Structural and conformational changes on chitosan after green heterogeneous synthesis of phenyl derivatives.

Four aromatic acid compounds: benzoic acid (Bz), 4-hydroxyphenylpropionic acid (HPPA), gallic acid (GA) and 4-aminobenzoic acid (PABA) were covalently bonded to chitosan in order to improve water solubility at neutral pH. The synthesis was performed via a radical redox reaction in heterogeneous phase by employing ascorbic acid and hydrogen peroxide (AA/H2O2) as radical initiators in ethanol. The analysis of chemical structure and conformational changes on acetylated chitosan was also the focus of this research. Grafted samples exhibited as high as 0.46 M degree of substitution (MS) and excellent solubility in water at neutral pH. Results showed a correlation between the disruption of C3-C5 (O3…O5) hydrogen bonds with increasing solubility in grafted samples. Spectroscopic techniques such as FT-IR and 1H and 13C NMR showed modifications in both glucosamine and N-Acetyl-glucosamine units by ester and amide linkage at C2, C3 and C6 position, respectively. Finally, loss of crystalline structure of 2-helical conformation of chitosan after grafting was observed by XRD and correlated with 13C CP-MAS-NMR analyses.

Pseudo-resonance structures in chiral alcohols and amines and their possible aggregation states.

We now report that some chiral compounds, like alcohols, which are not sterically hindered atropisomers nor epimer mixtures, exhibit two sets of simultaneous NMR spectra in CDCl3. Some other chiral alcohols also simultaneously exhibit two different NMR spectra in the solid state because two different conformers, A and B had different sizes because their corresponding bond lengths and angles are different. These structures were confirmed in the same solid state by X-ray. We designate these as pseudo-resonance for a compound exhibiting several different corresponding lengths that simultaneously coexist in the solid state or liquid state. Variable-temperature NMR, 2D NMR methods, X-ray, neutron diffraction, IR, photo-luminesce (PL) and other methods were explored to study whether new aggregation states caused these heretofore unknown pseudo-resonance structures. Finally, eleven chiral alcohols or diols were found to co-exist in pseudo-resonance structures by X-ray crystallography in a search of the CDS database.

CP-MAS and Solution NMR Studies of Allosteric Communication in CA-assemblies of HIV-1.

Solution and solid-state NMR spectroscopy are highly complementary techniques for studying structure and dynamics in very high molecular weight systems. Here we have analysed the dynamics of HIV-1 capsid (CA) assemblies in presence of the cofactors IP6 and ATPγS and the host-factor CPSF6 using a combination of solution state and cross polarisation magic angle spinning (CP-MAS) solid-state NMR. In particular, dynamical effects on ns to µs and µs to ms timescales are observed revealing diverse motions in assembled CA. Using CP-MAS NMR, we exploited the sensitivity of the amide/Cα-Cß backbone chemical shifts in DARR and NCA spectra to observe the plasticity of the HIV-1 CA tubular assemblies and also map the binding of cofactors and the dynamics of cofactor-CA complexes. In solution, we measured how the addition of host- and co-factors to CA -hexamers perturbed the chemical shifts and relaxation properties of CA-Ile and -Met methyl groups using transverse-relaxation-optimized NMR spectroscopy to exploit the sensitivity of methyl groups as probes in high-molecular weight proteins. These data show how dynamics of the CA protein assembly over a range of spatial and temporal scales play a critical role in CA function. Moreover, we show that binding of IP6, ATPγS and CPSF6 results in local chemical shift as well as dynamic changes for a significant, contiguous portion of CA, highlighting how allosteric pathways communicate ligand interactions between adjacent CA protomers.

Variations in the chemical structure and Carbon-13 natural abundance in water-stable macro- and microaggregates in Haplic Chernozem under the contrasting land use variants.

Water-stable macro- (WSAma) and free microaggregates (WSAmi) were isolated from the 2-1 mm air-dry macroaggregates from the surface horizons of Haplic Chernozem in contrasting variants of land use: the steppe and the bare fallow. The 13C NMR data and the 13C natural abundance of the Occluded organic matter (OM) (LFoc) and Clay within WSAs in the steppe obviously indicate a lower degree of microbiological processing of OM within WSAmi as compared with WSAma. This is reflected in lower degrees of decomposition (DI) and aromaticity (ARI) of OM and the C/N ratio, as well as lower 13C enrichment. This implies that the "labile" part of OM within WSAmi (LFoc and Clay, which are components of microaggregates within water-stable aggregates (mWSAs)) is more physically protected compared to that within WSAma. However, the heavier total δ13C signature of OM within WSAmi indicates its greater degree of microbiological processing compared to that within WSAma. This seems contrary to the concept of greater physical protection of OM within microaggregates as compared to macroaggregates. It was revealed that the heavier total δ13C signature of OM within WSAmi (greater degree of microbiological processing) is determined by the "oldest" OM located in the inter-aggregate space of WSAs, which is concentrated in the Residue fraction (Res). Due to its quantitative dominance, the Residue fraction is crucial for the total δ13C signature of WSAs. Negative changes in the quality of OM under the long-term bare fallow (52-yr) were reflected in a sharp increase in the integral indices of the chemical structure (DI, ARI), as well as the hydrophobicity index (HI) in all studied OM pools. It was accompanied by their 13C enrichment in the bare fallow compared to the steppe. Free microaggregates (WSAmi) are fragments of disintegrated macroaggregates (WSAma). We found no evidence of their formation within macroaggregates.

Effect of Impregnated Phenolic Resins on the Cellulose Membrane for Polymeric Insulator.

In this study, a cellulose membrane (CM) was chemically treated with phenolic (PF) resin to improve its performance as a polymeric insulator. The CM was prepared from kenaf pulp, and the PF was synthesized from oil palm empty fruit (EFB) fibre. Four different concentrations of synthesized PF resin (5, 10, 15, and 20 wt.%) were impregnated under wet or dry conditions. Thermal analysis of the phenolic cellulose membrane (PCM) showed that the samples had good chemical interaction and compatibility. The PF uptake in the wet phenolic cellulose membrane (PCMW) was higher than in the dry phenolic cellulose membrane (PCMD). During the PF uptake, the CM underwent solvent exchange and absorption in wet and dry membranes, respectively. This difference also affected the crosslinking of PCM samples via the formation of methylene bridges. Due to the PF treatment, the PCM showed lower water absorption than CM. The PF concentrations also affect the surface roughness and electrical properties of PCM samples. These findings prove that PCM can be used as a renewable and green polymer electrical insulator.

Mushroom and cereal ß-D-glucan solid state NMR and FTIR datasets.

In the associated published article Kremmyda et al. (2021), the C1 region of the NMR spectra were examined in detail, as the C1 carbon was common to the crucial linkages in the glucan, and the most clearly separated region in the spectra. We provide the original measurement data here in topspin format, in order that different authors can examine the regions corresponding to the other carbons and in addition repeat our processing of the FID's using different parameters. Mushroom, Cereal, Reference and other samples, such as salts and salt hydrates have been measured. A series of different experiments on individual samples is also given. All of the samples and experiments available in the database are summarised in the Table below. We also provide an FTIR database in the form of an excel workbook with spectra in frequency/absorbence pairs.

Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers.

The macromolecular dynamics of dendronized copolymer membranes (PECHs), obtained by chemical modification of poly(epichlorohydrin) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, was investigated. In response to a thermal treatment during membrane preparation, these copolymers show an ability to change their shape, achieve orientation, and slightly crystallize, which was also observed by CP-MAS NMR, XRD, and DSC. The phenomenon was deeply analyzed by dielectric thermal analysis. The dielectric spectra show the influence of several factors such as the number of dendritic side groups, the orientation, their self-assembling dendrons, and the molecular mobility. The dielectric spectra present a sub-Tg dielectric relaxation, labelled as γ, associated with the mobility of the benzyloxy substituent of the dendritic group. This mobility is not related to the percentage of these lateral chains but is somewhat hindered by the orientation of the dendritic groups. Unlike other less complex polymers, the crystallization was dismantled before the appearance of the glass transition (αTg). Only after that, clearing transition (αClear) can be observed. The PECHs were flexible and offered a high free volume, despite presenting a high degree of modifications. However, the molecular mobility is not independent in each phase and the self-assembling dendrons can be eventually fine-tuned according to the percentage of grafted groups.

Targeted delivery of flufenamic acid by V-amylose.

Aim: Controlled release of flufenamic acid by helical V-amylose to achieve enzyme-responsive, targeted release of the cargo drug. Materials & methods: Solid-state cross-polarization magic angle spinning carbon-13 nuclear magnetic resonance (CP/MAS NMR), Fourier transform IR and x-ray diffraction (XRD) analysis validated the entrapment of flufenamic acid inside the helical structure of V-amylose. Scanning electron microscopy (SEM) investigations established the morphology of conjugates in simulated gastric environment (pH 1.2) and simulated intestine media (pH 7.2) containing hydrolyzing enzyme. Results & discussion: V-amylose-flufenamic acid complex displayed a sustained release of flufenamic acid for 12 h with a marked stability in simulated gastric pH, while showing a controlled release of drug in simulated intestine media. Conclusion: The V-amylose-flufenamic acid system achieves intestine-targeted delivery of flufenamic acid. The controlled release of flufenamic acid may ensure minimal ulcerogenicity and application as enteric coatings.

The detection, purity and structural properties of partially soluble mushroom and cereal ß-D-glucans: A solid-state NMR study.

ß-D-glucans are proposed to have many health benefits. It is therefore important to have methods which can distinguish these from other carbohydrates present in natural products, as well as giving glucan content and structural information. Correlations between features in the CP/MAS spectra of ß-D-glucans and enzyme assay determined ß-D-glucan content were generally found to be poor. The ß-D-glucan in dry and hydrated forms of the mushroom Ganoderma lucidum was investigated in detail by spectral peak fitting to the anomeric carbon C1 region in CP/MAS NMR spectra. Hydrated samples gave spectra with enhanced resolution and suggested that a clear distinction between ß-D-glucans and other carbohydrates could be possible in the anomeric carbon C1 region. Chemical shift values for a range of carbohydrate polymers, which can be found alongside ß-D-glucans, as well as the values for various linkages are given. Contamination by other carbohydrates and buffer salts is discussed.

Sequential natural deep eutectic solvent pretreatments of apple pomace: A novel way to promote water extraction of pectin and to tailor its main structural domains.

To establish a "green" biorefinery extraction of apple pomace pectin, a sequential pretreatment with three natural deep eutectic solvents (NADES, choline chloride (CC): glycerol (G); CC: lactic acid (LA); potassium carbonate (K): G) was used prior to hot water extraction. A synergistic effect of CC:G and CC:LA pretreatments was observed and led to the highest recovery of pectin. The sequential NADES/water extraction process also provided a mean to tailor pectin main structure. It was explained as resulting from ion exchange and individual NADES components effects. The 13C solid state NMR T1ρH and THH parameters indicated a reorganization of cellulose in the residues following extraction of pectin, notably after alkaline K:G pretreatment/water extraction. Hence, sequential NADES pretreatments/water extraction represents a "green" alternative to mild mineral acid to extract pectin and to tailor its main structures, while the residual pomace can be further sources of valuable compounds and polymers.

Dextran hydrogels via disulfide-containing Schiff base formation: Synthesis, stimuli-sensitive degradation and release behaviors.

Dextran hydrogels (Dex-SS) containing both disulfide and Schiff base bonds were developed via facile method based on the dextran oxidation and subsequent formation of Schiff base linkages between polyaldehyde dextran and cystamine, denoted as the disulfide-containing Schiff base reactions. Results of rheology, swelling and 13C CP/MAS NMR study indicated that cross-linking degree of Dex-SS hydrogels depended strongly on the molar ratio of -CHO/-NH2. Acidic and reductive (GSH) environment sensitive degradation behaviors of Dex-SS hydrogels were then evidenced by SEM, rheology study and Ellman's assay. Moreover, doxorubicin (DOX) was loaded into the hydrogel matrix and pH/GSH-responsive release behaviors were demonstrated. Cytocompatibility of Dex-SS hydrogel and effective cell uptake of released DOX was finally proved by transwell assay with HepG2 cells. Take advantages of the abundance of vicinal hydroxyl on a variety of polysaccharides, the disulfide-containing Schiff base reactions is considered as versatile method to develop stimuli-sensitive hydrogels for local drug delivery.

Structural changes in cell wall of Japanese radish accompanied by release of rhamnogalacturonan during pressure cooker heating.

Changes in the cell wall of Japanese radish due to heating at 100 °C or 117 °C for 3 h were examined. Signals in 13C cross polarization magic angle spinning solid-state NMR (which detects rigid components) showed no differences between heating temperatures. 13C pulse saturation transfer magic angle spinning NMR (which detects flexible components) showed clear temperature-dependent changes in the rhamnose side chains of rhamnogalacturonan. Alcohol-insoluble solids isolated from raw samples were heated in water at 100 °C or 117 °C for 3 h. The concentrations of dissolved sugars and metal ions measured after heating in water at 117 °C were greater than in samples heated at 100 °C, indicating that loosening of cell wall structures increased with temperature, likely via degradation and elution of rhamnogalacturonan followed by ß-elimination of homogalacturonan, and fewer interactions between cell wall components, including divalent metal ions. Vegetable shape was retained despite fewer interactions.

Features of the chemical structure of different organic matter pools in Haplic Chernozem of the Streletskaya steppe: 13C MAS NMR study.

The aim of the current research was to study structural features of four organic matter (OM) pools isolated by the modified method of granulo-densimetric fractionation from two Сhernozems. We purposed to relate these features to the OM allocation and the transformation processes. The pools included: 1) free light fraction located in an inter-aggregate space, 2) light fraction occluded inside the microaggregates, 3) OM bound with clay particles, and 4) OM bound with a residual heavy fraction left after light fractions and clay separation. Soils of contrasting land uses: steppe and long-term permanent bare fallow were selected to assess changes that occur in soil OM during the degradation. We used 13C CP/MAS NMR spectroscopy controlling the quantitativeness of spectra with the aid of 13C DP/MAS NMR. The obtained spectra of the studied fractions clearly differed in the proportion of main functional groups. The occluded OM is more aromatic compared to the free OM. The structural changes observed at transition from the free light fraction to the occluded one indicate an active decomposition of lignin and carbohydrates in the latter fraction. This provides in the occluded OM appropriate conditions for the formation of "young HA": high local concentration of substrates and spatial proximity of enzymes. At C-deficiency (bare fallow) the chemical structure of the occluded OM is very close to that of humic acids. The chemical structure of the clay bound OM reflects high content of products of microbial origin. OM of the residual heavy fraction differs from that of the clay: the proportions of main functional groups in it are more close to that of the free light fraction, but with higher carboxyl content. Heavy fractions also differ under acid treatment: the residue losses less carbon. The above-mentioned differences show that the division of heavy fractions into two components is reasonable. Various acid hydrolyzability indicates a predominance of strong chemical bonds in the occluded OM and the significant contribution of weak bonds in the clay OM, i.e., the occluded OM is highly condensed, in contrast, components of the clay OM are largely interconnected by hydrogen-, coordinate, hydrophobic and other relatively weak bonds. Soil degradation under extreme land use leads not only to OM scarcity, but also to its greater hydrolyzability, strong enrichment with aromatic fragments and depletion of carbohydrate and aliphatic fragments in all studied fractions. Degradation changes in the occluded OM are most pronounced. Our results demonstrate that the applied fractionation scheme coupled with quantitative 13C CP/MAS NMR spectroscopy is a very promising approach for evaluating processes of soil OM transformation and degradation.

Chain-folded lamellar structure and dynamics of the crystalline fraction of Bombyx mori silk fibroin and of (Ala-Gly-Ser-Gly-Ala-Gly)n model peptides.

Solid-state NMR is a powerful analytical technique to determine the composite structure of Bombyx mori silk fibroin (SF). In our previous paper, we proposed a lamellar structure for Ala-Gly copolypeptides as a model of the crystalline fraction in Silk II. In this paper, the structure and dynamics of the crystalline fraction and of a better mimic of the crystalline fraction, (Ala-Gly-Ser-Gly-Ala-Gly)n (n = 2-5, 8), and 13C selectively labeled [3-13C]Ala-(AGSGAG)5 in Silk II forms, were studied using structural and dynamical analyses of the Ala Cß peaks in 13C cross polarization/ magic angle spinning NMR and 13C solid-state spin-lattice relaxation time (T1) measurements, respectively. Like Ala-Gly copolypeptides, these materials have lamellar structures with two kinds of Ala residues in ß-sheet, A and B, plus one distorted ß-turn, t, formed by repetitive folding using ß-turns every eighth amino acid in an antipolar arrangement. However, because of the presence of Ser residues at every sixth residue in (AGSGAG)n, the T1 values and mobilities of B decreased significantly. We conclude that the Ser hydroxyls hydrogen bond to adjacent lamellar layers and fix them together in a similar way to Velcro®.

Structural heterogeneities in starch hydrogels.

Hydrogels have a complex, heterogeneous structure and organisation, making them promising candidates for advanced structural and cosmetics applications. Starch is an attractive material for producing hydrogels due to its low cost and biocompatibility, but the structural dynamics of polymer chains within starch hydrogels are not well understood, limiting their development and utilisation. We employed a range of NMR methodologies (CPSP/MAS, HR-MAS, HPDEC and WPT-CP) to probe the molecular mobility and water dynamics within starch hydrogels featuring a wide range of physical properties. The insights from these methods were related to bulk rheological, thermal (DSC) and crystalline (PXRD) properties. We have reported for the first time the presence of highly dynamic starch chains, behaving as solvated moieties existing in the liquid component of hydrogel systems. We have correlated the chains' degree of structural mobility with macroscopic properties of the bulk systems, providing new insights into the structure-function relationships governing hydrogel assemblies.

Primary structure of gum arabic and its dynamics at oil/water interface.

Gum arabic (GA), an arabinogalactan-based gum, is a well-known powerful emulsifier. However, the poor stability of emulsion has often been pointed out. In order to clarify the origin, the structure-property relationship of GA, especially the interfacial property at oil/water interface, needs to be investigated. Here, we tried to correlate the primary structure with interfacial property at oil/water interface. A series of structural analyses by SEC-MALLS, SAXS, etc. showed that the primary structure of GA was a disk-like star shaped nanoparticle. The dynamic interfacial tension measurement showed that GA molecules adsorb onto oil surface in 2 steps: Firstly, the micron-aggregates of GA approach onto the oil surface, and then the aggregates are dissociated into nano-particles so that they cover the oil surface. Therefore, the emulsification and emulsion stability are controlled not by the property of the primary structure of GA but by the higher-order molecular network structure made of GA molecules.

Use of solid-state NMR spectroscopy for investigating polysaccharide-based hydrogels: A review.

Hydrogels find application in many areas of technology and research due to their ability to combine responsiveness and robustness. A detailed understanding of their molecular structure and dynamics (which ultimately underpin their functional properties) is needed for their design to be optimized and these hydrogels to be exploited effectively. In this review, we shed light on the unique capabilities of solid-state NMR spectroscopy to reveal this information in molecular detail. We review recent literature on the advancements in solid-state NMR techniques in resolving the structure, degree of grafting, molecular organization, water-biopolymer interactions and internal dynamical behavior of hydrogels. Among various solid-state NMR techniques, 13C cross polarization (CP) magic angle spinning (MAS) NMR is examined for its ability to probe the hydrogel and its trapped solvent. Although widely applicable to many types of polymeric and supramolecular hydrogels, the current review focuses on polysaccharide-based hydrogels.

Solid state 13C-NMR methodology for the cellulose composition studies of the shells of Prunus dulcis and their derived cellulosic materials.

Lignocellulosic fibers and microcellulose have been obtained by simple alkaline treatment from softwood almond shells. In particular, the Prunus dulcis Miller (D.A.) Webb. was considered as a agro industrial waste largely available in southern Italy. The materials before and after purification have been characterized by 13C CPMAS NMR spectroscopy methodology. A proper data analysis provided the relative composition of lignin and holocellulose at each purification step and the results were compared with thermogravimetric analysis and FT-IR. To value the possibility of using this material in a circular economy framework, the fibrous cellulosic material was used to manufacture a handmade cardboard. The tensile performances on the prepared cardboard proved its suitability for packaging purposes as a sustainable material. These fibers along with the obtained microcellulose can represent a new use for the almond shells that are mainly used as firewood.

Role of catechin on collagen type I stability upon oxidation: a NMR approach.

The study focuses on the understanding, at molecular level, the mechanism of interaction between protein and flavonoids. Collagen and catechin interactions were investigated by NMR in solution and solid state. The effect of catechin on the stability of collagen to oxidation was also explored. Collagen was treated with two concentrations of catechin solutions. Oxidation was carried out by incubation of collagen solution with three oxidation systems: Fe(II)/H2O2, Cu(II)/H2O2, and NaOCl/H2O2. The effects of oxidation systems were evaluated by high resolution 1 D and 2 D proton spectroscopy and solid state NMR (13C CP MAS) experiments. Interactions between collagen and catechin preferentially occur between catechin B ring and the amino acids Pro and Hyp of collagen. Results showed that both iron and copper oxidation systems were able to interact with collagen by site specific attack. Moreover, catechin protects collagen proline from oxidation by metal/H2O2 systems, preventing copper and iron approach to collagene molecule;this behaviour was more evident for the copper/H2O2 system.

Cellulose nanocrystals-starch nanocomposites produced by extrusion: Structure and behavior in physiological conditions.

Different amounts of cellulose nanocrystals (CNCs) were added to glycerol-plasticized thermoplastic starch (TPS) to obtain bio-based nanocomposites. First, nanocomposites are prepared by extrusion and their structure is studied at different scales using WAXS (Wide Angle X-ray Scattering) and solid-state NMR (Nuclear Magnetic Resonance) for local/crystalline organization, AF4 (Asymmetrical Flow Field-Flow Fractionation) for molecular weight and chain length, and SEM (Scanning Electron Microscopy) for the morphology at a larger scale. Then, relevant mechanical properties and behavior in physiological conditions (swelling, enzymatic degradation) are characterized. The results show that the incorporation of cellulose nanocrystals up to 2.5 wt% causes a mechanical reinforcement as determined by DMTA (Dynamic Mechanical Thermal Analysis) and reduces the swelling and the enzymatic degradation of the materials compared to reference TPS. This could be linked to the formation of starch-cellulose hydrogen and hydroxyl bonds. Conversely, above 5 wt% CNC content nanocrystals seem to aggregate which in turn worsens the behavior in physiological conditions.