Proton Nuclear Magnetic Resonance Spectroscopy Research Articles

Ultrasound-Assisted Extraction, Characterization and Assessment of Vegetable Tannins from Guava (Psidium guajava) Leaves for Leather Tanning

For commercial leather processing, chrome tanning is the most used approach but it significantly contributes to environmental pollution. Vegetable tannins, which are large polyphenolic compounds, form strong interactions with proteins and carbohydrates, thereby enhancing the adaptability and value of vegetable-tanned leather as well as reducing environmental impact. In this study, vegetable tannins were extracted from the leaves of Guava plants (Psidium guajava) using ethanol as the solvent, facilitated by ultrasound. Extracted tannins were quantified using the Folin–Ciocâlteu reagent with ultraviolet-visible spectroscopic method. Ultrasound enhanced the extraction process producing a high yield in less time due to its mechanical, thermal, and cavitation impacts. The extracted tannins were characterized by a variety of spectroscopic techniques, including Proton (1H) Nuclear magnetic resonance, Fourier-transform infrared, and ultraviolet-visible spectroscopy. The effect of various process variables, such as temperature, solid-liquid ratio, ultrasonic power, extraction period, and powder fineness, were also investigated to optimize the extraction process. Finally, the extracted tannins were employed in leather tanning processes to assess their potential as tanning agents. The extracted tannins ensured uniform diffusion of tannins, improved thermal stability and reduced the number of tannins in effluent by 68% making it an environmentally friendly leather tanning process.

Uracil as a biomarker for spatial pyrimidine metabolism in the development of gingivobuccal oral squamous cell carcinoma

No biomarker has yet been identified that allows accurate diagnosis and prognosis of oral cancers. In this study, we investigated the presence of key metabolites in oral cancer using proton nuclear magnetic resonance (NMR) spectroscopy to identify metabolic biomarkers of gingivobuccal oral squamous cell carcinoma (GB-OSCC). NMR spectroscopy revealed that uracil was expressed in 83.09% of tumor tissues and pyrimidine metabolism was active in GB-OSCC; these results correlated well with immunohistochemistry (IHC) and RNA sequencing data. Based on further gene and protein analyses, we proposed a pathway for the production of uracil in GB-OSCC tissues. Uridinetriphosphate (UTP) is hydrolyzed to uridine diphosphate (UDP) by CD39 in the tumor microenvironment (TME). We hypothesized that UDP enters the cell with the help of the UDP-specific P2Y6 receptor for further processing by ENTPD4/5 to produce uracil. As the ATP reserves diminish, the weakened immune cells in the TME utilize pyrimidine metabolism as fuel for antitumor activity, and the same mechanism is hijacked by the tumor cells to promote their survival. Correspondingly, the differential expression of ENTPD4 and ENTPD5 in immune and tumor cells, respectively, indicatedtheir involvement in disease progression. Furthermore, higher uracil levels were detected in patients with lymph node metastasis, indicating that metastatic potential is increased in the presence of uracil. The presence of uracil and/or expression patterns of intermediate molecules in purine and pyrimidine pathways, such asCD39, CD73, and P2Y6 receptors together with ENTPD4 and ENTPD5, hold promise as biomarker(s) for oral cancer diagnosis and prognosis.

Effect of Oligoricinoleic Acid on Degradation of Polylactic Acid

ABSTRACT The objective of this research is to explore the impact of oligoricinoleic acid (ORA) on the degradation of polylactic acid (PLA). ORA was synthesized from ricinoleic acid using tin (II) 2-ethylhexanoate as a catalyst. The chemical structures of the obtained ORA were confirmed by Fourier-transform infrared spectrometer (FT-IR) and proton nuclear magnetic resonance spectroscopy (1H-NMR). PLA/ORA films were prepared through the casting method by varying ORA concentrations as 0.1%wt, 0.3%wt, 0.5%wt, 1.0 wt%, and 3.0%wt. Degradation of the films via hydrolysis was studied by soaking the films in deionized water and stirring at 120 rpm in an incubator at 37°C. Alterations in the structure and properties of the films were investigated after soaking for 7, 14, 21, and 28 days using ultraviolet-visible spectroscopy (UV-Vis), Fourier-transform infrared spectrometer (FTIR), scanning electron microscope (SEM), X-ray diffraction (XRD), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), and universal testing machine (UTM). Gel permeation chromatography (GPC) was performed to confirm the decrease in molecular weight (MW). The presence of 3%wt ORA could promote both ductility and degradation of PLA films. ORA further enhances thermal stability, indicating potential for prevention of thermal degradation during melt processing.

Development and Validation of 1H Nuclear Magnetic Resonance Quantitative Method for Efavirenz API Quality Control

Background: The pharmaceutical industry is constantly looking for a better way to ensure and improve its products' safety, quality, and effectiveness. Since there are many attributes of the drug substance and excipients that could potentially affect the Critical Quality Attributes (CQAs) of the intermediates and the final product, the evaluation of the raw material's physicochemical characteristics is crucial as they directly affect the quality, safety, efficacy, and lot-to-lot consistency. Scientists rely on methods, like HPLC, HPTLC, LC-MS, GC-MS, and NMR, to analyze these substances. The advantage of NMR is that it is considered a primary analytical method compared to other analytical techniques. Objective: This work aimed to present a simple, rapid, specific, and accurate method by proton Nuclear Magnetic Resonance spectroscopy (1H-NMR) developed to determine the activity of the antiretroviral Efavirenz’s (EFZ) Active Pharmaceutical Ingredient (API). The method was based on quantitative NMR spectroscopy (qNMR). Methods: A Bruker Avance spectrometer (11.7 Tesla, 500 MHz for 1H) with a 5mm probe was used. The 1H-NMR signal at 7.54 ppm corresponding to the analyte of interest was employed to quantify the drug. The method was validated for specificity, selectivity, intermediate precision, linearity, range of work, accuracy, and robustness. Results: The method developed was specific and linear (r2 = 0.9998) with a value between 4.30 mg/mL and 12.40 mg/mL. The relative standard deviation for accuracy and precision was 0.4% or less. The method's robustness was demonstrated by changing four different parameters, and the difference among each was 1.2% or less. The results of this work have been found to be in agreement with those obtained from High-performance Liquid Chromatography (HPLC) analysis. result: The method developed was specific and linear (r2 = 0.9998) between 4.30 mg/mL and 12.40 mg/mL. The relative standard deviation for accuracy and precision was 0.4% or less. The method's robustness was demonstrated by changing four different parameters; the difference among each was 1.2% or less. The results in this work agreed with those obtained from high-performance liquid chromatography analysis (HPLC). Conclusion: The proposed method has been found to be a valuable and practical tool for quality control. Its applicability to determining many APIs and saving solvent use and time is highlighted.

Nuclear Magnetic Resonance (NMR) Metabolomics: Current Applications in Equine Health Assessment.

Metabolomics can allow for the comprehensive identification of metabolites within biological systems, at given time points, in physiological and pathological conditions. In the last few years, metabolomic analysis has gained popularity both in human and in veterinary medicine, showing great potential for novel applications in clinical activity. The aim of applying metabolomics in clinical practice is understanding the mechanisms underlying pathological conditions and the influence of certain stimuli (i.e., drugs, nutrition, exercise) on body systems, in the attempt of identifying biomarkers that can help in the diagnosis of diseases. Proton Nuclear Magnetic Resonance spectroscopy (1H-NMR) is well tailored to be used as an analytical platform for metabolites' detection at the base of metabolomics studies, due to minimal sample preparation and high reproducibility. In this mini-review article, the scientific production of NMR metabolomic applications to equine medicine is examined. The research works are very different in methodology and difficult to compare. Studies are mainly focused on exercise, reproduction, and nutrition, other than respiratory and musculoskeletal diseases. The available information on this topic is still scant, but a greater collection of data could allow researchers to define new reliable markers to be used in clinical practice for diagnostic and therapeutical purposes.

Waste snail shells-derived mixed oxide catalyst for efficient transesterification of vegetable oil: Towards sustainable biodiesel production

This study explores the transesterification process of soybean oil for the production of biodiesel, utilizing an innovative mixed oxide catalyst obtained from discarded snail shells powder. The catalyst synthesis involved a thermal treatment at 900°C for 120 min, predominantly yielding calcium oxide (CaO). In order to evaluate its properties, we carried out a thorough characterization using various analytical techniques. The study explores the impact of crucial variables on the transesterification reaction, such as reaction time (from 30 to 150 min), methanol-to-oil ratio (from 3:1–18:1), and catalyst concentration (from 0.5% to 4% by weight). Optimal conditions emerged with a 90-min reaction time, a 12:1 methanol-to-oil ratio, and a 2% catalyst loading, yielding an impressive biodiesel conversion rate of approximately 93%. The validity of biodiesel conversion was confirmed through Fourier transform infrared spectroscopy (FTIR) and Proton Nuclear Magnetic Resonance Spectroscopy (1 H NMR). The resultant biodiesel exhibited highly favorable characteristics, including an acid value of 0.85 mg of KOH/g, a density of 886.8 kg/m3, and a viscosity of 4.6 mm2/s. These measurements align with the standards set forth in EN 14214 and ASTM D6751 regarding biodiesel quality. The utilization of waste snail shells powder as a precursor for synthesizing the mixed oxide catalyst presents a promising approach for the sustainable production of biodiesel from soybean oil, offering a sustainable and efficient approach to biofuel production.

Quantitative analysis of molecular interactions in κ-carrageenan-Isovanillin biocomposite for biodegradable packaging and pharmaceutical applications using NMR, TOF-SIMS, and XPS approach

This study explores the molecular interactions and structural changes in κ-carrageenan crosslinked with isovanillin to create a biocomposite material suitable for hard capsule and bio-degradable packaging applications. Proton Nuclear Magnetic Resonance (1H NMR) spectroscopy revealed chemical changes in the conjugate molecule, indicating improved electronegativity due to intermolecular hydrogen bonding between κ-carrageenan and isovanillin. Time-of-flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis revealed enhanced ion intensity due to intermolecular interactions, particularly between sulphate and hydrogen ions. X-ray Photoelectron Spectroscopy (XPS) study demonstrated that κ-carrageenan and isovanillin form stronger hydrogen bonds, with a shift in binding energy indicating higher electronegativity. These findings shed light on the molecular mechanisms that underpin the formation of the biocomposite material, as well as its potential for use in hard capsule and biodegradable packaging materials, addressing the need for sustainable alternatives in the pharmaceutical and packaging industries while also contributing to environmental conservation.

Fermentation Analytical Technology (FAT): Monitoring industrial E. coli fermentations using absolute quantitative 1H NMR spectroscopy

BackgroundTo perform fast, reproducible, and (absolute) quantitative measurements in an automated manner has become of paramount importance when monitoring industrial processes, including fermentations. Due to its numerous advantages – including its inherent quantitative nature – Proton Nuclear Magnetic Resonance (1H NMR) spectroscopy provides an ideal tool for the time-resolved monitoring of fermentations. However, analytical conditions, including non-automated sample preparation and long relaxation times (T1) of some metabolites, can significantly lengthen the experimental time and make implementation in an industrial set up unfeasible. ResultsWe present a high throughput method based on Standard Operating Procedures (SOPs) and 1H NMR, which lays the foundation for what we call Fermentation Analytical Technology (FAT). Our method was developed for the accurate absolute quantification of metabolites produced during Escherichia coli industrial fermentations. The method includes: (1) a stopped flow system for non-invasive sample collection followed by sample quenching, (2) automatic robot-assisted sample preparation, (3) fast 1H NMR measurements, (4) metabolites quantification using multivariate curve resolution (MCR), and (5) metabolites absolute quantitation using a novel correction factor (k) to compensate for the short recycle delay (D1) employed in the 1H NMR measurements. The quantification performance was tested using two sample types: buffer solutions of chemical standards and real fermentation samples. Five metabolites – glucose, acetate, alanine, phenylalanine and betaine – were quantified. Absolute quantitation ranged between 0.64-3.40 mM in pure buffer, and 0.71-7.76 mM in real samples. SignificanceThe proposed method is generic and can be straight forward implemented to other types of fermentations, such as lactic acid, ethanol and acetic acid fermentations. It provides a high throughput automated solution for monitoring fermentation processes and for quality control through absolute quantification of key metabolites in fermentation broth. It can be easily implemented in an at-line industrial setting, facilitating the optimization of the manufacturing process towards higher yields and more efficiently/sustainable use of resources.

Synthesis and conformational aspects of 2-phenoxytetralones: Experimental verification and density functional theory (DFT) calculation

A series of 2-phenoxy-1-tetralones have been synthesized as conformationally constrained analogs of bioactive compounds 2-phenoxyacetophenones. A representative oxime derivative of 2-(3-methoxyphenoxy)-1-tetralone was selectively prepared and its (Z)-geometry was characterized by proton nuclear magnetic resonance (1H NMR) spectroscopy. Also, the conformational aspects of designed compounds were investigated by 1H NMR spectroscopy and density functional theory (DFT) calculations. The computational results showed that the more stable conformation in 5c is a conformer with equatorial orientation for 2-aryloxy group but the axial orientation in the related oxime 6 is predominated. Accordingly, it was demonstrated that the formation of (Z)-oxime on 1-position results in a remarkable conformational inversion on tetralin ring.

Direct electrospinning for producing multiple activity nanofibers consisting of aggregated luteolin/hydroxypropyl-gamma-cyclodextrin inclusion complex

Hydroxypropyl-gamma-cyclodextrin (HPγCD) inclusion complex nanofibers (Lut/HPγCD-IC-NF) containing Luteolin (Lut) were prepared by electrospinning technology. Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) spectra confirmed the formation of Lut/HPγCD-IC-NF. Scanning electron microscopy (SEM) images showed that the morphology of Lut/HPγCD-IC-NF was uniform and bead-free, suggesting that self-assembled aggregates, macromolecules with higher molecular weights, were formed by strong hydrogen bonding interactions between the cyclodextrin inclusion complexes. Confocal laser scanning microscopy (CLSM) images showed that Lut was distributed in Lut/HPγCD-IC-NF. Proton nuclear magnetic resonance (1H NMR) spectroscopy revealed the change in chemical shift of the proton peak between Lut and HPγCD, confirming the formation of inclusion complex. Thermogravimetric analysis (TGA) proved that Lut/HPγCD-IC-NF had good thermal stability. The phase solubility test confirmed that HPγCD had a solubilizing effect on Lut. When the solubility of HPγCD reached 10 mM, the solubility of Lut increased by 15-fold. The drug loading test showed that the content of Lut in fibers reached 8.57 ± 0.02 %. The rapid dissolution experiment showed that Lut/HPγCD-IC-NF dissolved within 3 s. The molecular simulation provides three-dimensional evidence for the formation of inclusion complexes between Lut and HPγCD. Antibacterial experiments showed that Lut/HPγCD-IC-NF had enhanced antibacterial activity against S. aureus. Lut/HPγCD-IC-NF exhibited excellent antioxidant properties with a free radical scavenging ability of 89.5 ± 1.1 %. In vitro release experiments showed Lut/HPγCD-IC-NF had a higher release amount of Lut. In conclusion, Lut/HPγCD-IC-NF improved the physicochemical properties and bioavailability of Lut, providing potential applications of Lut in the pharmaceutical field.

Controlled Magnetite Grafted Poly(glycidyl methacrylates) for Heavy Metal Absorption and Recovery via SET-LRP

A versatile magnetite based stringent polymer for effective metal capture was prepared by reacting iron oxide based initiator with glycidyl methacrylate monomer via single-electron transfer living radical polymerization (SET-LRP) technique. The versatile grafted polymer was successfully synthesized by metal catalyzed living radical polymerization using the catalyst system Cu/N,N,N',N'',N'''-pentamethyldiethylenetriamine as the ligand. The structural confirmation of the initiator and the grafted polymer was analyzed by using instrumentation methods such as proton nuclear magnetic resonance spectroscopy, UV-visible, TGA, SEM and gel permeation chromatography for molecular weight measurements. As the polymerization time increased, both the conversion and the molecular weight were observed to increase linearly with time. Narrow dispersed lower polydispersity index (PDI) and dispensable magnetite-g-PGMA was utilized for the extract of toxic lead from the wastewater. Sustained binding was observed due to the presence of epoxide ring in the repeating units of the polymer and recovered by magnetic effect. The material shows good stability as evident by TGA curves and better affinity to toxic lead as observed by UV-visible and SEM techniques.

Synthesis and Characterization of Hexahydropyrimidines and Their New Derivatives

Three new hexahydropyrimidine derivatives 1a – 1c were successfully synthesized using the Mannich-type reaction. Furthermore, the synthesis of three amino bases 2a – 2c was achieved through the reduction reaction of pyrimidine compounds using hydrazine, followed by the substitution reaction of nitro groups at diverse positions. Subsequently, one of the synthesized amino base derivatives 2c underwent conversion into seven Schiff bases 3a – 3g via a condensation reaction involving the aforementioned amino base derivative and a selection of benzaldehyde derivatives. Four amide compounds 4a – 4d have been synthesized by a reaction of the secondary amine group in the pyrimidine ring with benzoyl chloride. The products were subjected to comprehensive characterization employing rigorous analytical techniques, including FT-), 1H-NMR (Proton Nuclear Magnetic Resonance Spectroscopy), and LC-MS (Liquid Chromatography–Mass Spectrometry). Additionally, the Molecular Electrostatic Potential (MEP) study was carried out to further investigate the properties of the synthesized compounds. The yields of the three methods used to synthesise new hexahydropyrimidine derivatives varied depending on the specific substituents added to the aromatic ring.

1H-NMR metabolomics investigation of CSF from children with HIV reveals altered neuroenergetics due to persistent immune activation.

HIV can invade the central nervous system (CNS) early during infection, invading perivascular macrophages and microglia, which, in turn, release viral particles and immune mediators that dysregulate all brain cell types. Consequently, children living with HIV often present with neurodevelopmental delays. In this study, we used proton nuclear magnetic resonance (1H-NMR) spectroscopy to analyze the neurometabolic profile of HIV infection using cerebrospinal fluid samples obtained from 17 HIV+ and 50 HIV- South African children. Nine metabolites, including glucose, lactate, glutamine, 1,2-propanediol, acetone, 3-hydroxybutyrate, acetoacetate, 2-hydroxybutyrate, and myo-inositol, showed significant differences when comparing children infected with HIV and those uninfected. These metabolites may be associated with activation of the innate immune response and disruption of neuroenergetics pathways. These results elucidate the neurometabolic state of children infected with HIV, including upregulation of glycolysis, dysregulation of ketone body metabolism, and elevated reactive oxygen species production. Furthermore, we hypothesize that neuroinflammation alters astrocyte-neuron communication, lowering neuronal activity in children infected with HIV, which may contribute to the neurodevelopmental delay often observed in this population.

1H NMR spectroscopic analysis of metabolite changes in kauri leaf apoplastic washing fluid following inoculation with Phytophthora agathidicida

Phytophthora agathidicida is responsible for a devastating dieback disease that threatens the survival of Agathis australis (kauri), an ancient conifer species endemic to New Zealand. To develop durable control strategies against kauri dieback disease, a better understanding of the host metabolites necessary for the growth and survival of P. agathidicida during in planta growth, particularly during colonisation of the apoplastic environment, where early contact between host and pathogen cells is made, is required. As a starting point to address this knowledge gap, we investigated changes in the metabolite profile of apoplastic washing fluid (AWF) samples harvested from kauri leaves following either mock inoculation or inoculation with P. agathidicida. AWF was extracted from leaves of kauri saplings and inoculated with P. agathidicida on cellophane membranes or cellophane membranes without the pathogen as a control. The metabolite profile of the AWF samples was then analysed via proton nuclear magnetic resonance (1H NMR) spectroscopy at 24 hours and 10 days post-inoculation, and changes investigated relative to the control. Some changes in the metabolite profile of kauri AWF samples following P. agathidicida inoculation were observed using 1H NMR spectroscopy, including a decrease in sucrose and an increase in glucose resulting from the breakdown of more complex carbohydrates. Our results suggest that P. agathidicida modifies or utilises metabolites present in the leaf apoplast of kauri, including carbohydrates that serve as a source of nutrition. These results provide possible new insights into the nutritional requirements of P. agathidicida during apoplastic colonisation of kauri.

Recycling of polyester bottle waste to generate functional acid dye in situ on wool

AbstractNowadays, waste management is gaining popularity to reduce the environmental impact made by human beings. There is a dire need to decrease the pollution caused by plastic materials. A gradual rise in the demand for polyester bottles has generated a need to recycle these materials. In the present work, an aromatic amine (4,4′‐(1,4‐phenylenebis(1,3,4‐oxadiazole‐5,2‐diyl)) dianiline) was prepared from the polyester bottle waste. The successful synthesis and chemical structure of the amine was confirmed by various characterization techniques such as Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR), and 13C NMR. The amine was diazotized and coupled with H‐acid (4‐amino‐5‐hydroxy‐2,7‐naphthalene disulfonic acid)‐treated wool fabric to generate acid dye in situ on the fabric. The coloration (L*, a*, b*, and K/S) and fastness properties of dyed wool were evaluated, and the samples were further analyzed for antibacterial and UV‐protective properties. The dyed wool was also characterized by FTIR to confirm the presence of the aromatic group of the dye. The introduction of dye structure on the wool increased the thermal stability of the fabric, which was confirmed through thermogravimetric analysis analysis. Antibacterial activity (>70%) and excellent UV protection were retained by dyed wool after 20 washes. Furthermore, the dyed wool was found nontoxic under the cytotoxicity evaluation test.

Use of egg yolk phospholipids to improve the thermal-oxidative stability of fatty acids, capsaicinoids and carotenoids in chili oil

Phospholipids can act as antioxidants in food. In this study, egg yolk phospholipids (EPL) and sunflower oil were utilized in making chili oil, and proton nuclear magnetic resonance spectroscopy was employed to quantify the concentrations of fatty acyl groups, carotenoids, capsaicinoids in chili oil according to their specific signals in the spectra. The results showed that the changes in the concentrations of fatty acyl groups in the control samples were greater than those in the EPL-treated samples at the same frying temperature, while the contents of carotenoids and capsaicinoids were significantly lower than those of the EPL-treated samples when fried at 150 °C (p < 0.05). Two-way ANOVA indicated that frying temperature and EPL treatment, as well as their interaction had significant impacts on the thermal-oxidative stability of chili oil (p < 0.05). The results suggest that EPL may act as antioxidants during frying, and EPL can improve the thermal-oxidative stability of chili oil.

Novel axially di-substituted natural, cationic and zwitter ionic silicon phthalocyanine derivatives: Synthesis, characterization, sono-photochemical properties

This study focuses on investigating the sono-photophysicochemical properties of recently synthesized and characterized di-axially substituted silicon phthalocyanine complexes, incorporating schiff-base groups and zwitter ions, imparting novel features and potential therapeutic applications. Specifically, our research focused on evaluating the suitability of these complexes for photodynamic therapy (PDT), sonodynamic therapy (SDT), and the emerging field of sono-photodynamic therapy (SPDT). The characterization process involved the application of various analytical techniques, including UV–Vis spectroscopy, infrared (FT-IR) spectroscopy, and proton nuclear magnetic resonance (1H NMR) spectroscopy. Experimental results displayed highly promising outcomes, revealing that the synthesized sensitizers exhibited exceptional efficiency in generating reactive oxygen species, a critical attribute necessary for effective therapeutic interventions. This finding significantly contributes to the development of novel therapeutic agents with enhanced photodynamic and sonodynamic properties. Harnessing the power of light and sound simultaneously through sonophotodynamic therapy offers a unique and synergistic approach, potentially amplifying the therapeutic efficacy of these complexes. The combination of sonochemical and photochemical applications produced better results, for the studied compounds, the quaternized complexes (cationic compounds) showed the higher result. Overall, the results suggest that SPDT is a promising combination therapy for cancer treatment.

ABC block copolymer micelles driving the thermogelation: Scattering, imaging and spectroscopy

Thermoresponsive polymers have attracted much scientific attention due to their capacity for temperature-driven hydrogel formation. For biomedical applications, such as drug delivery, this transition should be tuned below body temperature to facilitate controlled and targeted drug release. We have recently developed a thermoresponsive polymer that forms gel at low concentrations (2 w/w%) in aqueous media and offers a cost-effective alternative to thermoresponsive systems currently being applied in clinics. This polymer is an ABC triblock terpolymer, where A, B, and C correspond to oligo(ethylene glycol) methyl ether methacrylate with average Mn 300 g mol−1 (OEGMA300), n-butyl methacrylate (BuMA), and di(ethylene glycol) methyl ether methacrylate (DEGMA). To investigate the self-assembly and the gelation mechanism in diluted solutions, we used small-angle neutron scattering (SANS) on 1 w/w% (below the gelation concentration) and 5 w/w% solutions (above the gelation concentration). As a comparison, we also investigated the solutions of the most studied thermoresponsive polymer, namely, Pluronic F127, an ABA triblock bipolymer made of ethylene glycol (A) and propylene glycol (B) blocks. SANS revealed that the in-house synthesised polymer forms elliptical cylinders, whose length increases significantly with temperature. In contrast, Pluronic F127 solutions form core-shell spherical micelles, which slightly elongate with temperature. Transmission electron microscopy images support the SANS findings, with tubular/worm structures being present. Variable-temperature circular dichroism (CD) and proton nuclear magnetic resonance (1H NMR) spectroscopy experiments reveal insights on the tacticity, structural changes, and molecular origin of the self-assembly.

Enhancing Corrosion Resistance of Mild Steel in 1M HCl: Investigation of New Benzoxazepine Derivatives Through Synthesis, Electrochemical Analysis, Surface Analysis, XPS, DFT, and Molecular Dynamics Simulation

AbstractThis research delineates the corrosion inhibitory efficiency of two newly synthesized benzoxazepine derivatives – [3,3‐dimethyl‐11‐phenyl‐3,4,5,11‐tetrahydrodibenzo[b,e] [1,4]oxazepine‐1(2 H)‐one (S1)] and [11‐(4‐chlorophenyl)‐3,3‐dimethyl‐3,4,5,11‐tetrahydrodibenzo[b,e][1,4]oxazepine‐1(2 H)‐one (S2)] – on mild steel in 1M HCl milieu. These derivatives were characterized by proton (1H NMR) and carbon (13C NMR) nuclear magnetic resonance spectroscopy. The experimental approach encompassed potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) techniques. The corrosion inhibition efficacy of S1 and S2 was concentration‐dependent, with their efficiencies peaking at 92.0 % and 92.1 %, respectively, at a 10−3 M concentration. Surface characterization, conducted using scanning electron microscopy (SEM), energy‐dispersive X‐ray analysis (EDS), X‐ray diffraction (XRD), contact angle measurements, and X‐ray photoelectron spectroscopy (XPS), corroborated the formation of a protective barrier layer on the mild steel surface. Additionally, using an inductive approach, UV‐visible spectrometry was employed to elucidate the adsorption behaviors of these inhibitors on the steel surface. Density functional theory (DFT) and molecular dynamics (MD) simulations were utilized to decipher the interaction mechanisms and adsorption modalities, unveiling critical insights into the interactions of S1 and S2 with the mild steel surface. This comprehensive analysis highlights the robust corrosion inhibition potential of the newly synthesized benzoxazepine derivatives and illuminates their prospective utility as effective inhibitors for mild steel in corrosive environments.

Synthesis and characterization of novel β-CD-Xanthate and its application in the treatment of heavy metal containing wastewater and lignin enriched paper industry wastewater

ABSTRACT Three grades of β-cyclodextrin xanthates (β-CDXs) have been synthesized by the reaction of β-cyclodextrin (β-CD) with CS2 in alkaline medium (NaOH), through xanthation process. The synthesized β-CDXs has been characterized by UV-visible (UV-Vis) spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy, Proton Nuclear Magnetic Resonance (1HNMR) spectroscopy, Thermogravimetric (TG) analysis, Differential Scanning Calorimetry (DSC) analysis, scanning electron microscopy (SEM) analysis and point of zero charge (ΔpHPZC) analysis. Further, β-CDXs and raw β-CD has been used for the heavy metals removal (Cu2+ and Ni2+) and also used for the treatment of lignin enriched paper industry wastewater (LEPIW). The maximum % removal by β-CDX3 for Cu2+ ion at optimum dosage of 2 g/L, optimum pH of 6.5, temperature of 45°C, initial concentration of 1000 mg/L and at contact time of 80 min was 95.8%. For Ni2+ ion the maximum % removal by β-CDX3 at optimum dosage of 2.5 g/L, optimum pH of 5.8, initial concentration of 1000 mg/L, temperature of 55°C and contact time of 100 min was 94.1%. While LEPIW treatment efficacy of 86% has been observed with β-CDX3. The calculated data fitted well in Langmuir isotherm model confirming that the adsorption of Cu2+ & Ni2+ ions onto the β-CDXs adsorbent is monolayer. The rate of adsorption of heavy metals (Cu2+ and Ni2+) on the β-CDXs adsorbent has been controlled by Pseudo second order kinetic model indicating the chemisorption process. The optimal adsorption capacity of β-CDX3 has been found to be 534.75 mg/g for Cu2+ and 423.72 mg/g for Ni2+ ions, respectively.