Assessing the concentration of conjugated fatty acids within pomegranate seed oil using quantitative nuclear magnetic resonance (qNMR).

INTRODUCTION: Pomegranate seed is rich in oil, and seed oil of pomegranate consists of conjugated fatty acids with different percentages. OBJECTIVES: The current contribution covers how to determine percentages of different isomeric conjugated fatty acids. METHODS: The percentages of these isomers are analysed by quantitative nuclear magnetic resonance (qNMR) using benzoic acid as an internal reference chemical with a well-defined amount. Linear mathematical equations are developed for the quantitative analysis of fatty acids found in pomegranate seed oil. RESULTS: The developed approach is utilised for the pomegranate seed oils prepared in the laboratory and tested for commercial samples. Among the oils derived at the laboratory, the Yeni Hicaz pomegranate cultivar seeds yielded the highest fraction of punicic acid. Among the acids, punicic acid was the one with the highest fraction, while linolenic acid was the one with the lowest percentage. CONCLUSIONS: These results are important in identifying pomegranate seed oils. Among the commercial samples tested with the current approach, only one of them showed similar content analysis as in the laboratory-derived oils.

A decade of innovation and progress in understanding the morphology and structure of heterogeneous polymers in rigid confinement.

When confined in nanoscale domains, polymers generally encounter changes in their structural, thermodynamics and dynamics properties compared to those in the bulk, due to the high amount of polymer/wall interfaces and limited amount of matter. The present review specifically deals with the confinement of heterogeneous polymers (i.e. polymer blends and block copolymers) in rigid nanoscale domains (i.e. bearing non-deformable solid walls) where the processes of phase separation and self-assembly can be deeply affected. This review focuses on the innovative contributions of the last decade (2010-2020), giving a summary of the new insights and understanding gained in this period. We conclude this review by giving our view on the most thriving directions for this topic.

Analysis of olive oil for authentication and shelf life determination.

High-field proton (1H) nuclear magnetic resonance (NMR) spectroscopy was applied for screening the fatty acyl contents of 33 olive oil samples from five different geographical regions of Turkey to do geographical discrimination analysis. The 1H NMR data were subjected to principal component analysis (PCA) and analysis of variance (ANOVA) to discriminate the origin of olive oils. The combination of discriminative screening by 1H NMR and ANOVA did not require further analysis of olive oil such as gas chromatography (GC). ANOVA was employed for samples from three regions separately: Marmara Region (MR), Aegean Region (AR), and Mediterranean Region (MeR). The best discriminative parameter was the 1H NMR signal of linoleoyl acyl content. Applying both quantitative NMR and statistical analysis indicated that samples from different provinces within each geographical region (MR, AR, and MeR) could be discriminated. Comparing the linoleoyl and oleoyl acyl contents of Turkish olive oils with these of some Mediterranean olive oils showed the possibility of distinguishing the Turkish olive oils. 1H NMR spectra of three olive oil samples with the production years of January 2013, January 2014, and January 2015 were acquired in 2016 for discussing shelf life of olive oil by quantifying fatty acyls content, and determining minor constituents and possible by-products during storage. The effects of altitude and soil quality on fatty acyl contents of olive oil samples from a small olive growing village in Northeastern Turkey were also tested.

Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study.

Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nanoporous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) were observed with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed nonporous, 12 nm particle size silica and a mesoporous silica with 200 nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. For pure methane, no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2, 32.6, 56.4, 65.1, 112.7, and 130.3 bar). However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD, and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.

Characterization and quantification of microstructures of a fluorinated terpolymer by both homonuclear and heteronuclear two-dimensional NMR spectroscopy.

Fluoropolymers are usually insoluble in organic solvents. Insolubility of fluoropolymers limits basic characterization such as microstructural investigations. In the family of fluoropolymers, terpolymer of tetrafluorethylene (TFE), hexafluoropropylene (HFP), and vinylidene fluoride (VDF), named THV is one of the newest members. There are nine grades of THV available. Among the nine grades, THV-221 G is an ideal model polymer for basic characterization purposes. THV-221 G is soluble in solvents such as acetone and ethyl acetate. In the current report, both homonuclear and heteronuclear 2D NMR experiments were employed in solution on THV-221 G. The homonuclear gradient correlation spectroscopy NMR measurement revealed that THV has two adjacent TFE units in addition to TFE-HFP sequence orders. The fraction of the microstructures is quantified by the analysis of 1D solution (19)F NMR spectrum. Further, the gradient heteronuclear single quantum coherence experiment helped with the clarification of chemical environments of the units TFE, HFP, and VDF. The 1D solution (13)C NMR spectrum was helpful in clarifying sequence assignments of VDF. It is concluded that THV is a random polymer with a limited fraction of TFE-TFE and TFE-HFP sequence orders in addition to head-to-tail polymerization of VDF unit.

Exploring the Gas Sensing Potential of Cross-Linked Asphaltene: A Promising Application of an Affordable Material.

In recent years, there has been significant research interest in carbon-based nanomaterials as promising candidates for sensing technologies. Herein, we present the first utilization of asphaltenes as an affordable, cost-efficient carbon-based material for gas sensing applications. Asphaltenes, derived from various oil sources, are subjected to facile cross-linking reactions to produce nanoporous carbon materials, where the asphaltene molecules from different layers are interconnected via covalent bonds. The characterization results of these cross-linked asphaltenes revealed substantial enhancement in their specific surface area and surface functionality. Quartz crystal microbalance sensors with sensing films derived from various asphaltene samples were prepared to detect different ethanol concentrations at room temperature. All the cross-linked asphaltene samples showed a significant enhancement in the sensing response (up to 430%) compared to that of their respective raw parent samples. Such a response of the cross-linked asphaltene samples was comparable to that obtained from graphene oxide. The sensor based on cross-linked asphaltenes demonstrated good linearity, with a response time of approximately 2.4 min, a recovery time of around 8 min, and an excellent response repeatability. After 30 days, the sensor based on cross-linked asphaltenes showed approximately 40% reduction in its response, suggesting long-term aging. This decline is partially attributed to the observed swelling. The current study opens the door to a deeper exploration of asphaltenes and highlights their potential as promising candidates for sensing applications.

Facile synthesis and characterization of novel pyrazole-sulfonamides and their inhibition effects on human carbonic anhydrase isoenzymes.

In the current study, a series of pyrazole-sulfonamide derivatives (2-14) were synthesized, characterized, and the inhibition effects of the derivatives on human carbonic anhydrases (hCA I and hCA II) were investigated as in vitro. Structures of these sulfonamides were confirmed by FT-IR, (1)H NMR, (13)C NMR and LC-MS analysis. (1)H NMR and (13)C NMR revealed the tautomeric structures. hCA I and hCA II isozymes were purified from human erythrocytes and inhibitory effects of newly synthesized sulfonamides on esterase activities of these isoenzymes have been studied. The K(i) values of compounds were 0.062-1.278 µM for hCA I and 0.012-0.379 µM for hCA II. The inhibition effects of 7 for hCA I and 4 for hCA II isozymes were almost in nanomolar concentration range.

Inhibitory effect of novel pyrazole carboxamide derivatives on human carbonic anhydrase enzyme.

The synthesis, characterization and biological evaluation of novel pyrazole carboxamide derivatives (2-9) are presented. (1)H and (13)C NMR have been used for the structure description, possible tautomeric structures determination and hydrogen bonding observation. FT-IR results have confirmed the synthesis of the pyrazole derivatives while thermal gravimetric analysis has confirmed thermal stability up to 300°C. The melting temperatures are strongly dependent on their crystal structure as confirmed by differential scanning calorimetry and X-ray diffraction measurements. Impacts of 2-9 as possible antiglaucoma agents were investigated on carbonic anhydrase I and II (CA-I and II) isozymes purified from human erythrocytes in vitro. Compounds 3 and 9 had the highest inhibitory effect while compounds 6 and 8 showed the lowest inhibition.

Low-field NMR investigations on dynamics of crude oil confined into nanoporous silica rods and white powder.

In the present study, to mimic the natural confinement of crude oils, model experiments are conducted with crude oils having different physical properties and maltenes of parent crude oils without asphaltenes confined into engineered nanoporous silica rods with pore diameters of 2.5 and 10.0 nm and white powdered nanoporous silica with pore diameters of 2.5 and 4.0 nm. This will help with suggesting potential treatments for enhancing crude oil recovery. Low-field nuclear magnetic resonance (LF-NMR) relaxometry has been applied to achieve this goal. The nanoporous proxies resemble real-life nanoporous rocks of reservoirs. The dynamics of confined crude oils with different oAPI gravity deviate from bulk dynamics, and deviation changes depending on the oAPI gravity. This suggests that treatments must be decided appropriately before crude oil production. Similar treatments could be applied for light and medium-heavy crude oils. Mathematical analysis of NMR relaxation curves of confined crude oils with different fractions of SARA (saturates, aromatics, resins, asphaltenes) indicates that the conventional SARA approach needs a better definition for the confined state of matter. The NMR relaxation behavior of confined maltenes shows that resin molecules might act like saturates in natural confinement with various scale pores from nano to micro and even macro, or aromatics might show resin-like behaviors. Confinement of brine and a light crude oil into white powdered nanoporous silica proxies demonstrates that brine could be utilized along with some additives such as nanoparticles for oil recovery. Therefore, these issues must be evaluated in deciding the proper treatments for crude oil production.

Surface Interactions and Nanoconfinement of Methane and Methane plus CO2 Revealed by High-Pressure Magic Angle Spinning NMR Spectroscopy and Molecular Dynamics.

This study explores the fundamental, molecular- to microscopic-level behavior of methane gas confined into nanoporous silica proxies with different pore diameters and surface-to-volume (S/V) ratios. Surfaces and pore walls of nanoporous silica matrices are decorated with hydroxyl (-OH) groups, resembling natural heterogeneity. High-pressure MAS NMR was utilized to characterize the interactions between methane and the engineered nanoporous silica proxies under various temperature and pressure regimes. There was a change in the chemical shift position of confined methane slightly in the mixtures with nanoporous silica up to 393 K, as shown by high-pressure 13C-NMR. The 13C-NMR chemical shift of methane was changed by pressure, explained by the densification of methane inside the nanoporous silica materials. The influence of pore diameter and S/V of the nanoporous silica materials on the behaviors and dynamics of methane were studied. The presence of CO2 in mixtures of silica and methane needs analysis with caution because CO2 in a supercritical state and gaseous CO2 change the original structure of nanoporous silica and change surface area and pore volume. According to simulation, the picosecond scale dynamics of methane confined in larger pores of amorphous silica is faster. In the 4 nm pore, the diffusivity obtained from MD simulations in the pore with a higher S/V ratio is slower due to the trapping of methane molecules in adsorbed layers close to the corrugated pore surface. In contrast, relaxation measured with NMR for smaller pores (higher S/V) exhibits larger T1, indicating slower relaxation.

Fluid Behavior in Nanoporous Silica.

We investigate dynamics of water (H2O) and methanol (CH3OH and CH3OD) inside mesoporous silica materials with pore diameters of 4.0, 2.5, and 1.5 nm using low-field (LF) nuclear magnetic resonance (NMR) relaxometry. Experiments were conducted to test the effects of pore size, pore volume, type of fluid, fluid/solid ratio, and temperature on fluid dynamics. Longitudinal relaxation times (T1) and transverse relaxation times (T2) were obtained for the above systems. We observe an increasing deviation in confined fluid behavior compared to that of bulk fluid with decreasing fluid-to-solid ratio. Our results show that the surface area-to-volume ratio is a critical parameter compared to pore diameter in the relaxation dynamics of confined water. An increase in temperature for the range between 25 and 50°C studied did not influence T2 times of confined water significantly. However, when the temperature was increased, T1 times of water confined in both silica-2.5 nm and silica-1.5 nm increased, while those of water in silica-4.0 nm did not change. Reductions in both T1 and T2 values as a function of fluid-to-solid ratio were independent of confined fluid species studied here. The parameter T1/T2 indicates that H2O interacts more strongly with the pore walls of silica-4.0 nm than CH3OH and CH3OD.

Large-Scale Diffusion of Entangled Polymers along Nanochannels.

Changes in large-scale polymer diffusivity along interfaces, arising from transient surface contacts at the nanometer scale, are not well understood. Using proton pulsed-gradient NMR, we here study the equilibrium micrometer-scale self-diffusion of poly(butadiene) chains along ∼100 µm long, 20 and 60 nm wide channels in alumina, which is a system without confinement-related changes in segmental relaxation time. Unlike previous reports on nonequilibrium start-up diffusion normal to an interface or into particulate nanocomposites, we find a reduction of the diffusivity that appears to depend only upon the pore diameter but not on the molecular weight in a range between 2 and 24 kg/mol. We rationalize this by a simple volume-average model for the monomeric friction coefficient, which suggests a 10-fold surface-enhanced friction on the scale of a single molecular layer. Further support is provided by applying our model to the analysis of published data on large-scale diffusion in thin films.

Synthesis, structure-activity relationships, and in vitro antibacterial and antifungal activity evaluations of novel pyrazole carboxylic and dicarboxylic acid derivatives.

A series of pyrazole-3-carboxylic acid and pyrazole-3,4-dicarboxylic acid derivatives were synthesized, the structures were confirmed by their NMR ((1)H and (13)C) and FT-IR spectra, and elemental analyses. The antibacterial and antifungal activities of the compounds against five bacterial and five fungal pathogens were screened using modified agar well diffusion assay. Most of the molecules have inhibitory effects on both standard and clinical Candida albicans strains. However, only the molecules 8, 10, 21, and 22 demonstrate some inhibitory effects on Candida parapsilosis, Candida tropicalis, and Candida glabrata strains. The structure-antifungal activity relationships of the compounds on the C. albicans strains were investigated by electron-conformational method. The pharmacophores and antipharmacophores responsible for the inhibition and non-inhibition of the C. albicans strains were obtained by electronic and geometrical characteristics of the reactive fragments of the molecules. These fragments along with the associated parameters can be used in designing the future more potent antifungal agents. It has been shown that both the positions of electronegative atoms like F and O in the pyrazole substituents and the amount of the associated charges on such atoms are crucial in regulating the strength of antifungal activity for the C. albicans strain.