1H Nuclear Magnetic Resonance Spectroscopy Research Articles

An Automated Purification Workflow Coupled with Material-Sparing High-Throughput 1H NMR for Parallel Medicinal Chemistry.

In medicinal chemistry, purification and characterization of organic compounds is an ever-growing challenge, with an increasing number of compounds being synthesized at a decreased scale of preparation. In response to this trend, we developed a parallel medicinal chemistry (PMC)-tailored platform, coupling automated purification to mass spectrometry (MS) and nuclear magnetic resonance spectroscopy (NMR) on a range of synthetic scales (∼3.0-75.0 μmol). Here, the generation and acquisition of 1.7 mm NMR samples is fully integrated into a high-throughput automated workflow, processing 36 000 compounds yearly. Utilizing dead volume, which is inaccessible in conventional liquid handling, NMR samples are generated on as little as 10 μg without consuming material prioritized for biological assays. As miniaturized PMC synthesis becomes the industry standard, we can now obtain quality NMR spectra from limited material. Paired with automated structure verification, this platform has the potential to allow NMR to become as important for high-throughput analysis as ultrahigh performance liquid chromatography (UPLC)-MS.

Longifolene-Derived Primary Amine Carboxylates for Sustainable Weed Management: Synthesis and Herbicidal Activity.

Twelve novel longifolene-derived primary amine carboxylates were synthesized and evaluated for herbicidal activity. The structures of title compounds were confirmed by Fourier-transform infrared spectroscopy, 1H nuclear magnetic resonance (NMR), 13C NMR, and high-resolution mass spectrometry. The results showed that all the synthesized compounds exhibited higher herbicidal activity than the corresponding carboxylic acids involved in the reaction and the commercial herbicide glyphosate; some of them even possessed inhibition rates of 100% against Lolium multiflorum Lam. and Brassica campestris at low concentrations (0.039-0.313 mmol/L). Moreover, structural factors, including types of carboxylates and carbon chain length, had a great influence on the herbicidal performance. The herbicidal activity of dicarboxylates was similar to or much higher than that of corresponding monocarboxylates and glyphosate. Furthermore, compound 5l was found to be the most active candidate against the root and shoot growth of L. multiflorum Lam. and B. campestris with half maximal inhibitory concentrations (IC50) of around 0.010 and 0.023 mmol/L. The present work indicated that those prepared compounds have great potential to serve as high-performance botanical herbicides used at low doses.

Automatic Chemical Profiling of Wine by Proton Nuclear Magnetic Resonance Spectroscopy.

We report the development of MagMet-W (magnetic resonance for metabolomics of wine), a software program that can automatically determine the chemical composition of wine via 1H nuclear magnetic resonance (NMR) spectroscopy. MagMet-W is an extension of MagMet developed for the automated metabolomic analysis of human serum by 1H NMR. We identified 70 compounds suitable for inclusion into MagMet-W. We then obtained 1D 1H NMR reference spectra of the pure compounds at 700 MHz and incorporated these spectra into the MagMet-W compound library. The processing of the wine NMR spectra and profiling of the 70 wine compounds were then optimized based on manual 1H NMR analysis. MagMet-W can automatically identify 70 wine compounds in most wine samples and can quantify them to 10-15% of the manually determined concentrations, and it can analyze multiple spectra simultaneously, at 10 min per spectrum. The MagMet-W Web server is available at https://www.magmet.ca.

Electroacupuncture at different frequencies improves visceral pain in IBS rats through different pathways.

The aim of this study was to investigate the frequency dependence of electroacupuncture (EA) in alleviating chronic visceral pain in patients with irritable bowel syndrome (IBS) and the differences in the gut microbiota and metabolites as potential mechanisms to explain frequency dependence. A visceral hyperalgesia model was established by colorectal instillation of 2,4,6-trinitrobenzene sulfonic acid in rats, and EA treatment at 2/10 Hz, 2/50 Hz and 2/100 Hz was applied at ST25. Visceral sensation was quantified by the abdominal withdrawal reflex score and the area under the curve of the rectus abdominis electromyogram in response to colorectal distension. Ultrastructural morphological damage of colonic tissue of the rats was examined by transmission electron microscopy. 16S rRNA gene sequencing and 1H-nuclear magnetic resonance spectroscopy were applied to study the differences in the gut microbiota and to perform metabonomic profiling of the colonic tissue. EA at ST25 at different frequencies attenuated chronic visceral pain, ultrastructural morphological damage to colonic tissue and disruption of the gut microbiota in IBS rats. The frequency of 2/100 Hz has more regulatory pathways than 2/10 Hz and 2/50 Hz. In addition, IBS rats exhibited colonic metabolic disorders, and pantothenate was significantly upregulated after EA treatment at different frequencies. Very low-density lipoprotein and 2-hydroxybutyrate were significantly increased in the 2/10 Hz group, while low density lipoprotein, very low-density lipoprotein, 2-hydroxybutyrate, methylmalonate and alpha-hydroxyisobutyric acid were significantly increased in the 2/100 Hz group. EA at ST25 at different frequencies attenuated chronic visceral pain through different gut microbiota and metabolic pathways.

Synthesis and characterisation of mixed oxides of Co–Ni catalyst and its application in microwave mediated synthesis of Benzo[b]Pyrans

We present an easy and sustainable procedure for the productive preparation of tetrahydrobenzo[b]pyran derivatives by means of many compounds condensation of dimedon, malononitrile and several aromatic aldehydes utilizing mixed bimetallic oxides of Co–Ni as a catalyst under microwave irradiation. Present protocol involves green synthesis of mixed Co–Ni oxide catalyst using milky latex of Euphorbia neriifolia. The prepared mixed Co and Ni oxide was analyzed by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier Transform Infra-Red Spectroscopy (FT-IR), Energy Dispersive X-ray Analysis (EDAX), X-ray Photoelectron Spectroscopy (XPS) & Brunauer-Emmett- Teller Analysis (BET). This green approach's significance is demonstrated by its one-pot synthesis, convenient without use of solvent shows good isolated yields. Multiple analytical techniques such as Fourier transform infrared spectroscopy (FT-IR), 1H and 13C nuclear magnetic resonance (NMR) spectroscopy are utilized to derive the structural properties. The mixed metal oxides of Co and Ni was found to be catalytically active and can be reused 12 times without significant loss of catalytic activity.

Synthesis, characterization and antioxidant screening of a 1,10-phenanthroline-based tetraza-macrocyclic ligand and its nickel complex with therapeutic potential and catalytic significance

Abstract In this study, we present a synthetic route for the preparation of a novel 1,10- phenanthroline-based tetraza-macrocyclic ligand, 5,12,25,28-tetraazaheptacyclo [14.8.4.2⁴,⁷.210,13.0⁶,11.019,27.022,26]dotriaconta-1 (25),4,6,8,10,12,16(28),17,19(27),20,22(26),23,29, 31-tetradecaene, 3 and its corresponding nickel complex, (28Z)-1,3,6,31-tetraaza-2-nickelaoctacyclo [17.9.3.2⁷,28.0³,16.0⁴,13.0⁵, 10.022,30.025,29]tritriaconta-4(13),5(10),6,8,11,14,16,19(31),20,22(30), 23,25(29),26,28(32)-tetradecaene, 8. The ligand was synthesized via a condensation reaction involving 2,9-dimethyl-1,10-phenanthroline and 2,9-dicarbaldehyde-1,10 phenanthroline, followed by nickel metal complexation. Fourier-transformed infrared (FT-IR) spectroscopy, gas chromatography-mass spectrometry (GC-MS), 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and thermal analyses were employed to characterize the ligand and its Ni complex. Their ADMET parameters and potential macromolecular targets calculations showed they have therapeutic potentials. The antioxidant assay shows that Ni-complex is approximately 9 times more potent than the ligand with IC50 values of 0.045 mg/ml and 0.404 mg/ml, respectively. Their microspecies distribution which was predicted using ChemAxon Predictor revealed their catalytic potentials The reaction mechanisms involved are discussed. The 1,10-phenanthroline-based macrocyclic ligand and its nickel complex significantly expand the structural diversity within the tetraza-macrocyclic ligand system and serve as base ligands for the development of possible derivatives, with concomitant applicability in drug development and catalysis.

Backbiting-minimized synthesis of fluorosilicone copolymers with promoter by anionic ring-opening polymerization

A back-biting reaction in fluorosilicone synthesis can compromise its precision–manufactured mechanical properties and deteriorate its molecular properties. This phenomenon can potentially disrupt the intricate structure of fluorosilicone, diminishing its durability and altering its properties over time. Cyclosiloxane with methyl and vinyl groups was added to overcome the limited properties of poly[methyl(trifluoropropyl)siloxane] and conventional rubber for harnessing versatile materials, such as vehicles and spacecraft. In this study, dimethyl carbonate, diethyl carbonate, and allyl methyl carbonate were used as promoters to suppress back-biting reactions, and an improved fluoro-vinyl-methyl silicone (FVMQ) was synthesized. 29Si nuclear magnetic resonance (NMR) spectroscopy showed that the cyclic by-products from the back-biting reaction were inhibited by adding carbonate materials. Moreover, the conversion of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane also increased as the amount of promoter increased. The roles of varying carbonate promoters in altering the properties of FVMQs were studied using 1H NMR spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. Furthermore, the intermediate of FVMQs was prepared and analyzed using Fourier transform infrared spectroscopy, 1H NMR spectroscopy, and gel permeation chromatography to determine the mechanism of suppressing back-biting. The results showed that controlled synthesis of FVMQs by inhibiting the production of cyclic by-products with promoters will improve silicone polymer synthesis and the vehicle industry requiring high yields of fluorosilicone copolymers.

Characteristics of phosphorus‑nitrogen based flame-retardant monomers for UV-curable coatings on battery PET pouches

In this study, photocurable monomers containing phosphorus–nitrogen groups were employed alongside UV curing technology to develop flame-retardant (FR) coatings pouch-type battery cells made from polyethylene terephthalate (PET). Three different monomers were synthesized: a phosphorus-containing urethane acrylate monomer (DUPPO), a phosphorus–nitrogen-containing urethane acrylate monomer (DA-Pi-U), and a phosphazene-containing phenyl methacrylate crosslinker (CP-PMA). These monomers, recognized for their flame-retardant properties, were utilized in binary and ternary coating formulations that were effectively cured via a UV-curing process. The molecular architectures of the synthesized monomers were verified through 1H and 31P nuclear magnetic resonance spectroscopy. The rheological curing behavior of the coating solutions was assessed using an oscillatory rheometer. In addition, the reactivity of the FR coating system was examined via Fourier transform infrared spectroscopy. The thermal and flame-retardant characteristics of the FR coatings were confirmed through thermogravimetric analysis, Raman spectroscopy, limiting oxygen index measurements, and scanning electron microscopy. The ternary FR coating system with CP-PMA exhibited superior thermal stability, flame retardancy, crosslinking density, and mechanical robustness, making it suitable for PET pouches. Furthermore, optimal coating conditions for the slot coating process were determined using a viscocapillary model, enhancing practical applicability in industrial settings.

Physicochemical properties of binary mixtures of cation-fluorinated ionic liquids with their non-fluorinated analogues

This work reports an investigation of the physicochemical properties (density, viscosity, refractive index and thermal stability) of four binary mixtures having a common acetate ([OAc]¯), trifluoromethanesulfonate ([OTf]¯) or bis(trifluoromethylsulfonyl)imide ([NTf2]¯) anion with either cation-fluorinated and non-fluorinated methylimidazolium (MIm) or pyridinium (Py) cations respectively, at various temperatures. The mixing behaviour of the binary mixtures was analysed by 1H and 19F Nuclear magnetic resonance (NMR) spectrometry, and the excess properties of the mixtures were calculated from the physicochemical data. The binary mixtures of fluorinated ionic liquids (FILs) with their non-fluorinated or alkyl-substituted analogues (AILs) showed an increase in density and viscosity but a decrease in refractive index with an increase in mole fraction of the pure FILs. The thermal stability of the AILs was higher than the FILs, however, an increase in the mole fraction of the pure FILs in the binary mixtures made a negligible impact on the thermal stability of the binary mixtures. These binary mixtures were found to deviate from ideal behaviour for the different physicochemical properties tending to vary between the extremes of the pure components. The large differences in properties of FILs compared with their non-fluorinated analogues were shown to be associated with the size of the fluorine atoms in the fluoro-alkyl chain, the tendency of the fluoro-alkyl chain to form aggregates with fluorinated anions, and the hydrogen bond acceptor strength of the anions. The excess properties were fitted to the Redlich-Kister polynomial equation, and no significant deviation was obtained. This study shows that the physicochemical properties of the fluorinated ionic liquids can conveniently be adjusted for specific applications by simply varying the amount of the cation-fluorinated component in binary mixtures.

L-Ornithine derivatives with structural hetaryl and alkyl moiety: Synthesis and antibacterial activity

Objectives. Cationic amphiphiles and antimicrobial peptidomimetics are widely investigated as antibacterial agents due to their membrane-active mechanism of action. Particular attention is focused on the rational design of compounds in this class to achieve high antimicrobial activity. The aim of the present work is to synthesize bivalent cationic amphiphiles with L-ornithine as a branching element and evaluate the effectiveness of their antibacterial action. The compounds differ in terms of hydrophobicity due to the variation of N-terminal aliphatic amino acids in the polar block and alternation of dialkyl and alkyl-hetaryl radicals in the lipophilic block.Methods. For the synthesis of nonpolar fragments of amphiphiles, methods for the alkylation of amines with alkyl bromides in the presence of carbonate salts were used. The formation of amide bonds of L-ornithine derivatives with amino acids was carried out using the carbodiimide method. For the reaction products recovery from the reaction mixture, column chromatography on silica gel and aluminum oxide activated Brockmann Grade II was used. The antimicrobial activity of the synthesized compounds against gram-positive B. subtilis 534 and gram-negative E. coli M17 bacterial strains was evaluated. Minimum inhibitory concentration (MIC) values were recorded using a serial microdilution method in a nutrient medium.Results. Developed schemes for the preparation of bivalent cationic amphiphiles based on L-ornithine derivatives are presented. Differences in the structure of aliphatic amino acids (glycine, β-alanine, γ-aminobutyric acid (GABA)), in the length of alkyl radicals (C8, C12), or in the presence of an indole moiety, were used in the design of target compounds. The high antibacterial activity of the synthesized compounds was demonstrated. The most active compounds were lipoamino acids with terminal GABA residues and asymmetrical non-polar block (tryptamyl–dodecylamine). The MIC values were 0.39 μg/mL for gram-positive bacteria and 1.56 μg/mL for gram-negative bacteria. A GABA derivative with a symmetrical lipophilic moiety based on dioctylamine demonstrated activity with an MIC of 0.78 μg/mL against B. subtilis and 3.12 μg/mL against E. coli.Conclusions. Nine new lipoamino acid cationic bivalent amphiphiles based on L-ornithine were synthesized. The structure of the obtained compounds was confirmed by nuclear magnetic resonance 1H spectroscopy and mass spectrometry data. Leading compounds in antimicrobial activity against both gram-positive and gram-negative strains of bacteria were determined. The influence of the degree of lipophilicity in the asymmetric nonpolar block on the level of exhibited antimicrobial activity is demonstrated.

Electroactive additives into polyurethanes for high corrosion resistance coatings for mild steel

AbstractThere is a demand for innovative coatings such as polyurethane (PU) in industrial and commercial sectors to effectively combat corrosion on mild steel substrates. In this work, novel redox‐active polyurea (PUr) additives such as PUr‐diamine capped trimer (DCTA) and PUr‐diamine‐capped tetraaniline (DCTAni), derived from DCTA and DCTAni, were synthesized to enhance the anticorrosion properties of PU coatings. These are characterized using 1H nuclear magnetic resonance spectroscopy, Fourier transformed infrared, and high‐resolution mass spectrometry technical methods. These additives (2, 5, and 10 wt%) were dispersed in a polyurethane‐urea (PUU) matrix, which was synthesized from PTMG‐2000, and IPDI with dihydrazide adipate as a chain extender. The electroactivity of the coatings were evaluated using cyclic voltammetry (CV) and ultraviolet–visible spectroscopy. Furthermore, anticorrosion performance was assessed through electrochemical impedance spectroscopy and Tafel potentiodynamic polarization measurements. The optimal corrosion protection was achieved with increasing weight percent (wt%) of additive in PUU, showing a trend of 10% > 5% > 2%. Coatings reported maximum polarization resistance (Rp) of 122.15 MΩ, with corrosion rates (CR) as low as 2.38 × 10−6 mm/year. Accelerated salt spray testing over 600 h in a 5 wt% NaCl salt fog confirmed the coatings' durability. The microstructures of PUr particles were determined through FESEM characterization. Additive‐blended PUUs exhibited moderate tensile strength and elongation at break compared to the reference PUU matrix. The hydrophobicity of both the reference sample (PUU) and the additive‐blended coatings was measured, with the highest recorded value being at 93.1 ± 0.048 for 10 wt%. Thermal gravimetric analysis demonstrated polymer degradation with a maximum of T5% observed at 304.1°C.

Carbazole derivatives as antioxidant and anticorrosion materials

In this study, a series of new carbazole derivatives were studied using several reactions, including the Vilsmeier–Haack reaction. A cyclization reaction within bromoacetic acid was reported to synthesize thiazolidinone compounds, followed by the Mannich reaction by reacting the prepared compound with formaldehyde and secondary amines, that is, diphenylamine, morpholine, and phthalimide. All synthesized compounds were characterized by infrared spectroscopy, liquid chromatography–mass spectrometry, and 1H and 13C nuclear magnetic resonance spectroscopy. The antioxidant activities of all prepared compounds were studied using the free-radical scavenging method using 2,2-diphenyl-1-picrylhydrazyl, demonstrating their moderate activity compared with ascorbic acid as the standard substance. The effectiveness of the prepared compounds as corrosion inhibitors was studied in an acidic medium of sulfuric acid (0.25 mol/L) using the electrochemical method. Acceptable corrosion-inhibition efficiency was achieved, with the highest inhibition rate of 55.21 % for compound VII.

Comprehensive analysis of alcohol compounds in commercial instant coffee: A validated 1H NMR spectroscopy study within the Islamic paradigm

Coffee, a globally consumed beverage, has raised concerns in Islamic jurisprudence due to the possible presence of alcohol compounds. This research aims to utilise the sensitivity and reliability of 1H NMR spectroscopy in the quantification of alcohol compounds such as ethanol, furfuryl alcohol, and 5-(hydroxymethyl) furfural (HMF) in commercial instant coffee. Analysis of seven products was performed using advanced 1H Nuclear Magnetic Resonance (NMR) spectroscopy together with Statistical Total Correlation Spectroscopy (STOCSY) and Resolution-Enhanced (RED)-STORM. The analysis of the 100 mg sample revealed the absence of ethanol. The amount of furfuryl alcohol and HMF in the selected commercial instant coffee samples was 0.817 μg and 0.0553 μg, respectively. This study demonstrates the utility of 1H NMR spectroscopy in accurate quantification of trace components for various applications.

Mesoporous MPC@TMG, a basic heterogeneous organocatalyst in C–C/C–N bond forming reactions: Tandem multicomponent synthesis of 5-amino-pyrazole-4-carbonitriles and 1H-pyrazolo [1,2-b] phthalazine-5, 10-dione derivatives under sustainable reaction conditions

A metal-free, effective, and sustainable protocol has been developed to carry out C–N and C–C bond-forming reactions leading to the formation of 5-amino-pyrazole-4-carbonitriles and 1H-pyrazolo [1,2-b] phthalazine-5, 10-dione derivatives via a tandem multicomponent reaction using mesoporous MPC@TMG as a basic heterogeneous organocatalyst. The reactions were performed in aqueous medium at room temperature. The synthesized organocatalyst MPC@TMG was characterized by numerous spectroscopic techniques such as Fourier Transform Infrared (FTIR), Powder X-ray diffraction (PXRD), Brunauer-Emmett-Teller (BET), Scanning Electron Microscope (SEM), Energy Dispersive X-ray (EDX), elemental mapping, and Thermal Gravimetric (TG) analyses. MPC@TMG displayed excellent catalytic potential, high thermochemical stability, and reusability for up to eight catalytic runs and offered the title compounds in excellent yields (>90 %) in a short reaction time (6–15 min). The synthesized compounds were characterized through FTIR, 1H, and 13C Nuclear Magnetic Resonance (NMR) spectroscopy. The use of water as a green solvent, the generality of the method, easy catalyst recovery, a simple work-up procedure, and zero involvement of any metal are the key features of the present protocol making it green and sustainable for the synthesis of the desired heterocycles and is supported by the calculations for green metrics parameters.

Complex Characterization of Nanofiber Biomaterials Based on Chitosan, Collagen and Fish Gelatine Produced by Electrospinning*

Electrospinning is an increasingly used technique for producing nanofibers from various types of polymers and biopolymers. These fibers are suitable for applications in tissue engineering, wound healing and drug delivery. In this study, we focused on biomaterials produced from raw marine fish collagen, fish gelatin and chitosan. Various collagen/chitosan and fish gelatin/chitosan in several ratios were dissolved in acetic acid. The formed solutions have concentrations in the range from 5 to 90% (g/ml). The effect of different molecular formats (native and denatured collagen) was studied. The prepared solutions were used in electrospinning experiments. The order degree of various phases of raw materials was established from x-ray diffraction (XRD) measurements. The raw materials, bio-polymeric solutions and finite nanofibers biomaterials were characterized using Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), low-field 1D NMR (nuclear magnetic resonance) relaxometry, 2D NMR T1-T2 COSY (correlation spectroscopy), T1-T2 EXSY (exchange spectroscopy) maps, and high field localized 1H NMR spectroscopy. The T 2-T 2 EXSY experiments showed that the number of components characterized by distinct dynamics is larger than those that can by estimated from 1D T 2-distributions due to molecular exchange. Moreover, the full complexity was also revealed by T 1-T 2 COSY maps. The study provides a better understanding of the nanofiber properties, demonstrates the potential of electrospinning for producing nanofibers, and highlights the importance of using multiple characterization methods for a better understanding of the properties of biological nanofibers.

Micro(nano)plastics from synthetic oligomers persisting in Mediterranean seawater: Comprehensive NMR analysis, concerns and origins

The presence in seawater of low-molecular-weight polyethylene (PE) and polydimethylsiloxane (PDMS), synthetic polymers with high chemical resistance, has been demonstrated in this study for the first time by developing a novel methodology for their recovery and quantification from surface seawater. These synthetic polymer debris (SPD) with very low molecular weights and sizes in the nano- and micro-metre range have escaped conventional analytical methods. SPD have been easily recovered from water samples (2 L) through filtration with a nitrocellulose membrane filter with a pore size of 0.45 μm. Dissolving the filter in acetone allowed the isolation of the particulates by centrifugation followed by drying. The isolated SPD were analysed by 1H nuclear magnetic resonance spectroscopy (1H NMR), identifying PE and PDMS. These polymers are thus persisting on seawater because of their low density and the ponderal concentrations were quantified in mg/m3. This method was used in an actual case study in which 120 surface seawater samples were collected during two sampling campaigns in the Mediterranean Sea (from the Gulf of Salerno to the Gulf of Policastro in South Italy). The developed analytical protocol allowed achieving unprecedented simplicity, rapidity and sensitivity. The 1H and 13C NMR structural analysis of the PE debris indicates the presence of oxidised polymer chains with very low molecular weights. Additionally, the origin of those low molecular weight polymers was investigated by analysing influents and effluents from a wastewater treatment plant (WWTP) in Salerno as a hot spot for the release of SPD: the analysis indicates the presence of low molecular weight polymers compatible with wax-PE, widely used for coating applications, food industry, cosmetics and detergents. Moreover, the origin of PDMS debris found in surface seawater can be ascribed to silicone-based antifoamers and emulsifiers.

Furcellaran: Impact of Concentration, Rheological Properties, and Structure on Ice Recrystallization Inhibition Activity.

Recrystallization is considered the main damaging mechanism during the frozen storage of biologic materials. In this study, furcellaran, a polysaccharide related to κ-carrageenan, was studied for its concentration-dependent effect on ice crystal growth and recrystallization. The structure and sulfate content of the utilized furcellaran was analyzed by 1H nuclear magnetic resonance spectroscopy, ion chromatography, and high-performance size-exclusion chromatography. Additionally, the rheological properties of furcellaran solutions were investigated. Our findings demonstrate that furcellaran inhibits ice growth as effectively as κ-carrageenan. Furthermore, the rheological properties change with increasing furcellaran concentration, resulting in a gel-like consistency at 5 g/L, which coincides with decreased recrystallization inhibition activity and larger crystals. This suggests that gel formation or a gel-like consistency has to be avoided for optimal recrystallization inhibition activity.

Hydrophilically-modified poly(ε-caprolactone) with zwitterionic sulfobetaine/tertiary amine and their self-assemblies in water

To achieve hydrophilic modification of poly(ε-caprolactone) (PCL), a series of amphiphilic copolymers, poly(ε-caprolactone)-b-poly(N,N-dimethylaminoethyl methacrylate-co-sulfobetaine methacrylate) (PCDSs), were synthesized with varying sulfobetaine compositions using a three-step synthetic strategy. Firstly, the hydroxyl-terminated polymer, PDMAEMA-OH was synthesized through free radical polymerization using AIBN as an initiator and 2-mercaptoethanol as a chain transfer agent. Subsequently, the block copolymer poly(ε-caprolactone)-b- poly(N,N-dimethylamino ethylmethacrylate) (PCD) was prepared through ring-opening polymerization of PDMAEMA-OH and ε-caprolactone employing Sn(OCt)2 as the catalyst. Finally, zwitterionization of the tertiary amine groups in PCD was achieved by treating it with 1,3-propane sultone (1,3-PS) in THF to obtain the desired PCDSs copolymers. The chemical compositions and the structures of PCDSs were confirmed by 1H nuclear magnetic resonance (1H NMR) spectroscopy and gel permeation chromatography (GPC). Additionally, self-assembly behavior in water was systematically investigated for both PCD and PCDSs copolymers. The results showed that these copolymers could form stable, pH-responsive micelles with diameters less than 150 nm via solvent evaporation method while also exhibiting efficient loading and release capabilities for the anti-tumor drug doxorubicin (DOX). Furthermore, cytotoxicity assay revealed low cell cytotoxicity of PCDS micelles towards L929, HeLa, and MCF-7 cells; however DOX-loaded PCDS micelles (PCDS/DOX), particularly those composed of 47% sulfobetaine content exhibited significant inhibitory effects on HeLa and MCF-7 cells along with enhanced cellular uptake efficiency. These findings highlight that pH-responsive zwitterionic sulfobetaine-based polymeric micelles derived from the PCDSs hold great promise for effective DOX delivery.

LC-QTOF/MS-Based Profiling of the Phytochemicals in Ice Plant (Mesembryanthemum crystallinum) and Their Bioactivities.

Recent assessments of the correlations between food and medicine underscore the importance of functional foods in disease prevention and management. Functional foods offer health benefits beyond basic nutrition, with fresh fruits and vegetables being particularly prominent because of their rich polyphenol content. In this study, we elucidated the phytochemicals in ice plant (Mesembryanthemum crystallinum), a globally consumed vegetable, using an LC-QTOF/MS-based untargeted detection method. The phytochemicals were clustered based on their structural similarity using molecular networking and annotated using the in silico tool for network annotation propagation. To identify the bioactive compounds, eight compounds were isolated from ice plant extracts. These compounds were identified using extensive spectroscopic methods, including 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. Additionally, we evaluated the antioxidant and anti-inflammatory activities of all the isolates. Among the tested compounds, three showed antioxidant activity and all eight showed anti-inflammatory activity, demonstrating the potential of ice plant as a functional food.

Impact of the delay in cryopreservation timing during biobanking procedures on human liver tissue metabolomics.

The liver is a highly specialized organ involved in regulating systemic metabolism. Understanding metabolic reprogramming of liver disease is key in discovering clinical biomarkers, which relies on robust tissue biobanks. However, sample collection and storage procedures pose a threat to obtaining reliable results, as metabolic alterations may occur during sample handling. This study aimed to elucidate the impact of pre-analytical delay during liver resection surgery on liver tissue metabolomics. Patients were enrolled for liver resection during which normal tissue was collected and snap-frozen at three timepoints: before transection, after transection, and after analysis in Pathology. Metabolomics analyses were performed using 1H Nuclear Magnetic Resonance (NMR) and Liquid Chromatography-Mass Spectrometry (LC-MS). Time at cryopreservation was the principal variable contributing to differences between liver specimen metabolomes, which superseded even interindividual variability. NMR revealed global changes in the abundance of an array of metabolites, namely a decrease in most metabolites and an increase in β-glucose and lactate. LC-MS revealed that succinate, alanine, glutamine, arginine, leucine, glycerol-3-phosphate, lactate, AMP, glutathione, and NADP were enhanced during cryopreservation delay (all p<0.05), whereas aspartate, iso(citrate), ADP, and ATP, decreased (all p<0.05). Cryopreservation delays occurring during liver tissue biobanking significantly alter an array of metabolites. Indeed, such alterations compromise the integrity of metabolomic data from liver specimens, underlining the importance of standardized protocols for tissue biobanking in hepatology.