Publications and source records attributed to Peter Lindner.

16 recordsLinked to original sources

The solution structure of stilbenoid dendrimers: a small-angle scattering study.

The spatial structure of a stilbenoid dendrimer is investigated by small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) in dilute solution. All measurements are performed in toluene. The dendrimer consists of a stilbenoid scaffold with appended hexyloxy chains. SAXS is mainly sensitive to the dendrimer scaffold whereas SANS intensity, measured in fully deuterated toluene, derives from the solute molecules. The resulting SAXS and SANS intensities are analyzed by comparison with various models. It is found that the model of a circular disk gives the best description of the data. SAXS data demonstrate that the stilbenoid scaffold is flat as expected for benzene rings conjugated through vinylene units. Thus, it can be described by a circular disk with a radius of 1.6 nm and a thickness of 0.7 nm. SANS, on the other hand, shows that the hexyloxy chains are not confined in the plane defined by the core. This is derived from modeling the SANS data with a much thicker circular disk (radius: 2.4 nm, thickness: 1.8 nm). The structure factor S(q), describing the interaction of the dendrimers at higher concentrations, is modeled quantitatively with the "polymer reference interaction site model" (PRISM) integral equation formalism for hard plates such as particles. Here the structural data obtained from the analysis of the SANS data are used so that no new adjustable parameter is necessary for this description.

Journal Article↗

pH-induced release from P2VP-PEO block copolymer vesicles.

The pH-induced release of hydrophilic dyes from poly(2-vinylpyridine-b-ethylene oxide) (P2VP-PEO) block copolymer vesicles is investigated. The structure of the vesicles is characterized using small-angle neutron scattering (SANS) and cryo-electron microscopy (cryo-TEM). A decrease of the pH below 5 leads to protonation and dissolution of the poly-2-vinylpyridine blocks which induces rupture and dissolution of the vesicle membrane. Details of the rupture, dissolution, and release process are studied by fluorescence video microscopy, gel electrophoresis, and high-performance ultrafiltration.

Cryoelectron Microscopy↗

Osmotic compression and expansion of highly ordered clay dispersions.

Aqueous dispersions of nanometric clay platelets (Laponite) have been dewatered through different techniques: centrifugation, mechanical compression, and osmotic stress (dialysis against a polymer solution). The positional and orientational correlations of the particles have been determined through small-angle neutron scattering. Uniaxial compression experiments produce concentrated dispersions (volume fraction > 0.03) in which the platelets have strong orientational and positional correlations. The orientational correlations cause the platelets to align with their normal along a common axis, which is the axis of compression. The positional correlations cause the platelets to be regularly spaced along this direction, with a spacing that matches the average volume per particle in the dispersion. The swelling law (volume fraction versus separation distance) is one-dimensional, as in a layered system. Changes in the applied osmotic pressure cause the water content of the dispersion to either rise or decrease, with time scales that are controlled by interparticle friction forces and by hydrodynamic drag. At long times, the dispersions approach osmotic equilibrium, which can be defined as the common limit of swelling and deswelling processes. The variation of the equilibrium water content with the applied osmotic pressure has been determined over 1 decade in volume fractions (0.03 < phi < 0.3) and 3 decades in pressures. This equation of state matches the predictions made from the knowledge of the forces and thermal agitation for all components in the dispersion (particles, ions, and water).

Journal Article↗

Logarithmic chain-exchange kinetics of diblock copolymer micelles.

We present a study of equilibrium chain-exchange kinetics of a well-defined model system for starlike polymeric micelles. The results show that the kinetics follows a logarithmic time dependence. The same feature has been confirmed for two other micellar systems. This is in sharp contrast to theoretical predictions and hints towards strongly coupled chain dynamics within the micellar cores induced by geometrical constraints.

Deuterium↗

Influence of shell thickness and cross-link density on the structure of temperature-sensitive poly-N-isopropylacrylamide-poly-N-isopropylmethacrylamide core-shell microgels investigated by small-angle neutron scattering.

Swelling properties of doubly temperature sensitive core-shell microgels consisting of two thermosensitive polymers with lower critical solution temperatures (LCTS) at, respectively, 34 degrees C in the core and 44 degrees C in the shell have been investigated by small-angle neutron scattering (SANS). A core-shell form factor has been employed to evaluate the structure, and the real space particle structure is expressed by radial density profiles. By this means, the influences of both shell/core mass composition and shell cross-linker content on the internal structure have been revealed at temperatures above, between, and below the LCSTs. Higher shell/core mass ratios lead to an increased expansion of the core at temperatures between the LCSTs, whereas a variation of cross-linker in the shell mainly effects the dimensions of the shell. The influence on the core structure was interpreted as resulting from an elastic force developed from the swollen shell. At temperatures below the core LCST, the core cannot swell to its native size (i.e., in the absence of a shell), because the maximum expanded shell network prohibits further swelling. Thus, depending on temperature, the shell either expands or compresses the core.

Journal Article↗

Structural changes and chain radius of gyration in cold-drawn polyethylene after annealing: small- and wide-angle X-ray scattering and small-angle neutron scattering studies.

Samples made from linear polyethylene were drawn at room temperature and subsequently annealed at high temperatures below the melting point. The structural changes of the crystalline lamellae and lamellar superstructures as well as the single chain radius of gyration were studied by means of combined small- and wide-angle X-ray scattering and small-angle neutron scattering (SANS). After drawing, the polymeric chain segments in the crystalline phase are preferentially oriented along the drawing direction with a high degree of orientation whereas the lamellae in the samples are found to be slightly sheared exhibiting oblique surfaces as evidenced by X-ray scattering. SANS indicates that the chains are highly elongated along the drawing direction. Annealing the deformed samples at temperatures where the mechanical alpha-process of polyethylene is active leads to a thickening of both crystalline lamellae and amorphous layers. The chains in the crystalline phase retain their high degree of orientation after annealing while the lamellae are sheared to a larger extent. In addition, there is also lateral growth of the crystalline lamellae during high-temperature annealing. Despite the structural changes of the crystalline and amorphous regions, there is no evidence for global chain relaxation. The global anisotropic shape of the chains is preserved even after prolonged annealing at high temperatures. The results indicate that the mobility of polyethylene chains-as seen, e.g., by 13C NMR-is a local phenomenon. The results also yield new insight into mechanical properties of drawn PE, especially regarding stress relaxation and creep mechanisms.

Journal Article↗

Are thermoresponsive microgels model systems for concentrated colloidal suspensions? A rheology and small-angle neutron scattering study.

The structure of concentrated temperature-sensitive poly(N-isopropylacrylamide) (PNiPAM) microgel suspensions has been investigated employing rheology and small-angle neutron scattering (SANS). A previously described model expression for the particle form factor P(inho)(q) is extended by a model hard sphere structure factor S(q), and the average radial density profiles phi(r) are calculated from the amplitude of the form factor A(q) and the structure factor S(q). By this procedure, a direct real space description of the spatial ordering in the neighborhood of a single particle is obtained. The overall particle size and the correlation length xi of the concentration fluctuations of the internal polymer network decrease with concentration, revealing the increasing compression of the spheres. Thus, the particle form factor P(inho)(q) of the swollen PNiPAM microgels depends on concentration. The particle-particle interaction potential does not change significantly between 25 and 32 degrees C. Even approximately 1 K below the lower critical solution temperature (LCST), the experimental scattering intensity distributions I(q)/c are described very well by the hard sphere structure factor when an equivalent hard sphere particle size R(HS) and volume fraction eta(HS) are used. Microgels with different degrees of cross-linking and particle size resemble true hard sphere behavior up to effective volume fractions of phi(eff) < 0.35. At higher effective volume fractions phi(eff) > 0.35 strong deviations from true hard spheres are observed. Interpenetration of the outer, less cross-linked regions of the soft spheres as well as particle compression occurred at higher concentrations. In agreement with this, the equilibrium colloidal phase behavior and rheology also has some features of soft sphere systems. At temperatures well above the LCST, the interaction potential becomes strongly attractive and the collapsed microgel spheres form aggregates consisting of flocculated particles without significant long-range order. Hence, an attractive interaction potential in concentrated suspensions of PNiPAM microgels leads to distinctively different structures as compared to attractive hard sphere colloids. When the peculiar structural properties of the PNiPAM microgels are considered, they can be used as model systems in colloidal science.

Journal Article↗

Shear-induced morphology transition and microphase separation in a lamellar phase doped with clay particles.

We report on the influence of shear on a nonionic lamellar phase of tetraethyleneglycol monododecyl ether (C12E4) in D2O containing clay particles (Laponite RD). The system was studied by means of small-angle light scattering (SALS) and small-angle neutron scattering (SANS) under shear. The SANS experiments were conducted using a H2O/D2O mixture of the respective scattering length density to selectively match the clay scattering. The rheological properties show the familiar shear thickening regime associated with the formation of multilamellar vesicles (MLVs) and a shear thinning regime at higher stresses. The variation of viscosity is less pronounced as commonly observed. In the shear thinning regime, depolarized SALS reveals an unexpectedly strong variation of the MLV size. SANS experiments using the samples with lamellar contrast reveal a change in interlamellar spacing of up to 30% at stresses that lead to MLV formation. This change is much more pronounced than the change observed, when shear suppresses thermal bilayer undulations. Microphase separation occurs, and as a consequence, the lamellar spacing decreases drastically. The coincidence of the change in lamellar spacing and the onset of MLV formation is a strong indication for a morphology-driven microphase separation.

Journal Article↗

Small-angle neutron scattering study of structural changes in temperature sensitive microgel colloids.

The structure of temperature-sensitive poly(N-isopropylacrylamide) microgels in dilute suspension was investigated by means of small-angle neutron scattering. A direct modeling expression for the scattering intensity distribution was derived which describes very well the experimental data at all temperatures over an extensive q range. The overall particle form as well as the internal structure of the microgel network is described by the model. The influence of temperature, cross-linking density, and particle size on the structure was revealed by radial density profiles and clearly showed that the segment density in the swollen state is not homogeneous, but gradually decays at the surface. The density profile reveals a box profile only when the particles are collapsed at elevated temperatures. An increase of the cross-linking density resulted in both an increase of the polymer volume fraction in the inner region of the particle and a reduction of the smearing of the surface. The polymer volume fraction inside the colloid decreased with increasing particle size. The structural changes are in good agreement with the kinetics of the emulsion copolymerization used to prepare the microgel colloids.

Acrylic Resins↗

Micelles of imidazolium-functionalized polystyrene diblock copolymers investigated with neutron and light scattering.

We synthesize a series of block copolymers comprising a polystyrene (PS) block and an imidazolium-functionalized PS (IL) block and characterize their assembly properties. We use small-angle neutron scattering and dynamic light scattering to determine the micelle size and shape in dilute solutions and to assess the micelle interactions in concentrated solutions. By studying a series of copolymers with fixed PS block length, we find that the length of the IL block governs the micelle dimensions. Our data suggest that these copolymers form elongated micelle structures where the IL block is extended in the micelle core. We find that these micelles can sequester water and that interactions between the micelles lead to structure factor peaks at elevated concentrations.

Binding Sites↗

Change of voice characteristics during +3 Gz acceleration.

BACKGROUND: This study was performed to test the feasibility of an experimental approach for assessing voice changes during exposure to increased +Gz acceleration. Such changes are probably due to mechanical alterations of the structures involved in voice production. This may be relevant to automatic speech analysis for flight control. Because voice control by means of auditory feedback may compensate for acceleration effects, the investigations included conditions with masked auditory feedback. METHOD: Four male subjects read standard speech test material while seated in a human centrifuge both during sustained +3 Gz acceleration and in a reference condition. Both test runs were repeated with masking of the auditory feedback by a white noise presented via headphones. Microphone and acceleration signals were recorded on a PC-based dynamic signal acquisition board. Long-time average spectra (LTAS), fundamental frequency (F0), and the frequency of the first, second, and third formant (F1, F2, F3) of the vowels /a/, /o/, and /i/ were extracted from the microphone signal for the different conditions. RESULTS: LTAS clearly differed between the masking conditions, but not between reference and +3 Gz conditions. F0 clearly rose with auditory masking and showed a small increase under +3 Gz acceleration. Several effects of +3 Gz acceleration on formant frequencies were found, all of rather small magnitude. Increased acceleration lowered F2 for the vowel /i/. A decrease of F3 was observed for vowels /i/ and /o/. CONCLUSION: This pilot study has shown the feasibility of an experimental approach to assessing voice changes during exposure to increased +Gz acceleration. Exposure to +3 Gz showed small effects on FO and several formant frequencies. A definitive forthcoming study should assess the significance of these effects by investigating a greater number of subjects during exposure to acceleration higher than +3 Gz.

Adult↗

Shear-banding and microstructure of colloids in shear flow.

We shall discuss the following phenomena found in various colloidal systems in shear flow. We recently observed shear-banding in suspensions of fd-virus in a cylindrical shear cell. Small angle light scattering experiments revealed that the shear-banding transition is preceded by a relatively fast process (minutes) of nematic-to-paranematic phase separation during which inhomogeneities on the micrometer length scale are formed. After the formation of these inhomogeneities, a slow (hours) appearence of shear-bands is observed, which have a height of a few mm. In the stationary state it is found, by means of polarization microscopy, that inhomogeneities exist within the bands. Small angle, time resolved light scattering experiments on near-critical microstructural order in a mixture of colloidal spheres and free polymer under stationary shear flow are discussed. The unexpected distortion of microstructure in directions perpendicular to the flow direction is quantitatively explained by extending an already existing theory, to include shear-induced short-ranged microstructural distortion. In colloidal systems consisting of "hairy colloids", where a spherical core is decorated with relatively long polymers, shear-induced polymer brush deformation might be important for its structural and rheological behavior. Preliminary neutron scattering and rheology experiments are performed to study polymer brush deformation in (semi-) dilute suspensions.

Journal Article↗

Dissociation of thixotropic clay gels.

Laponite dispersions in water, at moderate ionic strength and high pH, are thixotropic: depending on previous history, they can be fluids or gels. The mechanisms of the fluid-gel and gel-fluid transitions have been examined through ionic analysis of the aqueous phase, static light, and small-angle neutron scattering, rheological experiments, and centrifugation. The results indicate that the particles attract each other in edge-to-face configurations. These attractions cause the particles to gather in microdomains, which subsequently associate to form very large fractal superaggregates, containing all the particles in the dispersion. A gel state is obtained when the network of connections is macroscopic. This network is destroyed by the application of sufficient strain, but it heals at rest. The addition of peptizers weakens the edge-to-face attractions, and makes the healing times much slower.

Journal Article↗

Crystal structure of the anti-His tag antibody 3D5 single-chain fragment complexed to its antigen.

The crystal structure of a mutant form of the single-chain fragment (scFv), derived from the monoclonal anti-His tag antibody 3D5, in complex with a hexahistidine peptide has been determined at 2.7 A resolution. The peptide binds to a deep pocket formed at the interface of the variable domains of the light and the heavy chain, mainly through hydrophobic interaction to aromatic residues and hydrogen bonds to acidic residues. The antibody recognizes the C-terminal carboxylate group of the peptide as well as the main chain of the last four residues and the last three imidazole side-chains. The crystals have a solvent content of 77% (v/v) and form 70 A-wide channels that would allow the diffusion of peptides or even small proteins. The anti-His scFv crystals could thus act as a framework for the crystallization of His-tagged target proteins. Designed mutations in framework regions of the scFv lead to high-level expression of soluble protein in the periplasm of Escherichia coli. The recombinant anti-His scFv is a convenient detection tool when fused to alkaline phosphatase. When immobilized on a matrix, the antibody can be used for affinity purification of recombinant proteins carrying a very short tag of just three histidine residues, suitable for crystallization. The experimental structure is now the basis for the design of antibodies with even higher stability and affinity.

Alkaline Phosphatase↗

Self-immobilizing recombinant antibody fragments for immunoaffinity chromatography: generic, parallel, and scalable protein purification.

We present the directed immobilization of recombinant antibody fragments as ligands for general immunoaffinity chromatography methods. It is based on fusion proteins of scFv fragments with several chitin-binding domains which can be immobilized directly from a crude bacterial lysate on inexpensive chitin beads for the purification of proteins without any gradient or detector. It has been used with a positive pressure manifold, allowing the parallel processing of 24 different samples on a milligram scale, as convenient as plasmid isolation. The method is demonstrated with several anti-protein antibodies. In addition, methods are presented of using an anti-His tag antibody either alone or directly coupled to IMAC to obtain very pure protein. As those methods are scalable, they should prove very useful in the parallel purification of natural and recombinant proteins on small scales (for proteomics), medium scales (for crystallography and NMR), and very large scales (for therapeutic proteins).

Chromatography, Affinity↗