The influence of different rewetting procedures on the thrombogenicity of nanoporous poly(ether imide) microparticles.

Nanoporous microparticles prepared from poly(ether imide) (PEI) are discussed as candidate adsorber materials for the removal of uremic toxins during apheresis. Polymers exhibiting such porosity can induce the formation of micro-gas/air pockets when exposed to fluids. Such air presenting material surfaces are reported to induce platelet activation and thrombus formation. Physical or chemical treatments prior to implantation are discussed to reduce the formation of such gas nuclei. Here, we report about the influence of different rewetting procedures - as chemical treatments with solvents - on the thrombogenicity of hydrophobic PEI microparticles and PEI microparticles hydrophilized by covalent attachment of poly(vinyl pyrrolidone) (PVP) of two different chain lengths.Autoclaved dry PEI particles of all types with a diameter range of 200 - 250 µm and a porosity of about 84% ±2% were either rewetted directly with phosphate buffered saline (24 h) or after immersion in an ethanol-series. Thrombogenicity of the particles was studied in vitro upon contact with human sodium citrated whole blood for 60 min at 5 rpm vertical rotation. Numbers of non-adherent platelets were quantified, and adhesion of blood cells was qualitatively analyzed by bright field microscopy. Platelet activation (percentage of CD62P positive platelets and amounts of soluble P-Selectin) and platelet function (PFA100 closure times) were analysed.Retention of blood platelets on the particles was similar for all particle types and both rewetting procedures. Non-adherent platelets were less activated after contact with ethanol-treated particles of all types compared to those rewetted with phosphate buffered saline as assessed by a reduced number of CD62P-positive platelets and reduced amounts of secreted P-Selectin (P < 0.05 each). Interestingly, the hydrophilic surfaces significantly increased the number of activated platelets compared to hydrophobic PEI regardless of the rewetting agent. This suggests that, apart from wettability, other material properties might be more important to regulate platelet activation. PFA100 closure times were reduced and within the reference ranges in the ethanol group, however, significantly increased in the saline group. No substantial difference was detected between the tested surface modifications. In summary, rewetting with ethanol resulted in a reduced thrombogenicity of all studied microparticles regardless of their wettability, most likely resulting from the evacuation of air from the nanoporous particles.

Albumin solder covalently bound to a polymer membrane: New approach to improve binding strength in laser tissue soldering in-vitro.

Laser tissue soldering (LTS) based on indocyanine green (ICG)-mediated heat-denaturation of proteins might be a promising alternative technique for micro-suturing, but up to now the problem of too weak shear strength of the solder welds in comparison to sutures is not solved. Earlier reports gave promising results showing that solder supported by carrier materials can enhance the cohesive strength of the liquid solder. In these studies, the solder was applied to the carriers by dip coating. Higher reliability of the connection between the solder and the carrier material is expected when the solder is bound covalently to the carrier material. In the present study a poly(ether imide) (PEI) membrane served as carrier material and ICG-supplemented albumin as solder substrate. The latter was covalently coupled to the carrier membrane under physiological conditions to prevent structural protein changes. As laser source a diode continuous-wave laser emitting at 808 nm with intensities between 250 mW and 1500 mW was utilized. The albumin functionalized carrier membrane was placed onto the tunica media of explanted pig thoracic aortae forming an overlapping area of approximately 0.5×0.5 cm2. All tests were performed in a dry state to prevent laser light absorption by water. Infrared spectroscopy, spectro-photometrical determination of the secondary and primary amine groups after acid orange II staining, contact angle measurements, and atomic force microscopy proved the successful functionalization of the PEI membrane with albumin. A laser power of 450 mW LTS could generate a membrane-blood vessel connection which was characterized by a shear strength of 0.08±0.002 MPa, corresponding to 15% of the tensile strength of the native blood vessel. Theoretically, an overlapping zone of 4.1 mm around the entire circumference of the blood vessel could have provided shear strength of the PEI membrane-blood vessel compound identical to the tensile strength of the native blood vessel. These in-vitro results confirmed the beneficial effects of solder reinforcement by carrier membranes, and suggest LTS with covalently bound solders on PEI substrates for further studies in animal models.

Influence of different surface treatments of poly(n-butyl acrylate) networks on fibroblasts adhesion, morphology and viability.

BACKGROUND: Physical and chemical characteristics of implant materials determine the fate of long-term cardiovascular devices. However, there is still a lack of fundamental understanding of the molecular mechanisms occurring in the material-tissue interphase. In a previous study, soft covalently crosslinked poly(n-butyl acrylate) networks (cPnBA) were introduced as sterilizable, non-toxic and immuno-compatible biomaterials with mechanical properties adjustable to blood vessels. Here we study the influence of different surface treatments in particular oxygen plasma modification and fibrinogen deposition as well as a combinatorial approach on the adhesion and viability of fibroblasts. MATERIAL AND METHODS: Two types of cPnBA networks with Young's moduli of 0.19±0.01 MPa (cPnBA04) and 1.02±0.01 MPa (cPnBA73) were synthesized and post-modified using oxygen plasma treatment (OPT) or fibrinogen coating (FIB) or a combination of both (OPT+FIB). The water contact angles of the differently post-treated cPnBAs were studied to monitor changes in the wettability of the polymer surfaces. Because of the key role of vascular fibroblasts in regeneration processes around implant materials, here we selected L929 fibroblasts as model cell type to explore morphology, viability, metabolic activity, cell membrane integrity as well as characteristics of the focal adhesions and cell cytoskeleton on the cPnBA surfaces. RESULTS: Compared to non-treated cPnBAs the advancing water-contact angles were found to be reduced after all surface modifications (p < 0.05, each), while lowest values were observed after the combined surface treatment (OPT+FIB). The latter differed significantly from the single OPT and FIB. The number of adherent fibroblasts and their adherence behavior differed on both pristine cPnBA networks. The fibroblast density on cPnBA04 was 743±434 cells·mm-2, was about 6.5 times higher than on cPnBA73 with 115±73 cells·mm-2. On cPnBA04 about 20% of the cells were visible as very small, round and buckled cells while all other cells were in a migrating status. On cPnBA73, nearly 50% of fibroblasts were visible as very small, round and buckled cells. The surface functionalization either using oxygen plasma treatment or fibrinogen coating led to a significant increase of adherent fibroblasts, particularly the combination of both techniques, for both cPnBA networks. It is noteworthy to mention that the fibrinogen coating overruled the characteristics of the pristine surfaces; here, the fibroblast densities after seeding were identical for both cPnBA networks. Thus, the binding rather depended on the fibrinogen coating than on the substrate characteristics anymore. While the integrity of the fibroblasts membrane was comparable for both polymers, the MTS tests showed a decreased metabolic activity of the fibroblasts on cPnBA. CONCLUSION: The applied surface treatments of cPnBA successfully improved the adhesion of viable fibroblasts. Under resting conditions as well as after shearing the highest fibroblast densities were found on surfaces with combined post-treatment.

Strategy for the hemocompatibility testing of microparticles.

Polymer-based microparticles are applied as non-thrombogenic or thrombogenic materials in a wide variety of intra- or extra-corporeal medical devices. As demanded by the regulatory agencies, the hemocompatibility of these blood contacting biomaterials has to be evaluated in vitro to ensure that the particle systems appropriately fulfill the envisioned function without causing undesired events such as thrombosis or inflammation. Currently described in vitro assays for hemocompatibility testing of particles comprise tests with different single cell types (e.g. erythrocytes or leukocytes), varying concentrations/dilutions of the used blood cells or whole blood, which are not standardized.Here, we report about an in vitro dynamic test system for studying the hemocompatibility of polymeric microparticles utilizing fresh human whole blood from apparently healthy subjects, collected and processed under standardized conditions. Spherical poly(ether imide) microparticles with an average diameter of 140±30 µm were utilized as model systems. Reported as candidate materials for the removal of uremic toxins, these microparticles are anticipated to facilitate optimal flow conditions in a dialyzer with minimal backflow and blood cell damage. Pristine (PEI) and potassium hydroxide (PEI-KOH) functionalized microparticles exhibited similarly nanoporous surfaces (PEI: ØExternal pore = 90±60 nm; PEI-KOH ØExternal pore = 150±130 nm) but varying water wettabilities (PEI: θadv = 112±10° PEI-KOH θadv = 60±2°). The nanoporosity of the microparticle surfaces allows the exchange of toxic solutes from blood towards the interconnective pores in the particle core, while an immigration of the substantially larger blood cells is inhibited.Sterilized PEI microparticles were incorporated -air-free -in a syringe-based test system and exposed to whole blood for 60 minutes under gentle agitation. Thereafter, thrombi formation on the particles surfaces were analyzed microscopically. In the collected whole blood the non-adherent/circulating single blood cells were quantified via a differentiated complete blood cell count and the activation of platelets (P-Selectin expression, secretion and release), platelet function (PFA100 closure time) as well as thrombin formation (thrombin-antithrombin-complex) was analyzed. Free hemoglobin (HGB) levels were quantified as a measure of hemolysis.Microscopic evaluation revealed thrombi formation and particle aggregates for all tested microparticles. Reduction of circulating blood cells differed significantly between the particle types. Particularly, platelet and monocyte counts decreased up to 50% compared to the control (syringe filled with whole blood but without microparticles). In accordance, platelet activation, thrombin levels and degrees of hemolysis were clearly elevated in the particle loaded test systems and allowed a differentiation between the particle types. Increased PFA100 closure times (as activating agent a combination of collagen/ADP was used) indicated a similarly reduced ability of platelets to adhere and form stable aggregates independent from the particle type tested. This observation is most probably a consequence of the strong thrombus formation in the test system, which is associated with a reduction of the circulating blood cells.The reported in vitro dynamic whole blood test system allowed the sensitive analysis of the hemocompatibility of polymer-based microparticles and was successfully validated for porous PEI microparticles with different water wettabilities. Beyond the qualitative and quantitative analysis of cell-material interactions, the test also allowed the functional evaluation of platelets in whole blood.

Triple-shape effect in polymer-based composites by cleverly matching geometry of active component with heating method.

A triple-shape effect is created for a segmented device consisting of an active component encapsulated in a highly flexible polymer network. Segments with the same composition but different interface areas can be recovered independently either at specific field strengths (Hsw ) during inductive heating, at a specific time during environmentally heating, or at different airflow during inductive heating at constant H. Herein the type of heating method regulates the sequence order.

The influence of poly(n-butyl acrylate) networks on viability and function of smooth muscle cells and vascular fibroblasts.

BACKGROUND: The patency of small-diameter vascular prostheses is limited by several factors such as thrombogenicity, which is strongly influenced by surface roughness and chemical composition, or a mechanical mismatch between the elastic modulus of an artery and of the vascular prosthesis. A confluent layer of endothelial cells onto the inner surface of vascular prostheses could improve the hemocompatibility of the device. Biomaterials with adjustable elastic properties could be tailored to the values of human arteries so that a prothesis mismatch could be avoided. It was recently demonstrated that a co-culture of endothelial cells with angiogenically stimulated monocytes (aMO2) shows an accelerated formation of a functional confluent endothelial cell monolayer on soft hydrophobic poly(n-butyl acrylate) (cPnBA) networks. In addition, the cell compatibility with vascular smooth muscle cells and aortic fibroblasts, which are other important cell types of the vessel wall, is essential for a vascular prosthesis material and must therefore be explored. PURPOSE: Here we investigated the interaction of human vascular smooth muscle cells and aortic fibroblasts with cPnBA04 and cPnBA73. MATERIAL AND METHODS: Human primary vascular smooth muscle cells and aortic fibroblasts were seeded on the two cPnBAs with different elastic moduli (cPnBA04 - 250 kPa and cPnBA73 - 1100 kPa) over 72 h. A live-dead staining (fluorescein diacetate/propium iodide) was performed to determine the morphology and viability of adherent cells. Furthermore, the extracellular matrix components, the actin cytoskeleton, the cell-material-contacts and the cytokine profiles were analysed. RESULTS: Both cell types adhered and were viable on cPnBA04 and cPnBA73. The level of pro-inflammatory cytokine secretion (IFN-γ and TNF-α) by smooth muscle cells and vascular fibroblasts was comparable to that of cells cultivated on a control material. The release of these cytokines by human fibroblasts was higher on cPnBA73 compared to cPnBA04. Both cell types secreted an extracellular matrix comparable to cells seeded on a control material. CONCLUSION: The study revealed, that cPnBA with varying elastic moduli are not only suitable for the cultivation of endothelial cells, but also for human vascular smooth muscle cells and aortic fibroblasts. Therefore, cPnBA could be a potential candidate material for the development of cardiovascular prostheses.

Behaviour of fibroblasts on water born acrylonitrile-based copolymers containing different cationic and anionic moieties.

The chemical composition of a substrate can influence the adhesion, viability and proliferation of cells seeded on the substrate. The aim of this work was to investigate the influence of different cationic or anionic moieties in acrylonitrile-based copolymers on the interaction with fibroblasts. A series of ten different types of acrylonitrile-based copolymers with a random sequence structure was prepared using a water born synthesis process to exclude potential residues of organic solvents. As charged comonomers cationic methacrylic acid-2-aminoethylester hydrochloride (AEMA), N-3-amino-propyl-methacrylamide hydrochloride (APMA) and anionic 2-methyl-2-propene-1-sulfonic acid sodium salt (NaMAS) were utilized. By application of a specific sintering procedure the copolymer materials were processed into transparent disks for conducting cell tests in direct contact. The copolymers were analyzed with respect to their composition and surface properties. Cytotoxicity tests of the polymer extracts, as well as of the disks were performed with L929 mouse fibroblasts. All copolymers showed no cytotoxic effects. Furthermore, for higher molar ratios of AEMA an increase in cell growth could be observed, which might be a hint that higher charge densities are favorable for the proliferation of L929 cells.

Immuno-compatibility of soft hydrophobic poly (n-butyl acrylate) networks with elastic moduli for regeneration of functional tissues.

The need for engineered devices to treat cardiovascular diseases is increasing due to an aging population and a changing lifestyle. Soft poly(n-butyl acrylate) (cPnBA) networks were recently described as polymer networks with adjustable mechanical properties and suggested as soft substrates for cells, which could potentially be used for cardiovascular implants. Vascular prostheses designed to be implanted in arteries should have an elasticity similar to blood vessels (elastic modulus at body temperature between 100 and 1200 kPa). Therefore, cPnBA networks with E-moduli of 250 kPa (cPnBA0250) and 1100 kPa (cPnBA1100) were developed. Recently, it was shown that both materials were non-cytotoxic for murin fibroblasts, human primary endothelial cells and human monocytes. However, before such newly developed polymers can be used in vivo, it has to be assured that the sterilized materials have a very low endotoxin load to avoid an unspecific activation of the immune system, which otherwise might cause local or systemic inflammatory responses and could lead to severe pathologies. In this study we investigated the immuno-compatibility of sterilized cPnBA0250 and cPnBA1100 with the help of an immuno-competent macrophage cell line as well as with whole human blood.

Viability, morphology and function of primary endothelial cells on poly(n-butyl acrylate) networks having elastic moduli comparable to arteries.

Soft hydrophobic poly(n-butyl acrylate) networks (cPnBA) were developed as entropy elastic substrates for passive mechanical stimulation of cells, where the elastic modulus of the cPnBAs could be systematically adjusted by variation of the cross-link density. The networks were synthesized by thermally-induced radical polymerization from n-butyl acrylate, with poly(propylene glycol) dimethacrylate (PPGDMA) acting as cross-linker, whereby the purity of the cPnBAs was confirmed by(1) H-NMR spectroscopy and gas chromatography. In this work two cPnBA polymer networks with an elastic modulus around 200 kPa and 1 MPa were investigated having an elastic modulus similar to that of arteries. Both cPnBAs exhibited an almost smooth surface with a surface roughness (R q) in the wet state ranging from 17 to 37 nm and a similar zetapotential, indicating an almost identical chemical composition within the topmost surface layer in terms of functional groups. In contrast, wettability of the samples was found to be different with an advancing angle ( advancing) of 123 ± 3.8° for cPnBA0250, while for cPnBA1100 significantly lower values for advancing (111 ± 3.8°) were obtained. First in vitro tests were performed with primary endothelial cells (HUVEC) to study its effects on vascular cell functions. Within the time period of cultivation (72 h), the cells on the cPnBA samples reached subconfluence and showed a viability rate of almost 100%. Although cell density differed after 72 h with more cells on cPnBA0250 than on cPnBA1100, both materials showed no significant effect on the cell morphology, the cellular LDH-release, which was used as marker for the integrity of the cell membrane, and the organisation of the VE-cadherin. However, lower cell density and less actin stress fibre formation on cPnBA1100 might indicate that cell-material interaction was weaker on cPnBA1100 than on cPnBA0250. The secretion of the vasoactive cytokines prostacyclin (PGI2) and thromboxane A2 (TXA2) was low compared to previously reported values. However, the anti-thrombogenic ratio of PGI2/TXA2 - which is balanced under physiological conditions - with much higher PGI2 compared to TXA2 (up to 17.6-fold after 72 h for cPnBA1100) suggests that this material might be effective to preventing thrombosis.

Hemocompatibility of soft hydrophobic poly(n-butyl acrylate) networks with elastic moduli adapted to the elasticity of human arteries.

Small calibre vascular prostheses (<6 mm) still lack medium and long term patency. Inelasticity of the prosthesis is one of the characteristics, which is involved in the mechanisms of failure (e.g. the development of neointimal hyperplasia at the distal anastomosis). Here we report about covalently crosslinked poly(n-butyl acrylate) networks (cPnBA) with adjustable elastic moduli, which can be tailored to values of human arteries (between 100 and 1000 kPa). Motivated by the potential application of such polymer networks as cardiovascular prosthesis, adhesion, activation and thrombus formation of human platelets on cPnBA networks were evaluated. All cPnBA-samples displayed a high thrombogenicity compared to the control (silicone). Significantly less platelets adhered on the surface of the soft cPnBA04 than on cPnBA73. All cPnBA samples displayed a higher number of platelet aggregates and a lower number of inactivated platelets in comparison to the control. While the elastic modulus of cPnBA networks could be successfully adjusted to that of human arteries, the tested polymers did not show an optimal hemocompatibility. Future studies aim at improving the biofunctionality by surface modification of these polymer networks.

In vivo evaluation of the angiogenic effects of the multiblock copolymer PDC using the hen's egg chorioallantoic membrane test.

Multiblock copolymers with shape-memory capability attracted tremendous interest as promising candidate materials for smart, degradable implants. In the present study the hen's egg-chorioallantoic membrane test (HET-CAM test) was used to investigate the angiogenic properties of a thermoplastic, biodegradable multiblock copolymer PDC composed of poly(p-dioxanone) hard segments (PPDO) and crystallizable poly(ε-caprolactone) switching segments (PCL), whereby PPDO and PCL homopolymers were investigated as controls. According to our HET-CAM test data, only PDC induced significant microvessel attraction and formation in the contact area of the test specimen after 48 hours of incubation showing newly formed blood vessels along the outer edge of the material. In contrast, no newly formed blood vessels were observed around the PPDO or PCL specimen after the same incubation period. These in vivo results indicate that the multiblock copolymer PDC possibly possesses an angiogenic effect and it can induce blood vessel formation in its direct vicinity when it is implanted in vivo.

Degradation of and angiogenesis around multiblock copolymers containing poly(p-dioxanone)- and poly(epsilon-caprolactone)-segments subcutaneously implanted in the rat neck.

The degradation behavior and the effect on angiogenesis of multiblock copolymers based on poly(p-dioxanone)- and poly(epsilon-caprolactone)-segments (PDC) were studied in vivo. PDC is a multifunctional biomaterial combining degradability and shape-memory capabilities. The "in vivo" degradation of PDC is characterized by a fragmentation occurring at the material tissue interface. This observation is consistent with the enzyme supported degradation behaviour, which was determined "in vitro". PDC revealed to induce the formation of blood micro-vessels nearby in the periimplantary tissues. Both might explain the good PDC integration into tissues in terms of a strong connection between the implant and the periimplantary tissue. Micro blood-vessels might be involved in the clearance of the small particles, which appear in the periimplantary tissue when PDC degrades.

Melt-processable hydrophobic acrylonitrile-based copolymer systems with adjustable elastic properties designed for biomedical applications.

Acrylonitrile-based polymer systems (PAN) are comprehensively explored as versatile biomaterials having various potential biomedical applications, such as membranes for extra corporal devices or matrixes for guided skin reconstruction. The surface properties (e.g. hydrophilicity or charges) of such materials can be tailored over a wide range by variation of molecular parameters such as different co-monomers or their sequence structure. Some of these materials show interesting biofunctionalities such as capability for selective cell cultivation. So far, the majority of AN-based copolymers, which were investigated in physiological environments, were processed from the solution (e.g. membranes), as these materials are thermo-sensitive and might degrade when heated. In this work we aimed at the synthesis of hydrophobic, melt-processable AN-based copolymers with adjustable elastic properties for preparation of model scaffolds with controlled pore geometry and size. For this purpose a series of copolymers from acrylonitrile and n-butyl acrylate (nBA) was synthesized via free radical copolymerisation technique. The content of nBA in the copolymer varied from 45 wt% to 70 wt%, which was confirmed by 1H-NMR spectroscopy. The glass transition temperatures (Tg) of the P(AN-co-nBA) copolymers determined by differential scanning calorimetry (DSC) decreased from 58 degrees C to 20 degrees C with increasing nBA-content, which was in excellent agreement with the prediction of the Gordon-Taylor equation based on the Tgs of the homopolymers. The Young's modulus obtained in tensile tests was found to decrease significantly with rising nBA-content from 1062 MPa to 1.2 MPa. All copolymers could be successfully processed from the melt with processing temperatures ranging from 50 degrees C to 170 degrees C, whereby thermally induced decomposition was only observed at temperatures higher than 320 degrees C in thermal gravimetric analysis (TGA). Finally, the melt processed P(AN-co-nBA) biomaterials were sterilized with ethylene oxide and tested for cytotoxicity in direct contact tests with L929 cells according to the EN DIN ISO standard 10993-5. All tested samples exhibited non-toxic effects on the functional integrity of the cell membrane and the mitochondrial activity. However, the morphology of the cells on the samples was different from that observed on polystyrene as control, indicating slightly cytotoxic effects according to the evaluation guide of the US Pharmacopeial Convention. Thus, the melt-processable, hydrophobic P(AN-co-nBA) copolymers with adjustable mechanical properties are promising candidates for in vitro investigations of tissue growth kinetics.

Nuclear spins and magnetic moments of 71,73,75Cu: inversion of pi2p3/2 and pi1f5/2 levels in 75Cu.

We report the first confirmation of the predicted inversion between the pi2p3/2 and pi1f5/2 nuclear states in the nu(g)9/2 midshell. This was achieved at the ISOLDE facility, by using a combination of in-source laser spectroscopy and collinear laser spectroscopy on the ground states of 71,73,75Cu, which measured the nuclear spin and magnetic moments. The obtained values are mu(71Cu)=+2.2747(8)mu(N), mu(73Cu)=+1.7426(8)mu(N), and mu(75Cu)=+1.0062(13)mu(N) corresponding to spins I=3/2 for 71,73Cu and I=5/2 for 75Cu. The results are in fair agreement with large-scale shell-model calculations.

Selective enzymatic degradation of poly(epsilon-caprolactone) containing multiblock copolymers.

The hydrolytic and Pseudomonas lipase catalysed enzymatic degradation was studied for PDC multiblock copolymers consisting of poly(epsilon-caprolactone) (PCL) segments and poly(p-dioxanone) (PPDO) segments with variable composition. The enzymatic degradation of these multiblock copolymers is significantly accelerated by Pseudomonas lipase in contrast to the hydrolytic degradation where the degradation behaviour is determined by the PPDO segments. Degradation time intervals up to 200h are selected, where the PPDO segments remain stable and do not contribute to the degradation process. A linear correlation between weight loss and increasing PCL content of the multiblock copolymers was found. X-ray diffraction data confirm that both crystalline and amorphous PCL are attacked by the enzymes. SEM cross-section images reveal that Pseudomonas lipase penetrates into the PDC polymers. The present study impressively demonstrates that selective enzymatic degradation of PCL containing multifunctional polymers is a beneficial tool for controlling their degradation properties.

Enzymatic chain scission kinetics of poly(epsilon-caprolactone) monolayers.

The hydrolytic and enzymatic degradation behavior of poly(epsilon-caprolactone) (PCL) is investigated using the Langmuir monolayer technique, and an improved data acquisition and data reduction procedure is presented. Hydrolytic and enzymatic monolayer degradation experiments of PCL with various molecular weights by Pseudomonas cepacia lipase have been carried out to analyze the influence of subphase pH, subphase temperature, enzyme concentration, and the packing density of polymer chains on the degradation kinetics. The enzymatic monolayer degradation results in an exponential increase in the number of dissolved degradation fragments with increasing degradation time, which confirms random chain scission to be the dominant scission mechanism. The increase in the enzymatic scission rate constant with decreasing initial average molecular weight of the polymers is assigned to the influence of the area density of polar terminal groups on the substrate-enzyme complex formation.

Reduction of the spin-orbit splittings at the n = 28 shell closure.

The N = 28 shell closure has been investigated via the 46Ar(d,p)47Ar transfer reaction in inverse kinematics. Energies and spectroscopic factors of the neutron p(3/2), p(1/2), and f(5/2) states in 47Ar were determined and compared to those of the 49Ca isotone. We deduced a reduction of the N = 28 gap by 330(90) keV and spin-orbit weakenings of approximately 10(2) and 45(10)% for the f and p states, respectively. Such large variations for the f and p spin-orbit splittings could be accounted for by the proton-neutron tensor force and by the density dependence of the spin-orbit interaction, respectively. This contrasts with the picture of the spin-orbit interaction as a surface term only.

Initiation of shape-memory effect by inductive heating of magnetic nanoparticles in thermoplastic polymers.

In shape-memory polymers, changes in shape are mostly induced by heating, and exceeding a specific switching temperature, T(switch). If polymers cannot be warmed up by heat transfer using a hot liquid or gaseous medium, noncontact triggering will be required. In this article, the magnetically induced shape-memory effect of composites from magnetic nanoparticles and thermoplastic shape-memory polymers is introduced. A polyetherurethane (TFX) and a biodegradable multiblock copolymer (PDC) with poly(p-dioxanone) as hard segment and poly(epsilon-caprolactone) as soft segment were investigated as matrix component. Nanoparticles consisting of an iron(III)oxide core in a silica matrix could be processed into both polymers. A homogeneous particle distribution in TFX could be shown. Compounds have suitable elastic and thermal properties for the shape-memory functionalization. Temporary shapes of TFX compounds were obtained by elongating at increased temperature and subsequent cooling under constant stress. Cold-drawing of PDC compounds at 25 degrees C resulted in temporary fixation of the mechanical deformation by 50-60%. The shape-memory effect of both composite systems could be induced by inductive heating in an alternating magnetic field (f = 258 kHz; H = 30 kA x m(-1)). The maximum temperatures achievable by inductive heating in a specific magnetic field depend on sample geometry and nanoparticle content. Shape recovery rates of composites resulting from magnetic triggering are comparable to those obtained by increasing the environmental temperature.

Dhea supplementation and cognition in postmenopausal women.

Previous work has suggested that DHEA supplementation may have adverse cognitive effects in elderly women. This article analyzed 24-h measurements of DHEA, DHEAS, and cortisol to determine if cognitive decrease with treatment is mediated by DHEA's impact on endogenous cortisol. It was found that DHEA administration increased cortisol at several hours during the day. In the treatment group, cortisol was positively associated with cognition at study completion. An increase in negative associations between DHEA(S) levels and cognition was found at completion. Increased cortisol does not explain the cognitive deficits associated with DHEA, suggesting a direct negative effect of exogenous DHEA on cognition.

Smart implant materials.

The combination of stimuli-sensitive implant materials and minimally invasive surgery techniques is expected to give rise to numerous applications. Biodegradable thermoplastic elastomers are presented here as an example of a group of biodegradable implant materials with shape-memory properties. Their capabilities and use in a smart suture are described.