Search Results (953)

The control of crystal form in chiral active pharmaceutical ingredients (APIs) is a critical challenge in pharmaceutical development, as differences in solid-state structure can significantly influence physical properties and manufacturing performance. Troglitazone, a molecule with two chiral centers, exists as four stereoisomers (RR, SS, RS, SR) that crystallize as two enantiomeric pairs: RR/SS and RS/SR. This study aims to elucidate the relationship between solution-state molecular interactions and crystallization behavior of these diastereomeric pairs. Antisolvent crystallization experiments were conducted for both mixed solutions containing all four isomers and solutions of individual pairs. Crystallization kinetics were monitored by HPLC, and the resulting solids were characterized by PXRD, DSC, TG, and microscopic observation. Nucleation induction times were determined over a range of supersaturation levels. To probe intermolecular interactions in solution, NOESY and targeted NOE NMR experiments were performed, and the results were compared with crystallographic data. The RS/SR crystals(H-form) consistently exhibited shorter induction times and faster crystallization rates than the RR/SS crystals (L-form), even under conditions where RR/SS solutions were more supersaturated. In mixed solutions, H-form crystallized preferentially, with L-form either remaining in solution or being incorporated into H-form crystals as a solid solution. NOESY and NOE analyses revealed intermolecular proximities between protons that are distant in the molecular structure, indicating the presence of ordered aggregates in solution. These aggregates were more structurally compatible with the H-form than with the L-form crystal lattice, as supported by crystallographic distance analysis. The results demonstrate that differences in nucleation kinetics between troglitazone diastereomers are closely linked to solution-state molecular arrangements. Understanding these relationships provides a molecular-level basis for the rational design of selective crystallization processes for chiral APIs. Full article

The applications of electromagnetic (EM) field treatment on water in agriculture have garnered increasing attention as a sustainable method to enhance plant growth, water-use efficiency, and metabolic performance. A growing body of evidence suggests that exposure to EM fields can affect water molecules, possibly by influencing hydrogen bonding dynamics, the structuring of water clusters, and electrokinetic properties of the water molecules. These alterations are thought to correlate with plant physiological performance. The methodology of the study was divided into two parts. The first part focused on the preparation of electromagnetically treated water. The second part involved applying this treated water to spinach plants. The present study investigates the physiological responses of Spinacia oleracea L. to irrigation with electromagnetically treated water (EMTW), focusing on elucidating the potential mechanisms that may underlie the observed effects. EMTW was generated using a solenoid-based system operating in dual-frequency ranges (100–1000 Hz and 10–100 kHz), which has been previously shown to influence both the microbiological and electrokinetic properties of aqueous systems. To evaluate the structural and functional implications of EMTW, a combined methodological approach was employed, integrating proton nuclear magnetic resonance (¹H-NMR) spectroscopy, density functional theory (DFT) modeling of water hydrogen bonds and clusters, and comprehensive plant physiological assessments. Plants were cultivated under both controlled and field conditions to assess consistency across environmental settings. Physiological measurements demonstrated that EMTW irrigation increased photosynthetic rate by ~80%, transpiration by 49–67%, stomatal conductance by 78–129%, intercellular CO₂ concentration by 42–80%, and chlorophyll content by 9.3–9.5% compared to control samples. Additionally, phenoloc and flavonoid contents were elevated by 7.4% and 7.6%, respectively, in field-grown plants. These enhancements were statistically significant (p < 0.001 or p < 0.01) under both laboratory and field conditions, confirming the robustness of the observed effects. Full article

To address issues of traditional coalbed methane (CBM) fracturing fluids (high displacement, weak sand-carrying, poor stability, severe coal seam damage), this study synthesized CO₂-responsive erucamide propyl dimethylamine surfactant (C₂₂ZEA, yield 99%), with molecular structure verified by ¹H NMR (400 MHz, CDCl₃) matching the target. Molecular simulation showed CO₂ protonates C₂₂ZEA into EA⁺: 1 wt% forms a simple micelle network, while 3 wt% enhances entanglement into a dense 3D network. Experiments indicated: 3 wt% solution reaches 160 mPa·s viscosity in 200 s under CO₂ (0.2 L·min⁻¹); 1.5–4.5 wt% solutions are pseudoplastic (n = 0.14–0.18), with G′ > G″ when concentration > 2 wt%; viscosity recovery rate > 95% after alternating shear (170 s⁻¹/10 s⁻¹); viscosity remains > 160 mPa·s after 1 h shear (170 s⁻¹) at 70 °C; gel breaks to 0.01–0.02 Pa·s in 15 min with N₂ at 45 °C; 1.0–3.0 wt% solutions meet non-toxic standards via EC₅₀/96 h LC₅₀. This study supports high-efficiency low-damage smart fracturing fluids, boosting CBM extraction efficiency. Full article

Cyclodextrins in metal oxide nanoparticles (NPs) serve as stabilizing, dispersing, and functionalizing agents that enhance antimicrobial performance through better nanoparticle stability, synergistic action, and potential controlled release mechanisms, making them ideal for advanced biomedical and environmental antimicrobial applications. In this study, NPs of vanadium pentoxide (V₂O₅) were obtained by the precipitation method, and, following a supramolecular assembly, were synthesized using the impregnation method via addition of β-cyclodextrin (BCD) and its derivatives, such as hydroxypropyl-β-cyclodextrin (HCD) and methyl-β-cyclodextrin (MCD). The formation of the V₂O₅:CDs was driven by non-covalent host–guest interactions, leading to a stable supramolecular structure with enhanced physicochemical properties. Morphological analysis using scanning electron microscopy (SEM) revealed uniformly distributed V₂O₅ NPs within the CD matrix. Structural characterization was further supported by proton nuclear magnetic resonance (NMR) spectroscopy, which confirmed the inclusion interactions between V₂O₅ and CDs. The synthesized NPs demonstrated significant antimicrobial activity against Gram-positive and fungal strains, indicating a synergistic enhancement in bioactivity due to the supramolecular architecture. This work highlights the potential of CD-assisted V₂O₅ NPs as promising antimicrobial agents for biomedical and environmental applications. Full article

Bacterial cellulose, a biopolymer synthesised by microorganisms, exhibits remarkable structural, optical, and electronic properties. This study utilised a range of photon- and electron-based techniques, including X-ray diffraction, proton nuclear magnetic resonance (¹H-NMR), photoacoustic spectroscopy, and scanning electron microscopy, to thoroughly characterise BC. While XRD and NMR directly employ photons to probe the structure and composition, PAS indirectly converts absorbed photons into phonons to evaluate optoelectronic features. SEM revealed a dense nanofibrillar network with fibrils measuring 10–75 nm in diameter. XRD confirmed the crystalline nature of BC, identifying characteristic peaks associated with cellulose Iα. ¹H-NMR relaxation analysis differentiated between the ordered and disordered cellulose regions. PAS determined an optical bandgap of 2.97 eV and identified defect states between 3.6 and 2.9 eV, including a prominent peak at 3.35 eV, likely resulting from oxygen vacancies, hydroxyl modifications, or UV-induced rearrangements. These defects modify BC’s electronic structure, suggesting potential for bandgap engineering. The integration of these complementary techniques provides a multidimensional understanding of BC’s morphology, crystallinity, and electronic behaviour, underscoring its potential in bioelectronics, advanced composites, and biomedical applications. Full article

Gastroesophageal reflux disease (GERD) is associated with symptoms such as heartburn, resulting from gastric content reflux. Alginate-based raft-forming gel formulations represent a non-pharmacological strategy for GERD management by forming a floating gel barrier in the stomach. This study evaluated three commercial anti-reflux oral gel systems under simulated fed-state gastric conditions, using in vitro magnetic resonance relaxometry techniques. Magnetic resonance imaging (MRI) was performed in 0.01 M hydrochloric acid (HCl) to visualize gel raft formation, spatial structure, and spatial distribution of effective T₂ relaxation time. Nuclear magnetic resonance (NMR) relaxometry in 0.01 M deuterium chloride (DCl) measured T₁ and T₂ relaxation times of the protons that were initially included in the preparation to assess its molecular mobility within the gel matrix. Two formulations formed floating, coherent gels, whereas the remaining one exhibited only polymer swelling without flotation. In one case, relaxometry data revealed a solid-like component that can be detected, indicating enhanced mechanical stability. The performance of each formulation was influenced by interactions among alginate, bicarbonates, and calcium ions, which determined gel consistency and flotation behavior. MRI and NMR relaxometry in vitro provide valuable non-invasive insights into the structural and functional behavior of alginate-based gel formulations. This approach supports the rational design of advanced gel-based therapies for GERD by linking molecular composition with in situ performance. Full article

Sodium magadiite (Na-Mgd) was hydrothermally prepared and converted to its protonic (H-Mgd) form by reaction with hydrochloric (HCl) solution. The obtained products were studied as adsorbents for basic blue 41 (BB-41) removal from polluted aqueous solution. Na-Mgd and H-Mgd were characterized by different techniques. Powder X-ray (PXRD) diffraction data confirmed a pure Na-Mag phase and its conversion to acidic form (H-Mgd) with shift in d₀₀₁ value from 1.54 nm to 1.12 nm. X-ray fluorescence (XRF) data supported the exchange of Na cations by protons for H-Mag. ²⁹Si magic angle spinning nuclear magnetic resonance (MAS-NMR) indicated a change in the local environment of silicon nucleus when Na-Mgd was treated with HCl solution. The BB-41 removal dyes were investigated throughout the batch process. Effects of selected parameters, for example, the adsorbent dosage, pH of the BB-41 solution, pH of the H-Mag solid, and starting concentration, were explored. The equilibrium data were fitted to the Langmuir and Freundlich isotherm models. The maxima removal capacities of Na-Mgd and H-Mgd were 219 mg/g and 114 mg/g, respectively. The regeneration and reusability tests were performed using initial concentrations of 50 mg/L and 200 mg/L for seven cycles. The efficiency was maintained for 5 to 6 cycles with a decline of 10% using low initial concentration; however, a decline of efficiency to 30 to 50% was achieved when a higher initial concentration was employed after 3 to 4 regeneration tests for Na-Mgd and H-Mgd samples. Adsorber batch design using the Langmuir and Freundlich isotherm parameters was used to predict its performance for commercial usage. The predicted masses of H-Mgd were higher than those of Na-Mgd to treat different effluent volumes contaminated with 200 mg/L of BB-41 dyes at desired removal percentages. Full article

Solid solutions of the metallocenes ferrocene (Cp₂Fe), nickelocene (Cp₂Ni), and cobaltocene (Cp₂Co) have been prepared by manually grinding the components together, or by co-crystallizing them from solution. In the solid solutions Cp₂Fe/Cp₂Ni and Cp₂Co/Cp₂Ni, the cyclopentadienyl (Cp) protons relax via dipolar electron–proton interactions, which represent the dominant relaxation mechanism. The ¹H T₁ relaxation times of the molecules Cp₂Ni and Cp₂Co, dissolved in CDCl₃, and in the solid solutions, show that the relaxation takes place intramolecularly. The relaxation of the protons is propagated exclusively via the unpaired electrons of the metal centers to which their Cp rings are coordinated, due to the large intermolecular distances that are greater than 3.91 Å. In contrast, the intramolecular distances between the electrons of the metal atoms and the protons of their coordinated Cp rings are merely 2.70 Å. Using these intramolecular distances and the ¹H T₁ relaxation times, the electron relaxation times T_1e have been determined as 17 × 10⁻¹³ s in CDCl₃ solutions and 45 × 10⁻¹³ s in the solid state for Cp₂Ni. The corresponding T_1e times for Cp₂Co are calculated as ca. 5 × 10⁻¹³ s and 20 × 10⁻¹³ s. Grinding Cp₂Fe and Cp₂Ni together leads to two different ¹H T₁ relaxation times for the protons of Cp₂Fe. The longer T₁ relaxation time indicates domains that consist mostly of Cp₂Fe molecules. The short T₁ times show a close contact of Cp₂Fe and Cp₂Ni molecules. An analysis of the short ¹H T₁ times reveals the presence of at least two to three short distances of 3.91 Å between Cp₂Fe and Cp₂Ni molecules. These results support the hypothesis that dry grinding of the metallocenes Cp₂Fe and Cp₂Ni in ratios that were changed in 10% increments from 90%/10% to 30%/70% leads to domains that mostly consist of Cp₂Fe molecules, and additionally to domains that contain a mixture of the components on the molecular level. Full article

Small ruminant production is a significant sector of agricultural industry in Texas, USA. Heat stress has a negative effect on productivity and animal health. Cholecalciferol, a form of vitamin D₃, may enhance the function of immune cells and help ensure healthy immune function in farm animals exposed to heat stress. Practical applications of vitamin D₃ against infectious diseases can benefit from the protective effects of a delivery system comprised of soy protein isolate and stachyose in emulsion gel. The prebiotic oligosaccharide stachyose has shown to have a great potential as a substrate for beneficial intestinal bacteria, which are thought to modulate the immune system. Cellular and humoral immunity are both impaired in dairy animals under heat stress. The delivery of vitamin D₃ embedded within the soy protein isolate-stachyose emulsion gel resulted in a marked increase in 25-hydroxyvitamin D₃ [25-(OH)-D₃] concentration in blood serum. Chicken egg albumin (OVA)-immunized goats produced low anti-OVA immunoglobulin G (IgG) responses. In contrast, OVA-immunized goats fed vitamin D₃ within the soy protein isolate-stachyose emulsion gel diet strongly stimulated antibody production. These results show that anti-OVA IgG responses can be modulated in dairy goats using vitamin D₃, particularly if this vitamin is delivered in the form of emulsion gel. The results seem to depend on the highly hydrated gel matrix of soy protein isolate-stachyose at the low pH of the stomach as monitored by oxygen-17 (¹⁷O) and proton (¹H) nuclear magnetic resonance (NMR). In addition, the prebiotic nature of stachyose may boost beneficial gut bacteria, most notably for immune health and reducing the risk of infectious diseases. Full article

The reaction of the bulky ligand 1,2-bis-(di-tert-butylphosphinomethyl)benzene, 1 with [Ni(DME)Cl₂], 3, DME = 1,2-dimethoxyethane, at room temperature over extended periods, affords the new blue Zwitterionic complex [2-(C₆H₄-CH₂P(H)^tBu₂-1-(CH₂P^tBu₂NiCl₃)], 4, which contains a phosphonium group and an anionic nickel trichloride. This complex decomposes in alcohols such as methanol and the solution turns yellow. A discussion of the possible mechanism leading to the observed product is presented. Key to this is identification of the source of the phosphonium proton, which we speculated to arise from trace water in the initial nickel complex. To prove that trace water was present in [Ni(DME)Cl₂], a sample of this precursor was reacted under similar condition with anhydrous DMF alone. In addition to the known complex [Ni(DMF)₆)]²⁺[NiCl₄]²⁻, 5, we identified the trans-diaqua complex [Ni(Cl)₂(H₂O)₂(DMF)₂], 6, which proved the presence of trace water. Interestingly in dimethylformamide, [2-(C₆H₄-CH₂P(H)^tBu₂-1-(CH₂P^tBu₂NiCl₃)] exhibits thermochromic properties: an solution that is pale blue at ambient temperature reversibly changes colour to yellow upon cooling. This behaviour is specific to DMF and is related to the solvato-chromic behaviour exhibited by related DMF–nickel complexes. A discussion of the NMR spectra of compound 4 in a range of solvents is presented. The structures of the previously prepared molybdenum complex, [1,2-(C₆H₄-CH₂P^tBu₂)₂Mo(CO)₄] and the bis-(phosphine sulphide) of the ligand, [1,2-(C₆H₄-H₂P(S)^tBu₂)₂], 5, are described for structural comparative purposes. Full article

Phenytoin is an anticonvulsant drug that suffers from low aqueous solubility. The formation of phenytoin salts is a strategy employed to address this issue. A phenytoin–piperidine salt (PPD–PNT) was synthesized by solvent-assisted grinding and characterized by infrared (IR) spectroscopy, ¹H and ¹³C Nuclear Magnetic Resonance (NMR), and powder and single crystal X-ray diffraction. The IR and NMR spectra obtained differed from those of the starting compounds, showing shifts in the N-H and C=O group signals, as well as the appearance of NH⁺ signals, indicating proton transfer and salt formation. Powder X-ray diffraction confirmed the formation of a new solid phase corresponding to the salt. Single crystal X-ray diffraction showed the molecular structure of the PPD–PNT salt. Full article

The consumption of animal- and plant-based protein food is increasing as the world population grows. Alternative protein sources that are nutritious, safe and sustainable are needed. There is a growing research interest in integrating wheat-based staple foods, such as pasta, with new ingredients that could also provide nutritional and health benefits. Despite their unquestionable nutritional value, new pasta formulations need to be evaluated in terms of technological/sensory quality. In this study, we assessed the quality and flavour of traditional egg pasta fortified with two alternative protein sources: hazelnut flour and cricket powder. It is known that a quality pasta tends to lose fewer solids during cooking. In parallel with classical evaluation of cooking and sensory characteristics, proton nuclear magnetic resonance (¹H NMR) spectroscopy of the metabolites released during the cooking process and volatile fingerprint analysis with quartz microbalance (QMB) electronic nose (E-nose) were performed. These approaches showed results complementary to those obtained from classical quality and sensory analyses, thus demonstrating the potential of ¹H NMR and E-nose in pasta quality assessment. Overall, the pasta fortification with cricket powder and hazelnut flour affected the matrix mobility by modulating the release of chemical components into the water during cooking and overcooking processes; moreover, it significantly altered the pasta sensory profile in terms of aroma and texture. This finding highlights the complexity of balancing technological improvement with sensory appeal in food product development. Full article

The state of the art in the thermodynamics of calix[4]resorcinarene derivatives and its metal ion complexes is briefly discussed in the introduction. This is followed by the synthesis and characterization of a recyclable calix[4]resorcinarene amide derivative (L). The 1H NMR analyses in CD3CN and CD3OD showed solvent-dependent conformational changes with a notable downfield chemical shift in the aromatic proton (H-2) in moving from deuterated methanol to acetonitrile, indicating an interaction of the solvent within the ligand cavity as suggested by molecular dynamic simulations. 1H NMR complexation in acetonitrile revealed that L forms relatively strong 1:1 complexes with cations, with selectivity for Ca(II) and, to lesser extent, with Pb(II) over other metal cations. The composition of the complexes is corroborated by conductance measurements. The thermodynamics of these systems indicate that the complexation process is predominantly enthalpy controlled in acetonitrile, while it is entropy controlled in methanol. A remarkable outcome of fundamental studies is found in its application as new material for the removal of Ca(II) from water. The capacity of L to remove Ca(II) from water is 24 mmol/g which exceeds by far the capacity of cation exchange resins. Full article

Because allopregnanolone and derivatives represent biologically active molecules, in this letter, we present the synthesis of a new bioconjugate steroid pyridinium salt derived from allopregnanolone in three steps. The key steps involve the formation of the hydrazone intermediate, followed by condensation with bromoacetyl bromide and subsequent coupling with pyridine to generate the pyridinium bromide salt. The new bioconjugate steroid pyridinium salt, 4, was fully characterized by proton and carbon nuclear magnetic resonance (¹H and ¹³C NMR) spectroscopy, mass spectrometry (MS), and Fourier transform infrared spectroscopy (FTIR). ¹H-NMR analysis revealed the presence of a dynamic rotameric mixture in a 7:3 ratio of Z/E amide conformers, which were identified by a 2D NOESY experiment. Full article

In this report, we describe the synthesis of a compound derived from the natural compound celastrol, which is connected to a phthalimide moiety via an ester linkage. The compound was fully characterized by proton (¹H), carbon-13 (¹³C), heteronuclear single-quantum coherence (HSQC), and distortionless enhancement by polarization transfer (DEPT) NMR. Ultraviolet–visible spectroscopy (UV-Vis), Fourier-transform infrared (FTIR), and elementary analysis were also performed. Full article