In situ kinetics studies of Zn-Al LDH intercalation with corrosion related species.

Kinetic parameters for three anion exchange reactions - Zn-LDH-NO3→ Zn-LDH-Cl, Zn-LDH-NO3→ Zn-LDH-SO4 and Zn-LDH-NO3→ Zn-LDH-VOx- were obtained by in situ synchrotron study. The first and the second ones are two-stage reactions; the first stage is characterized by the two-dimensional diffusion-controlled reaction following deceleratory nucleation and the second stage is a one-dimensional diffusion-controlled reaction also with a decelerator nucleation effect. In the case of exchange NO3-→ Cl- host anions are completely released, while in the case of NO3-→ SO42- the reaction ends without complete release of nitrate anions. The exchange of Zn-LDH-NO3→ Zn-LDH-VOx is a one-stage reaction and goes much slower than the previous two cases. The latter is characterized by a one stage two-dimensional reaction with an instantaneous nucleation. As a result, at the end of this process there are two crystalline phases with different polyvanadate species, presumably V4O124- and V2O74-, nitrate anions were not completely released. The rate of replacing NO3- anions by guest ones can be represented as Cl- > SO42- > VOxy-.

Influence of the Molecular Weight and the Presence of Calcium Ions on the Molecular Interaction of Hyaluronan and DPPC.

Hyaluronan is an essential physiological bio macromolecule with different functions. One prominent area is the synovial fluid which exhibits remarkable lubrication properties. However, the synovial fluid is a multi-component system where different macromolecules interact in a synergetic fashion. Within this study we focus on the interaction of hyaluronan and phospholipids, which are thought to play a key role for lubrication. We investigate how the interactions and the association structures formed by hyaluronan (HA) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) are influenced by the molecular weight of the bio polymer and the ionic composition of the solution. We combine techniques allowing us to investigate the phase behavior of lipids (differential scanning calorimetry, zeta potential and electrophoretic mobility) with structural investigation (dynamic light scattering, small angle scattering) and theoretical simulations (molecular dynamics). The interaction of hyaluronan and phospholipids depends on the molecular weight, where hyaluronan with lower molecular weight has the strongest interaction. Furthermore, the interaction is increased by the presence of calcium ions. Our simulations show that calcium ions are located close to the carboxylate groups of HA and, by this, reduce the number of formed hydrogen bonds between HA and DPPC. The observed change in the DPPC phase behavior can be attributed to a local charge inversion by calcium ions binding to the carboxylate groups as the binding distribution of hyaluronan and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine is not changed.

Thermoresponsive Pentablock Copolymer on Silica: Temperature Effects on Adsorption, Surface Forces, and Friction.

The adsorption of hydrophilic or amphiphilic multiblock copolymers provides a powerful means to produce well-defined "smart" surfaces, especially if one or several blocks are sensitive to external stimuli. We focus here on an A-B-A-B-A copolymer, where A is a cationic poly((3-acrylamido-propyl)-trimethylammonium chloride) (PAMPTMA) block containing 15 (end blocks) or 30 (middle block) repeat units and B is a neutral thermosensitive water-soluble poly(2-isopropyl-2-oxazoline) (PIPOZ) block with 50 repeat units. X-ray reflectivity and quartz crystal microbalance with dissipation monitoring were employed to study the adsorption of PAMPTMA15-PIPOZ50-PAMPTMA30-PIPOZ50-PAMPTMA15 on silica surfaces. The latter technique was employed at different temperatures up to 50 °C. Surface forces and friction between the two silica surfaces across aqueous pentablock copolymer solutions at different temperatures were determined with the atomic force microscopy colloidal probe force and friction measurements. The cationic pentablock copolymer was found to have a high affinity to the negatively charged silica surface, leading to a thin (2 nm) and rigid adsorbed layer. A steric force was encountered at a separation of around 3 nm from hard wall contact. A capillary condensation of a polymer-rich phase was observed at the cloud point of the solution. The friction forces were evaluated using Amontons' rule modified with an adhesion term.

Influence of high hydrostatic pressure on solid supported DPPC bilayers with hyaluronan in the presence of Ca2+ ions.

The molecular mechanisms responsible for outstanding lubrication of natural systems, like articular joints, have been the focus of scientific research for several decades. One essential aspect is the lubrication under pressure, where it is important to understand how the lubricating entities adapt under dynamic working conditions in order to fulfill their function. We made a structural investigation of a model system consisting of two of the molecules present at the cartilage interface, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine and hyaluronan, at high hydrostatic pressure. Phospholipid layers are found at the cartilage surfaces and are able to considerably reduce friction. Their behavior under load and varied solution conditions is important as pressures of 180 bar are encountered during daily life activities. We focus on how divalent ions, like Ca2+, affect the interaction between DPPC and hyaluronan, as other investigations have indicated that calcium ions influence their interaction. It could be shown that already low amounts of Ca2+ strongly influence the interaction of hyaluronan with DPPC. Our results suggest that the calcium ions increase the amount of adsorbed hyaluronan indicating an increased electrostatic interaction. Most importantly, we observe a modification of the DPPC phase diagram as hyaluronan absorbs to the bilayer which results in an Lα-like structure at low temperatures and a decoupling of the leaflets forming an asymmetric bilayer structure.

Macromolecular pHPMA-Based Nanoparticles with Cholesterol for Solid Tumor Targeting: Behavior in HSA Protein Environment.

Nanoparticles (NPs) that form by self-assembly of amphiphilic poly(N-(2-hydroxypropyl)-methacrylamide) (pHPMA) copolymers bearing cholesterol side groups are potential drug carriers for solid tumor treatment. Here, we investigate their behavior in solutions of human serum albumin (HSA) in phosphate buffered saline. Mixed solutions of NPs, from polymer conjugates with or without the anticancer drug doxorubicin (Dox) bound to them, and HSA at concentrations up to the physiological value are characterized by synchrotron small-angle X-ray scattering and isothermal titration calorimetry. When Dox is absent, a small amount of HSA molecules bind to the cholesterol groups that form the core of the NPs by diffusing through the loose pHPMA shell or get caught in meshes formed by the pHPMA chains. These interactions are strongly hindered by the presence of Dox, which is distributed in the pHPMA shell, meaning that the delivery of Dox by the NPs in the human body is not affected by the presence of HSA.

Solution structure of monomeric and trimeric photosystem I of Thermosynechococcus elongatus investigated by small-angle X-ray scattering.

The structure of monomeric and trimeric photosystem I (PS I) of Thermosynechococcus elongatus BP1 (T. elongatus) was investigated by small-angle X-ray scattering (SAXS). The scattering data reveal that the protein-detergent complexes possess radii of gyration of 58 and 78 Å in the cases of monomeric and trimeric PS I, respectively. The results also show that the samples are monodisperse, virtually free of aggregation, and contain empty detergent micelles. The shape of the protein-detergent complexes can be well approximated by elliptical cylinders with a height of 78 Å. Monomeric PS I in buffer solution exhibits minor and major radii of the elliptical cylinder of about 50 and 85 Å, respectively. In the case of trimeric PS I, both radii are equal to about 110 Å. The latter model can be shown to accommodate three elliptical cylinders equal to those describing monomeric PS I. A structure reconstitution also reveals that the protein-detergent complexes are larger than their respective crystal structures. The reconstituted structures are larger by about 20 Å mainly in the region of the hydrophobic surfaces of the monomeric and trimeric PS I complexes. This seeming contradiction can be resolved by the addition of a detergent belt constituted by a monolayer of dodecyl-ß-D-maltoside molecules. Assuming a closest possible packing, a number of roughly 1024 and 1472 detergent molecules can be determined for monomeric and trimeric PS I, respectively. Taking the monolayer of detergent molecules into account, the solution structure can be almost perfectly modeled by the crystal structures of monomeric and trimeric PS I.

Structure of DPPC-hyaluronan interfacial layers - effects of molecular weight and ion composition.

Hyaluronan and phospholipids play an important role in lubrication in articular joints and provide in combination with glycoproteins exceptionally low friction coefficients. We have investigated the structural organization of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) Langmuir layers at the solution-air interface at different length scales with respect to the adsorption of hyaluronan (HA). This allows us to assemble a comprehensive picture of the adsorption and the resulting structures, and how they are affected by the molecular weight of HA and the presence of calcium ions. Brewster angle microscopy and grazing incident diffraction were used to determine the lateral structure at the micro- and macro scale. The data reveals an influence of HA on both the macro and micro structure of the DPPC Langmuir layer, and that the strength of this effect increases with decreasing molecular weight of HA and in presence of calcium ions. Furthermore, from X-ray reflectivity measurements we conclude that HA adsorbs to the hydrophilic part of DPPC, but data also suggest that two types of interfacial structures are formed at the interface. We argue that hydrophobic forces and electrostatic interactions play important rules for the association between DPPC and HA. Surface pressure area isotherms were used to determine the influence of HA on the phase behavior of DPPC while electrophoretic mobility measurements were used to gain insight into the binding of calcium ions to DPPC vesicles and hyaluronan.

Mixed Layers of Nonionic Dendritic Amphiphiles and DPPC at the Water Surface.

Nonionic dendritic amphiphiles that self-assemble into defined supramolecular aggregates are useful for the efficient solubilization of active agents, for example, in drug delivery. We investigated a new class of dendritic amphiphiles based on a hydrophilic polyol dendron head connected to a two-chain hydrophobic block. In analogy to phospholipids, these molecules form well-organized layers in bulk (vesicles) or at the water surface (Langmuir monolayer). The actual study focuses on the phase behavior and microscopic structure of mixed Langmuir layers of theses dendritic amphiphiles with the well-known phospholipid DPPC. The combination of surface pressure area isotherms with X-ray grazing incident diffraction and Brewster angle microscopy gives us information on the phase behavior of the mixed monolayers and the orientation of the amphiphiles inside the condensed domains with molecular resolution. We could prove that the dendritic generation and, by this, the headgroup size of the amphiphilic molecules have a significant influence on their interaction with DPPC at the air-water interface. Thus, our findings are important for the understanding of mixed lipid membranes in general as well as for the preparation of artificial membranes and vesicles with adjustable properties, e.g., their drug delivery potential.

Data analysis of the influence of microstructure, composition, and loading conditions on stress corrosion cracking behavior of Mg alloys.

Stress corrosion cracking (SCC) can be a crucial problem in applying rare earth (RE) Magnesium alloys in environments where mechanical loads and electrochemical driven degradation processes interact. It has been proven already that the SCC behavior is associated with microstructural features, compositions, loading conditions, and corrosive media, especially in-vivo. However, it is still unclear when and how mechanisms acting on multiple scales and respective system descriptors predictable contribute to SCC for the wide set of existing Mg alloys. In the present work, suitable literature data along SCC of Mg alloys has been analyzed to enable the development of a reliable SCC model for MgGd binary alloys. Pearson correlation coefficient and linear fitting are utilized to describe the contribution of selected parameters to corrosion and mechanical properties. Based on our data analysis, a parameter ranking is obtained, providing information on the SCC impact with regard to ultimate tensile strength (UTS) and fracture elongation of respective materials. According to the analyzed data, SCC susceptibility can be grouped and mapped onto Ashby type diagrams for UTS and elongation of respective base materials tested in air and in corrosive media. The analysis reveals the effect of secondary phase content as a crucial materials descriptor for our analyzed materials and enables better understanding towards SCC model development for Mg-5Gd alloy based implant.

Multifaceted bone response to immunomodulatory magnesium implants: Osteopromotion at the interface and adipogenesis in the bone marrow.

Orthopedic implants made of biodegradable magnesium (Mg) provide an alternative to nondegradable implants for fracture repair. Widely reported to be pro-osteogenic, Mg implants are also believed to be anti-inflammatory and anti-osteoclastic, but this is difficult to reconcile with the early clinical inflammation observed around these implants. Here, by surveying implant healing in a rat bone model, we determined the cellular responses and structural assembly of bone correlated with the surface changes of Mg implants inherent in degradation. We show that, compared to titanium, both high-purity (99.998 %) and clinical-grade, rare earth-alloyed (MgYREZr) Mg implants create an initial, transient proinflammatory environment that facilitates inducible nitric oxide synthase-mediated macrophage polarization, osteoclastogenesis, and neoangiogenesis programs. While this immunomodulation subsequently reinforces reparative osteogenesis at the surface of both Mg implants, the faster degradation of high-purity Mg implants, but not MgYREZr implants, elicits a compositional alteration in the interfacial bone and a previously unknown proadipogenic response with persistent low-grade inflammation in the surrounding bone marrow. Beyond the need for rigorous tailoring of Mg implants, these data highlight the need to closely monitor osseointegration not only at the immediate implant surface but also in the peri-implant bone and adjacent bone marrow.

Sheep Bone Ultrastructure Analyses Reveal Differences in Bone Maturation around Mg-Based and Ti Implants.

Magnesium alloys are some of the most convenient biodegradable materials for bone fracture treatment due to their tailorable degradation rate, biocompatibility, and mechanical properties resembling those of bone. Despite the fact that magnesium-based implants and ZX00 (Mg-0.45Zn-0.45Ca in wt.%), in particular, have been shown to have suitable degradation rates and good osseointegration, knowledge gaps remain in our understanding of the impact of their degradation properties on the bone's ultrastructure. Bone is a hierarchically structured material, where not only the microstructure but also the ultrastructure are important as properties like the local mechanical response are determined by it. This study presents the first comparative analysis of bone ultrastructure parameters with high spatial resolution around ZX00 and Ti implants after 6, 12, and 24 weeks of healing. The mineralization was investigated, revealing a significant decrease in the lattice spacing of the (002) Bragg's peak closer to the ZX00 implant in comparison to Ti, while no significant difference in the crystallite size was observed. The hydroxyapatite platelet thickness and osteon density demonstrated a decrease closer to the ZX00 implant interface. Correlative indentation and strain maps obtained by scanning X-ray diffraction measurements revealed a higher stiffness and faster mechanical adaptation of the bone surrounding Ti implants as compared to the ZX00 ones. Thus, the results suggest the incorporation of Mg2+ ions into the bone ultrastructure, as well as a lower degree of remodeling and stiffness of the bone in the presence of ZX00 implants than Ti.

Multi-modal investigation of the bone micro- and ultrastructure, and elemental distribution in the presence of Mg-xGd screws at mid-term healing stages.

Magnesium (Mg) - based alloys are becoming attractive materials for medical applications as temporary bone implants for support of fracture healing, e.g. as a suture anchor. Due to their mechanical properties and biocompatibility, they may replace titanium or stainless-steel implants, commonly used in orthopedic field. Nevertheless, patient safety has to be assured by finding a long-term balance between metal degradation, osseointegration, bone ultrastructure adaptation and element distribution in organs. In order to determine the implant behavior and its influence on bone and tissues, we investigated two Mg alloys with gadolinium contents of 5 and 10 wt percent in comparison to permanent materials titanium and polyether ether ketone. The implants were present in rat tibia for 10, 20 and 32 weeks before sacrifice of the animal. Synchrotron radiation-based micro computed tomography enables the distinction of features like residual metal, degradation layer and bone structure. Additionally, X-ray diffraction and X-ray fluorescence yield information on parameters describing the bone ultrastructure and elemental composition at the bone-to-implant interface. Finally, with element specific mass spectrometry, the elements and their accumulation in the main organs and tissues are traced. The results show that Mg-xGd implants degrade in vivo under the formation of a stable degradation layer with bone remodeling similar to that of Ti after 10 weeks. No accumulation of Mg and Gd was observed in selected organs, except for the interfacial bone after 8 months of healing. Thus, we confirm that Mg-5Gd and Mg-10Gd are suitable material choices for bone implants.

Multiscale morphological analysis of bone microarchitecture around Mg-10Gd implants.

The utilization of biodegradable magnesium (Mg)-based implants for restoration of bone function following trauma represents a transformative approach in orthopaedic application. One such alloy, magnesium-10 weight percent gadolinium (Mg-10Gd), has been specifically developed to address the rapid degradation of Mg while enhancing its mechanical properties to promote bone healing. Previous studies have demonstrated that Mg-10Gd exhibits favorable osseointegration; however, it exhibits distinct ultrastructural adaptation in comparison to conventional implants like titanium (Ti). A crucial aspect that remains unexplored is the impact of Mg-10Gd degradation on the bone microarchitecture. To address this, we employed hierarchical three-dimensional imaging using synchrotron radiation in conjunction with image-based finite element modelling. By using the methods outlined, the vascular porosity, lacunar porosity and the lacunar-canaliculi network (LCN) morphology of bone around Mg-10Gd in comparison to Ti in a rat model from 4 weeks to 20 weeks post-implantation was investigated. Our investigation revealed that within our observation period, the degradation of Mg-10Gd implants was associated with significantly lower (p < 0.05) lacunar density in the surrounding bone, compared to Ti. Remarkably, the LCN morphology and the fluid flow analysis did not significantly differ for both implant types. In summary, a more pronounced lower lacunae distribution rather than their morphological changes was detected in the surrounding bone upon the degradation of Mg-10Gd implants. This implies potential disparities in bone remodelling rates when compared to Ti implants. Our findings shed light on the intricate relationship between Mg-10Gd degradation and bone microarchitecture, contributing to a deeper understanding of the implications for successful osseointegration.

On the material dependency of peri-implant morphology and stability in healing bone.

The microstructural architecture of remodeled bone in the peri-implant region of screw implants plays a vital role in the distribution of strain energy and implant stability. We present a study in which screw implants made from titanium, polyetheretherketone and biodegradable magnesium-gadolinium alloys were implanted into rat tibia and subjected to a push-out test four, eight and twelve weeks after implantation. Screws were 4 mm in length and with an M2 thread. The loading experiment was accompanied by simultaneous three-dimensional imaging using synchrotron-radiation microcomputed tomography at 5 µm resolution. Bone deformation and strains were tracked by applying optical flow-based digital volume correlation to the recorded image sequences. Implant stabilities measured for screws of biodegradable alloys were comparable to pins whereas non-degradable biomaterials experienced additional mechanical stabilization. Peri-implant bone morphology and strain transfer from the loaded implant site depended heavily on the biomaterial utilized. Titanium implants stimulated rapid callus formation displaying a consistent monomodal strain profile whereas the bone volume fraction in the vicinity of magnesium-gadolinium alloys exhibited a minimum close to the interface of the implant and less ordered strain transfer. Correlations in our data suggest that implant stability benefits from disparate bone morphological properties depending on the biomaterial utilized. This leaves the choice of biomaterial as situational depending on local tissue properties.

Light-Harvesting Complex II Adopts Different Quaternary Structures in Solution as Observed Using Small-Angle Scattering.

The high-resolution crystal structure of the trimeric major light-harvesting complex of photosystem II (LHCII) is often perceived as the basis for understanding its light-harvesting and photoprotective functions. However, the LHCII solution structure and its oligomerization or aggregation state may generally differ from the crystal structure and, moreover, also depend on its functional state. In this regard, small-angle scattering experiments provide the missing link by offering structural information in aqueous solution at physiological temperatures. Herein, we use small-angle scattering to investigate the solution structures of two different preparations of solubilized LHCII employing the nonionic detergents n-octyl-ß-d-glucoside (OG) and n-dodecyl-ß-D-maltoside (ß-DM). The data reveal that the LHCII-OG complex is equivalent to the trimeric crystal structure. Remarkably, however, we observe─for the first time─a stable oligomer composed of three LHCII trimers in the case of the LHCII-ß-DM preparation, implying additional pigment-pigment interactions. The latter complex is assumed to mimic trimer-trimer interactions which play an important role in the context of photoprotective nonphotochemical quenching.

High-resolution ex vivo analysis of the degradation and osseointegration of Mg-xGd implant screws in 3D.

Biodegradable magnesium (Mg) alloys can revolutionize osteosynthesis, because they have mechanical properties similar to those of the bone, and degrade over time, avoiding the need of removal surgery. However, they are not yet routinely applied because their degradation behavior is not fully understood. In this study we have investigated and quantified the degradation and osseointegration behavior of two biodegradable Mg alloys based on gadolinium (Gd) at high resolution. Mg-5Gd and Mg-10Gd screws were inserted in rat tibia for 4, 8 and 12 weeks. Afterward, the degradation rate and degradation homogeneity, as well as bone-to-implant interface, were studied with synchrotron radiation micro computed tomography and histology. Titanium (Ti) and polyether ether ketone (PEEK) were used as controls material to evaluate osseointegration. Our results showed that Mg-5Gd degraded faster and less homogeneously than Mg-10Gd. Both alloys gradually form a stable degradation layer at the interface and were surrounded by new bone tissue. The results were correlated to in vitro data obtained from the same material and shape. The average bone-to-implant contact of the Mg-xGd implants was comparable to that of Ti and higher than for PEEK. The results suggest that both Mg-xGd alloys are suitable as materials for bone implants.

Intercalation in layered metal-organic frameworks: reversible inclusion of an extended π-system.

We report the synthesis of layered [Zn(2)(bdc)(2)(H(2)O)(2)] and [Cu(2)(bdc)(2)(H(2)O)(2)] (bdc = benzdicarboxylate) metal-organic frameworks (MOF) carried out using the liquid-phase epitaxy approach employing self-assembled monolayer (SAM) modified Au-substrates. We obtain Cu and Zn MOF-2 structures, which have not yet been obtained using conventional, solvothermal synthesis methods. The 2D Cu(2+) dimer paddle wheel planes characteristic for the MOF are found to be strictly planar, with the planes oriented perpendicular to the substrate. Intercalation of an organic dye, DXP, leads to a reversible tilting of the planes, demonstrating the huge potential of these surface-anchored MOFs for the intercalation of large, planar molecules.

Nonlinear pressure dependence of the interaction potential of dense protein solutions.

The influence of pressure on the structure and protein-protein interaction potential of dense protein solutions was studied and analyzed using small-angle x-ray scattering in combination with a liquid state theoretical approach. The structural as well as the interaction parameters of dense lysozyme solutions are affected by pressure in a nonlinear way. The structural properties of water lead to a modification of the protein-protein interactions below 4 kbar, which might have significant consequences for the stability of proteins in extreme natural environments.

Dissolution of iron oxide nanoparticles inside polymer nanocapsules.

The structure of poly(organosiloxane) nanocapsules partially filled with iron oxide cores of different sizes was revealed by small angle X-ray scattering and X-ray diffraction. The nanocapsules are synthesized by the formation of a poly(organosiloxane) shell around iron oxide nanoparticles and the simultaneous partial dissolution of these cores. Due to the high scattering contrast of the iron oxide cores compared to the polymer shell, the particle size distribution of the cores inside the capsules can be measured by small angle X-ray scattering. Additional information can be revealed by X-ray diffraction, which gives insights into the formation of the polymer network and the structure of the iron oxide cores. The study shows how the crystallinity and size of the nanoparticles as well as the shape and width of the size distribution can be altered by the synthesis parameters.

High-pressure SAXS study of folded and unfolded ensembles of proteins.

A structural interpretation of the thermodynamic stability of proteins requires an understanding of the structural properties of the unfolded state. High-pressure small-angle x-ray scattering was used to measure the effects of temperature, pressure, denaturants, and stabilizing osmolytes on the radii of gyration of folded and unfolded state ensembles of staphylococcal nuclease. A set of variants with the internal Val-66 replaced with Ala, Tyr, or Arg was used to examine how changes in the volume and polarity of an internal microcavity affect the dimensions of the native state and the pressure sensitivity of the ensemble. The unfolded state ensembles achieved for these proteins with high pressure were more compact than those achieved at high temperature, and were all very sensitive to the presence of urea and glycerol. Substitutions at the hydrophobic core detectably altered the conformation of the protein, even in the folded state. The introduction of a charged residue, such as Arg, inside the hydrophobic interior of a protein could dramatically alter the structural properties, even those of the unfolded state. The data suggest that a charge at an internal position can interfere with the formation of transient hydrophobic clusters in the unfolded state, and ensure that the pressure-unfolded form of a protein occupies the maximum volume possible. Only at high temperatures does the radius of gyration of the unfolded state ensemble approach the value for a statistical random coil.