RESUMEN
A Model mesogen and its symmetrical Dimer made up of phenyl benzoate core unit are investigated by 13C NMR spectroscopy. The existence of layer order in smectic A and smectic C phases of Dimer mesogen is established by powder X-ray diffraction. The chemical shift anisotropy (CSA) tensors of Model mesogen are determined by 2D separation of undistorted powder patterns by effortless recoupling (SUPER) experiment and are utilized for calculating the order parameters employing the alignment-induced chemical shifts (AIS). Additionally, 2D separated local field (SLF) NMR is availed for extracting 13C-1H dipolar couplings for both mesogens and used for computing the order parameters. A good agreement in the order parameters calculated from 13C-1H dipolar couplings and AIS is observed. Accordingly, the main order parameter (Szz) for the phenyl rings of the Model mesogen is found to be in the range 0.54 - 0.82, and for the Dimer mesogen, the values span 0.64 - 0.82 across mesophases. Since the phenyl benzoate core unit is frequently employed structural moiety for constructing the main chain as well as side chain liquid crystalline polymers and liquid crystalline elastomers, the CSA tensors reported here will be of immense utility for the structural characterization of these materials.
RESUMEN
Collagen-based materials have a wide range of applications in wound care, tendon repair, cartilage repair, etc. Improving certain properties such as hydrophobicity can diversify the application areas. In this work, we investigated the noncovalent interactions of suitably functionalized silica nanoparticles with collagen for the possibility of improving hydrophobicity. Functionalization on silica nanoparticles was achieved via Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) or "click" reaction using surface grafting methods. Furthermore, we synthesized two different silica nanoparticles (SiNPs) functionalized with the fluorine-containing substrate or only with an aryl moiety (silica-g-4EMB and silica-g-ETFMB) for comparison. The functionalized SiNPs immobilized along with the model system trans-4-hydroxy-l-proline (HPA) (usually present in abundant quantities in collagen) have been probed using nuclear magnetic resonance (NMR) spin relaxation to appreciate the influence of SiNPs on HPA. Furthermore, we effectively utilized a saturated transfer difference (STD) NMR experiment to measure the interaction parameters between judiciously functionalized silica nanoparticles and substrates of interest. In essence, such a detailed study on noncovalent interactions employing an arsenal of experimental approaches facilitated the immobilization of suitably functionalized silica nanoparticles to collagen and leather (where collagen is a major constituent), leading to improvements in hydrophobicity.
RESUMEN
A set of mesogens considered as model molecules to the technologically important twist-bend (NTB) nematogens are investigated. They consist of a three-ring core connected to a phenyl ring via a flexible spacer and displayed enantiotropic nematic and smectic C mesophases. In such systems, odd or even number of atoms present in the spacer could influence the orientation of the terminal phenyl ring and thus have a bearing on designing the NTB phase, considered as intermediate between the nematic and the cholesteric phases. One-dimensional (1D) and two-dimensional (2D) 13C NMR spectra have been recorded in the liquid crystalline phases and the alignment-induced chemical shifts (AIS) and the 13C-1H dipolar couplings obtained. The order parameters of the phenyl rings reveal features relatable to the odd/even number of atoms of the flexible spacer and the type of linkage. The AIS plots of the phenyl rings of the even spacer-based mesogen showed the usual behavior for all of the phenyl rings with a decrease in AIS with increasing temperature. However, for the odd-spacer mesogens, unusual behaviors are noted for the terminal phenyl ring. Thus, two of the mesogens showed an increase of AIS in the smectic C phase that continued till the middle of the nematic phase temperature range, followed by a decrease. The other two odd-spacer mesogens also showed different behaviors. These observations indicate that the terminal phenyl ring is oriented at an angle with respect to the long molecular axis for the odd-spacer mesogens that changes as a function of temperature. The angles have been found to depend on the nature of the atom/group connecting the spacer to the terminal ring and the spacer length. Thus, the present study provides critical information on the design of the odd dimers that are recognized to generate fascinating NTB mesophases.
RESUMEN
In this study, we present a facile method for introducing hydrophilic ureido groups (NH2-CO-NH-) into chitosan using a microwave-assisted reaction with molten urea, with the aim of enhancing chitosan's interaction with blood components for improved hemostasis. The formation of the ureido groups through nucleophilic addition reaction between the amine groups in chitosan and in situ generated isocyanic acid was confirmed by FTIR, CP/TOSS 13C NMR, and CP/MAS 15N NMR spectroscopic techniques. However, in stark contrast to the glucans, the said modification introduced extensive crosslinking in chitosan. Spectroscopic studies identified these crosslinks as carbamate bridges (-NH-COO-), which were likely formed by the reaction between the ureido groups and hydroxyl groups of adjacent chains through an isocyanate intermediate. These carbamate bridges improved ureido chitosan's environmental stability, making it particularly resistant to changes in pH and temperature. In comparison to chitosan, the crosslinked ureido chitosan synthesized here exhibited good biocompatibility and cell adhesion, rapidly arrested the bleeding in a punctured artery with minimal hemolysis, and induced early activation and aggregation of platelets. These properties render it an invaluable material for applications in hemostasis, particularly in scenarios that necessitate stability against pH variations and degradation.
Asunto(s)
Quitosano , Hemostáticos , Quitosano/química , Microondas , Hemostasis , CarbamatosRESUMEN
The successful N-carboxymethylation and concomitant crosslinking of solid chitosan upon heating its mixture with solid monochloroacetic acid, without the use of solvents or catalysts, is reported. The N-carboxymethylation was confirmed through the analysis of the partially depolymerized product using NMR spectroscopy, as well as a control reaction with lysine. This transformation was facilitated by the nucleophilic nature of the free amine group in the repeating unit of chitosan, which possesses lone pair of electrons capable of attacking the carbon center bearing the leaving group and displacing the leaving group in a concerted manner. The crosslinking, on the other hand, was established by the observed insolubility in aqueous acidic solutions, even when subjected to prolonged heating at 60 °C. This crosslinking occurs due to the electrostatic interactions between the carboxylate groups and the adjacent ammonium groups, as supported by evidence from FTIR spectroscopy and a control reaction involving ethyl chloroacetate. The resulting crosslinked carboxymethyl chitosan demonstrated its usefulness in the adsorption of methyl orange and fluorescein, as well as functioning as an organic catalyst for aza-Michael addition, Hantzsch reaction, and substituted perimidine synthesis.
Asunto(s)
Quitosano , Quitosano/química , Solventes , Electricidad Estática , Espectroscopía de Resonancia Magnética , Agua/química , AdsorciónRESUMEN
For the design of an efficient drug delivery system utilizing an ionic liquid (IL) as a carrier, it is prudent to gain molecular/atomistic level insights of a drug with IL in terms of binding and dynamics. In this scenario, the influence of anionic counterpart of imidazolium-based ILs, namely, 1-butyl-3-methyl-imidazolium octyl sulfate [BMIM][OSU] and 1-butyl-3-methyl-imidazolium chloride [BMIM][Cl] in their submicellar region ([IL] = 20 mM) on the model water-soluble anticancer drug doxorubicin hydrochloride (DOX) was probed by employing an arsenal of nuclear magnetic resonance (NMR) approaches. The salient feature of the present study includes the significant interaction of DOX with [BMIM][OSU], whereas the lack of such an interaction with [BMIM][Cl] is gauged by 1H NMR translation self-diffusometry and is further corroborated by 13C chemical shift perturbation. The two-step model was utilized to estimate the bound fraction (pb) and equivalent partition coefficient (K) of DOX with [BMIM][OSU]. A combination of selective and nonselective spin-lattice relaxation rates (R1SEL and R1NS, respectively) enables to gauze the significant interaction of DOX with [BMIM][OSU] over [BMIM][Cl]. Furthermore, 1D transient and truncated driven nuclear Overhauser enhancement (NOE) data analyses in the initial rate limit permits the evaluation of the cross-relaxation efficacy of DOX with the investigated ILs. An Arrhenius-type temperature dependence of the drug's self-diffusion was observed for DOX, DOX-[BMIM][OSU], and DOX-[BMIM][Cl] aqueous mixtures and the corresponding activation energies were evaluated.
Asunto(s)
Antineoplásicos , Líquidos Iónicos , Líquidos Iónicos/química , Doxorrubicina , Espectroscopía de Resonancia Magnética , Imagen por Resonancia Magnética , AguaRESUMEN
New ¹³C-detected NMR experiments have been devised for molecules in solution and solid state, which provide chemical shift correlations of methyl groups with high resolution, selectivity and sensitivity. The experiments achieve selective methyl detection by exploiting the one bond J-coupling between the ¹³C-methyl nucleus and its directly attached ¹³C spin in a molecule. In proteins such correlations edit the ¹³C-resonances of different methyl containing residues into distinct spectral regions yielding a high resolution spectrum. This has a range of applications as exemplified for different systems such as large proteins, intrinsically disordered polypeptides and proteins with a paramagnetic centre.
Asunto(s)
Resonancia Magnética Nuclear Biomolecular/métodos , Péptidos/química , Proteínas/química , Isótopos de Carbono/química , SolucionesRESUMEN
The vast application potentials of bacterial cellulose (BC)-based materials for developing leather-like materials, wound-healing materials and electronic materials have been realized very recently. Surface functionalization of these materials can help in improvement of certain properties such as water repellency, mechanical strength, and so forth. In this paper, we reported functionalization of BC surfaces using "click" polymerization for the first time. By this methodology, dense aromatic groups have been incorporated for the improvement of hydrophobicity. For comparative studies, various fluorine-based compounds have been introduced using conventional click reactions. The surface-modified BC materials have been confirmed by various spectroscopic methods. Particularly, the chemical structures of the materials were studied by solid-state 13C NMR spectroscopy and attenuated total reflection-infrared spectroscopy. X-ray photoelectron spectroscopy was used to study the elemental composition of the materials. Moreover, the crystallite changes of modified BC surfaces were investigated by X-ray diffraction. Further, the changes in the morphology of the material after functionalization were evaluated by scanning electron microscopy and atomic force microscopy. Finally, water contact angle measurement revealed manyfold increase in hydrophobicity after click polymerization. A video is also provided in the Supporting Information to show the application potential of this material for developing leather-like materials.