Hydrogen atoms play a crucial role in the aggregation of organic (bio)molecules through diverse number of noncovalent interactions that they mediate, such as electrostatic in proton transfer systems, hydrogen bonding, and CH–π interactions, to mention only the most prominent. To identify and adequately describe such low-energy interactions, increasingly sensitive methods have been developed over time, among which quantum chemical computations have witnessed impressive advances in recent years. For reaching the present state-of-the-art, computations had to rely on a pool of relevant experimental data, needed at least for validation, if not also for other purposes. In the case of molecular crystals, the best illustration for the synergy between computations and experiment is given by the so-called NMR crystallography approach. Originally designed to increase the confidence level in crystal structure determination of organic compounds from powders, NMR crystallography is able now to offer also a wealth of information regarding the noncovalent interactions that drive molecules to pack in a given crystalline pattern or another. This is particularly true for the noncovalent interactions which depend on the exact location of labile hydrogen atoms in the system: in such cases, NMR crystallography represents a valuable characterization tool, in some cases complementing even the standard single-crystal X-ray diffraction technique. A concise introduction in the field is made in this mini-review, which is aimed at providing a comprehensive picture with respect to the current accuracy level reached by NMR crystallography in the characterization of hydrogen-mediated noncovalent interactions in organic solids. Different types of practical applications are illustrated with the example of molecular crystals studied by our research group, but references to other representative developments reported in the literature are also made. By summarizing the major concepts and methodological progresses, the present work is also intended to be a guide to the practical potential of this relatively recent analytical tool for the scientists working in areas where crystal engineering represents the main approach for rational design of novel materials.
1 May 2017 in Journal of Pharmaceutical and Biomedical Analysis
Skin, the largest organ of the human body, serves as a critical physico-chemical barrier against environmental insults and plays essential roles in hydration, thermoregulation, immune defense, and metabolic functions. Wound healing is a complex, multistage biological process involving hemostasis, inflammation, proliferation, and remodeling. Hydrogels have emerged as a promising class of wound dressings due to their high moisture retention, biocompatibility, and ability to mimic the extracellular matrix, thereby supporting accelerated healing and controlled drug delivery. This review provides a comprehensive overview of current hydrogel types—classified by origin, crosslinking mechanisms, and responsiveness to stimuli—and evaluates their use in experimental research on in vitro, ex vivo, and in vivo wound healing models. Furthermore, clinical applications of hydrogels in wound therapy are discussed. Advances in semisynthetic and stimuli-responsive hydrogels, along with improved testing models, offer enhanced therapeutic potential and underscore the need for continued innovation to optimize wound care outcomes and alleviate healthcare burdens.
1 May 2016 in Journal of Pharmaceutical and Biomedical Analysis
Coating the surfaces of implantable materials with various active principles to ensure inhibition of microbial adhesion, is a solution to reduce infections associated with dental implant. The aim of the study was to optimize the polydopamine films coating on the Ti-6Al-6V alloy surface in order to obtain a maximum of antimicrobial/antibiofilm efficacy and reduced cytotoxicity. Surface characterization was performed by evaluating the morphology (SEM, AFM) and structures (Solid-state 13C NMR and EPR). Antimicrobial activity was assessed by logarithmic reduction of CFU/mL, and the antibiofilm activity by reducing the adhesion of Escherichia coli, Staphylococcusaureus, and Candida albicans strains. The release of NO was observed especially for C. albicans strain, which confirms the results obtained for microbial adhesion. Among the PDA coatings, for 0.45:0.88 (KMnO4:dopamine) molar ratio the optimal compromise was obtained in terms of antimicrobial activity and cytotoxicity, while the 0.1:1.5 ratio (KMnO4:dopamine) led to higher NO release and implicitly the reduction of the adhesion capacities only for C. albicans, being slightly cytotoxic but with moderate release of LDH. The proposed materials can be used to reduce the adhesion of yeast to the implantable material and thus inhibit the formation of microbial biofilms.
In this work, a systematic 15N/13C solid-state NMR investigation is performed on three dopamine (DA) conjugates of hyaluronic acid, considered in both its native (HA) and NaIO4-oxidized (HAOx) forms. Two of them, here named HAEDC-DA and HAOx-DA, have been previously introduced as covalent conjugates involving DA amine nitrogen: the former by EDC-mediated amide bond formation, and the latter by reaction of the Schiff base with the aldehyde moieties presumed to exist in HAOx. The third conjugate, HA-DA, is reported here for the first time; it is obtained by simply mixing hyaluronan with DA∙HCl at pH 5. The 15N ss-NMR spectra were found to be consistent in all the systems, and the DA molecules were found to be in their charged -NH3+ form, which contradicts the HAEDC-DA/HAOx-DA covalent bonding schemes proposed in the literature. The 13C ss-NMR results add useful new insights into the structure and interaction patterns of the conjugates. All of our findings are relevant for future practical applications, for instance in developing novel HA-based hydrogels. In addition, the present study demonstrates the importance of using the most appropriate analytical tools when investigating composite systems due to the complexity of hyaluronic acid conjugates. Solid-state NMR proved essential to answering the question in the title: actually, there is nothing wrong with hyaluronic acid chemistry; the claimed covalent bonds between DA and the HA(HAOx) chain do not exist in these systems, because the conditions for their formation do not hold in practice.