Adsorption of novel thermosensitive graft-copolymers: Core-shell particles prepared by polyelectrolyte multilayer self-assembly

The adsorption properties of thermosensitive graft-copolymers are investigated with the aim of developing self-assembled multilayers from these copolymers. The copolymers consist of a thermoreversible main chain of poly(N-isopropylacrylamid) and a weak polyelectrolyte, poly(2-vinylpyridine), as grafted side chains. Zeta-potential, single particle light scattering and adsorption isotherms monitor the adsorption of the thermoreversible copolymers to precoated colloidal particles. The results show a smaller surface coverage for a larger density of grafted chains. The surface coverage is discussed in terms of surface charge density in the adsorbed monolayer. Taking into account the monolayer adsorption properties, conditions are developed for the multilayer formation from these copolymers. A low pH provides a sufficient charge density of the grafted chains to achieve a surface charge reversal of the colloids upon adsorption. The charge reversal after each adsorbed layer is monitored by zeta-potential and the increase of the thickness is determined by light scattering. Stable and reproducible multilayers are obtained. The results imply that the conformation of the thermosensitive component in multilayers depends strongly on the grafting density, where the polymer with a higher grafting density adsorbs in a flat conformation while that with a lower grafting density adsorbs with more loops.     

A novel low-cost and easy to develop functionalization platform. Case study: Aptamer-based detection of thrombin by surface plasmon resonance

A novel low-cost platform to assess biomolecular interactions was investigated using surface plasmon resonance and an aptamer-based assay for thrombin detection. Gold SPR surface functionalized with a carboxylated cross-linked BSA film (cBSA) and commercially available carboxymethylated dextran chip (CM5) were used as immobilization platforms for the thrombin binding aptamer. The high end commercial instrument Biacore 3000 and a custom made FIA set-up involving TI Spreeta sensor (TSPR2K23) were used to assess different concentrations of thrombin within the range 0.1-150 nM both in buffer and in a complex matrix (plasma) using the obtained aptasensors. Based on data derived from both CM5 and cBSA platforms, the cBSA aptasensor exhibited good selectivity, stability and regeneration ability, both in buffer and in complex matrices (plasma), comparable with CM5.     

Uniqueness of solutions to inverse Sturm–Liouville problems with potential using three spectra

The uniqueness of solutions to two inverse Sturm–Liouville problems using three spectra is proven, based on the uniqueness of the solution-pair to an overdetermined Goursat–Cauchy boundary value problem. We discuss the uniqueness of the potential for a Dirichlet boundary condition at an arbitrary interior node, and for a Robin boundary condition at an arbitrary interior node, whereas at the exterior nodes we have Dirichlet boundary conditions in both situations. Here we are particularly concerned with potential functions that are L²(0,a).     

Dipeptidyl Peptidase 3 Activity as a Promising Biomarker of Bone Fragility in Postmenopausal Women

The dipeptidyl peptidase 3 (Dpp3) is a ubiquitous zinc-dependent aminopeptidase, participating in the activation or degradation of signaling peptides and in the Keap1–Nrf2 antioxidant pathway. The absence of Dpp3 in the Dpp3 knockout mouse model causes increased osteoclast activity, altered osteogenic function, sustained oxidative stress in the bone tissue, and bone loss. We aimed to assess the association of Dpp3 activity with bone fragility in postmenopausal osteoporosis and the impact of denosumab on enzymatic activity. We conducted a two-phase study including 69 postmenopausal women with severe osteoporosis and 36 postmenopausal women without osteometabolic conditions, as controls (cross-sectional phase). Subjects with severe osteoporosis were assessed at baseline and 14 days after the first denosumab administration (prospective phase). The results showed significant reduction in serum Dpp3 activity (expressed as nmoles of formed product/mg proteins/min) in patients vs. controls (0.791 ± 0.232 vs. 1.195 ± 0.338; p < 0.001), and significant association with bone mass at the femoral neck (r = 0.28, p = 0.02) in patients prior to treatment. We found a negative correlation between C-terminal telopeptide (CTX) or N-terminal pro-peptide of type 1 procollagen (P1NP) levels and Dpp3 activity (respectively, r = −0.29, p = 0.012; and r = −0.2572, p = 0.033). Dpp3 activity did not change after denosumab injection. Our findings support a critical role played by Dpp3 in bone homeostasis as a potential bone protective factor. Additional clinical studies in larger cohorts might explore the implementation of Dpp3 assessment as a biomarker of bone health status.     

Exploring the Research Progress about the Applications of Cyclodextrins and Nanomaterials in Electroanalysis

Cyclodextrins and nanomaterials are widely used in the achievement of powerful platforms in supramolecular chemistry and nanotechnology. The relatively hydrophobic internal cavity of the CDs selectively retains molecules having the proper geometry, while the hydrophilic exterior allows CDs to improve the dispersibility and molecular recognition. The nanomaterials provide higher surface area, good conductivity, and electrocatalytic effect. The use of nanomaterials and CDs in electrochemical sensors’ design allows the development of a large variety of devices, explaining the increasing number of papers in the last years that are discussed in this review.     

Nanotopography Engineering on Homopolymeric Surfaces Using Cold Plasma Generated Charges

Summary : Cold plasma as source for charged particles was used to induce nanotopographies on homopolymeric surfaces (nylon 12, PMMA, PMA, etc.). Hydrogen and helium plasmas were successfully used for surface nanoengineering of polymers using inductively coupled or atmospheric pressure non-equilibrium barrier discharge reactors. AFM analyses reveal the presence of nanotopographies on the treated surfaces. Physical factors control the process below the T_g and chemical factors dominate the process above T_g. Pyrolysis GC/MS analyses have been performed in order to obtain more information about the plasma processes. Cold plasma chemical processes, including charges effects are discussed as tools that open-up new ways for nanoengineering of the polymers' surfaces with specific functionalities and / or topography. Future nanomanufacturing techniques can generate anti-scratch, superhydrophobic or superhydrophilic properties on surface of every day use polymeric products by simple and convenient plasma enhanced processes.     

Mapping the Distribution of Melanin Concentration in Different Fitzpatrick Skin Types Using Hyperspectral Imaging Technique

Measuring skin melanin concentration in order to assess skin phototype according to Fitzpatrick's classification is a constant research goal. In this study, a new approach for assessing skin melanin concentration based on hyperspectral imaging combined with an appropriate analytical model that exploits specific spectral bands to generate maps of melanin content distribution on different Fitzpatrick skin phototypes is presented. Hyperspectral images from the proximal inner side of the forearms of 51 young volunteers covering the first four classes of Fitzpatrick's phototypes were acquired using a hyperspectral imaging system. The images were analyzed using a modified Beer–Lambert law that segregates the contribution of melanin from the other constituents to the skin absorption spectrum. The performance of the model was evaluated using the coefficient of determination (r-squared). The results revealed that the approach proposed in this study generated accurate melanin concentration distribution maps that allowed a correct classification of skin phototype. In conclusion, the proposed approach for assessing skin melanin concentration proved to be very reliable for classifying skin phototypes, and, as it provides maps that are easily read, it has the advantage of a possible extension of its applications to other research concerning skin pigmentation.     

Copper-mediated ATRP of methyl methacrylate in polar solvents using a bifunctional pyridinal diimine ligand

The bifunctional pyridinal diimine ligand, bis(2-pyridinal)ethylenediimine, was employed in copper-mediated ATRP of methylmethacrylate using solvents such as acetonitrile, N,N-dimethyl formamide and dimethylsulfoxide. Solvent polarity was found to play a crucial role in determining the extent of control in the ATRP process. Acetonitrile showed the best control when used at a level of 33 vol.-%.