Temperature Dependence of the Lattice Constants and Thermal Expansion Coefficients of UMn2Si2 and UMn2Ge2 Compounds

Lattice constants of polycrystalline UMn2Si2 and UMn2Ge2 samples were measured in the temperature range 80-300 K using the X-ray diffraction method. The anomalous behaviour of the lattice constant and the expansion coefficient, a, of UMn2Ge2 was observed at 150 K. The magnetostriction contribution of uranium sublattice is responsible for these anomalies

Covalent and non-covalent in-flow biofunctionalization for capture assays on silicon chips : white light reflectance spectroscopy immunosensor combined with TOF-SIMS resolves immobilization stability and binding stoichiometry

Immunosensors that combine planar transducers with microfluidics to achieve in-flow biofunctionalization and assay were analyzed here regarding surface binding capacity, immobilization stability, binding stoichiometry, and amount and orientation of surface-bound IgG antibodies. Two IgG immobilization schemes, by physical adsorption [3-aminopropyltriethoxysilane (APTES)] and glutaraldehyde covalent coupling (APTES/GA), followed by blocking with bovine serum albumin (BSA) and streptavidin (STR) capture, are monitored with white light reflectance spectroscopy (WLRS) sensors as thickness dΓ of the adlayer formed on top of aminosilanized silicon chips. Multi-protein surface composition (IgG, BSA, and STR) is determined by time of flight secondary ion mass spectrometry (TOF-SIMS) combined with principal component analysis (applying barycentric coordinates to the score plot). In-flow immobilization shows at least 1.7 times higher surface binding capacity than static adsorption. In contrast to physical immobilization, which is unstable during blocking with BSA, chemisorbed antibodies desorb (reducing d$_{\Gamma}$) only when the bilayer is formed. Also, TOF-SIMS data show that IgG molecules are partially exchanged with BSA on APTES but not on APTES/GA modified chips. This is confirmed by the WLRS data that show different binding stoichiometry between the two immobilization schemes for the direct binding IgG/anti-IgG assay. The identical binding stoichiometry for STR capture results from partial replacement with BSA of vertically aligned antibodies on APTES, with fraction of exposed Fab domains higher than on APTES/GA

Thermoresponsive smart copolymer coatings based on P(NIPAM co-HEMA) and P(OEGMA-co-HEMA) brushes for regenerative medicine

The fabrication of multifunctional, thermoresponsive platforms for regenerative medicine based on polymers that can be easily functionalized is one of the most important challenges in modern biomaterials science. In this study, we utilized atom transfer radical polymerization (ATRP) to produce two series of novel smart copolymer brush coatings. These coatings were based on copolymerizing 2-hydroxyethyl methacrylate (HEMA) with either oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or N-isopropylacrylamide (NIPAM). The chemical compositions of the resulting brush coatings, namely, poly(oligo(ethylene glycol) methyl ether methacrylate-co-2-hydroxyethyl methacrylate) (P(OEGMA-co-HEMA)) and poly(N-isopropylacrylamide-co-2- hydroxyethyl methacrylate) (P(NIPAM-co-HEMA)), were predicted using reactive ratios of the monomers. These predictions were then verified using time-of-flight-secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The thermoresponsiveness of the coatings was examined through water contact angle (CA) measurements at different temperatures, revealing a transition driven by lower critical solution temperature (LCST) or upper critical solution temperature (UCST) or a vanishing transition. The type of transition observed depended on the chemical composition of the coatings. Furthermore, it was demonstrated that the transition temperature of the coatings could be easily adjusted by modifying their composition. The topography of the coatings was characterized using atomic force microscopy (AFM). To assess the biocompatibility of the coatings, dermal fibroblast cultures were employed, and the results indicated that none of the coatings exhibited cytotoxicity. However, the shape and arrangement of the cells were significantly influenced by the chemical structure of the coating. Additionally, the viability of the cells was correlated with the wettability and roughness of the coatings, which determined the initial adhesion of the cells. Lastly, the temperature-induced changes in the properties of the fabricated copolymer coatings effectively controlled cell morphology, adhesion, and spontaneous detachment in a noninvasive, enzyme-free manner that was confirmed using optical microscopy

Implementation of NSOM to biological samples

Near-field scanning optical microscopy is a technique providing images of structures with spatial resolution better than $\lambda/2$, which is undetectable in far-field where the Abbe law of limiting resolution is critical. In parallel to the optical imaging, topography maps are also acquired. Near-field scanning optical microscopy measurements can be performed both in air and liquid environments. The later makes the technique very useful for biomaterials analysis offering information that could not be obtained with other methods. Our work presents the results of recent studies on application of near-field scanning optical microscopy to imaging of cells in air as well as in physiological buffers. Differences in cell's topography and morphology have been noticed between two cell lines from human bladder non-malignant (HCV29) and malignant (T24) cancers. Presented results are part of the research that characterizes physiological changes of cells depending on stage of cancer

Temperature- and pH-responsive schizophrenic copolymer brush coatings with enhanced temperature response in pure water

Novel brush coatings were fabricated with glass surface-grafted chains copolymerized using surface-initiated atom transfer radical polymerization (SI-ATRP) from 2-(2-methoxyethoxy)ethyl methacrylate (OEGMA188) and acrylamide (AAm), taken in different proportions. P(OEGMA188-co-AAm) brushes with AAm mole fraction >44% (determined with XPS and TOF-SIMS spectroscopy) and nearly constant with the depth copolymer composition (TOF-SIMS profiling) exhibit unusual temperature-induced transformations: The contact angle of water droplets on P(OEGMA188-co-AAm) coatings increases by ~45° with temperature, compared to 17−18° for POEGMA188 and PAAm. The thickness of coatings immersed in water and the morphology of coatings imaged in air show a temperature response for POEGMA188 (using reflectance spectroscopy and AFM, respectively), but this response is weak for P(OEGMA188-co-AAm) and absent for PAAm. This suggests mechanisms more complex than a simple transition between hydrated loose coils and hydrophobic collapsed chains. For POEGMA188, the hydrogen bonds between the ether oxygens of poly(ethylene glycol) and water hydrogens are formed below the transition temperature T$_{c}$ and disrupted above T$_{c}$ when polymer−polymer interactions are favored. Different hydrogen bond structures of PAAm include free amide groups, cis-trans-multimers, and trans-multimers of amide groups. Here, hydrogen bonds between free amide groups and water dominate at T T$_{c}$, such as cis-trans-multimers and trans-multimers of amide groups, can still be hydrated. The enhanced temperature-dependent response of wettability for P(OEGMA188-co-AAm) with a high mole fraction of AAm suggests the formation at T$_{c}$ of more hydrophobic structures, realized by hydrogen bonding between the ether oxygens of OEGMA188 and the amide fragments of AAm, where water molecules are caged. Furthermore, P(OEGMA188-co-AAm) coatings immersed in pH buffer solutions exhibit a 'schizophrenic' behavior in wettability, with transitions that mimic LCST and UCST for pH = 3, LCST for pH = 5 and 7, and any transition blocked for pH = 9

Fabrication and impact of fouling-reducing temperature-responsive POEGMA coatings with embedded CaCO3 nanoparticles on different cell lines

In the present work, we have successfully prepared and characterized novel nanocomposite material exhibiting temperature-dependent surface wettability changes, based on grafted brush coatings of non-fouling poly(di(ethylene glycol)methyl ether methacrylate) (POEGMA) with the embedded CaCO3 nanoparticles. Grafted polymer brushes attached to the glass surface were prepared in a three-step process using atom transfer radical polymerization (ATRP). Subsequently, uniform CaCO3 nanoparticles (NPs) embedded in POEGMA-grafted brush coatings were synthesized using biomineralized precipitation from solutions of CaCl2 and Na2CO3. An impact of the low concentration of the embedded CaCO3 NPs on cell adhesion and growth depends strongly on the type of studied cell line: keratinocytes (HaCaT), melanoma (WM35) and osteoblastic (MC3T3-e1). Based on the temperature-responsive properties of grafted brush coatings and CaCO3 NPs acting as biologically active substrate, we hope that our research will lead to a new platform for tissue engineering with modified growth of the cells due to the release of biologically active substances from CaCO3 NPs and the ability to detach the cells in a controlled manner using temperature-induced changes of the brush

Structures in multicomponent polymer films : their formation, observation, applications in electronics and biotechnology

Several strategies to form multicomponent films of functional polymers, with micron, submicron and nanometer structures, intended for plastic electronics and biotechnology are presented. These approaches are based on film deposition from polymer solution onto a rotating substrate (spin-casting), a method implemented already on manufacturing lines. Film structures are determined with compositional (nanometer) depth profiling and (submicron) imaging modes of dynamic secondary ion mass spectrometry, near-field scanning optical microscopy (with submicron resolution) and scanning probe microscopy (revealing nanometer features). Self-organization of spin-cast polymer mixtures is discussed in detail, since it offers a one-step process to deposit and align simultaneously domains, rich in different polymers, forming various device elements: (i) Surface segregation drives self-stratification of nanometer lamellae for solar cells and anisotropic conductors. (ii) Cohesion energy density controls morphological transition from lamellar (optimal for encapsulated transistors) to lateral structures (suggested for light emitting diodes with variable color). (iii) Selective adhesion to substrate microtemplates, patterned chemically, orders lateral structures for plastic circuitries. (iv) Submicron imprints of water droplets (breath figures) decorate selectively micron-sized domains, and can be used in devices with hierarchic structure. In addition, selective protein adsorption to regular polymer micropatterns, formed with soft lithography after spin-casting, suggests applications in protein chip technology. An approach to reduce lateral blend film structures to submicron scale is also presented, based on (annealed) films of multicomponent nanoparticles