1H NMR Spectroscopy Research Articles

Design, Synthesis and in Silico Studies of New 2-MethylQuinazolin-4(3H)- Ones Derivatives

The concept of the green chemistry consists in the development of an environmentally friendly approach for organic synthesis using ecological and efficient protocols. In order to develop a methodology that could fit into the green chemistry field, for the synthesis of new quinazolin-4(3H)-ones derivatives via benzoxazinone, the choice was made on the use of both as catalysts, known for their efficiency, and microwave irradiations for time saving.The quinazolinone core and its derivatives form an important class of compounds, as they are present in a large family of products with broad biological activities. They generally display useful therapeutic and pharmacological properties such as anti-inflammatory, anti-convulsant, antihypertensive and antimalarial activity.The derivatives of the 2-metylquinazolin-4(3H)-ones 3a-d series was synthesized from 2- methyl benzoxazin-4(3H)-one 1 and aniline in the presence of H3PW12O40 (PW12) under microwave irradiation and solvent free conditions. The compound structures were established using IR, 1H-NMR, 13C-NMR and mass spectroscopy. The toxicity of the hydrazone derivatives was studied through ADMET (Absorption, Distribution, Metabolism, Excretion, and Toxicity) simulations using ADMET Lab 2.0 server.

Design, Synthesis, and Invitro Pharmacological Evaluation of Novel Resveratrol Surrogate Molecules against Alzheimer's Disease.

A series of resveratrol surrogate molecules were designed, synthesized and biologically evaluated for inhibition of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) along with anti-oxidant activity as potential novel multifunctional agents against Alzheimer's disease (AD). Six novel compounds were synthesized by reacting (E)-4-(3,5-Dimethoxystyryl) aniline with benzaldehyde and some selected derivatives of benzaldehyde in the presence of ethanol and a few drops of glacial acetic acid which followed the general scheme involved in the formation of Schiff bases. The spectral analysis data including FT-IR, 1H-NMR, 13C-NMR, and Mass spectroscopy results were found to be in good agreement with the newly synthesized compounds (Resveratrol Surrogate Molecules 1-6). The synthesized compounds were evaluated for their dual cholinesterase inhibitory activities, cytotoxic effect, and anti-oxidant potential. The results showed that compound RSM5 showed potent inhibitory activity against AChE and BChE. In, addition the cytotoxicity of the compound RSM5 is less and found to be within the desirable limit indicating the potential safety of RSM5. Also, it possesses substantial anti-oxidant activity which qualifies RSM5 as an anti-AD agent. Taken together, these findings demonstrate that the molecule RSM5 had the most multifunctional properties and could be a promising lead molecule for the future development of drugs for Alzheimer's treatments.

Photoprocesses in Bis-Diethylamino Derivatives of 1,4- and 1,3-Distyrylbenzene.

The photoprocesses of diethylamino derivatives of 1,4- and 1,3-distyrylbenzenes in MeCN were studied using absorption, luminescence, 1H NMR, and laser kinetic spectroscopy. Compounds 1 and 2 undergo intersystem crossing to the triplet state and exhibit delayed fluorescence. It was concluded that dye radical anions and radical cations are formed upon dismutation of the triplet state in the presence of an electron donor or acceptor. Quantum mechanical calculations for the structures of diethylamino distyrylbenzenes in the ground and excited states were carried out, making it possible to establish the structures of isomers and the most stable conformers for both compounds.

RAPID AND AN EFFICIENT ONE-POT THREE-COMPONENT SYNTHESIS OF ISOXAZOLES PROMOTED BY CAS

A straightforward, practical, and economical process for producing isoxazole derivatives is described. It makes use of ethylacetoacetate, hydroxylamine hydrochloride, and substituted aromatic aldehydes with promoted camphor sulfonic acid as a catalyst in a solvent. No toxic organic solvents are used in the current procedure. Shortest reaction time, high product yields, easy work-up process, and non-chromatographic product purification are only a few of this catalysts encouraging reaction response characteristics. The derivatives of desired compounds were analyzed advanced spectroscopic data by 1H NMR, 13CNMR and mass spectrometry was used to verify the products structures. Products were chosen, and their antibacterial activity was examined.

Titanium Complex with New Schiff Base 4-(N, N-dimethylaminobenzylidene)-1- phenylsemicarbazide: Synthesis, Thermal, XRD, and Antibacterial properties

4-(N, N-dimethylaminobenzylidene) 1-phenylsemicarbazide Schiff base (SB) was synthesized from 1-phenylsemicarbazide and 4-(N,N-dimethylaminobenzaldehyde). Numerous analytical approaches, such as ele-mental analysis, 1HNMR, 13CNMR, electronic spectra, and FT-IR spectroscopy were utilized to analyze the newly synthesized Schiff base. The Ti (IV) Schiff base complex was produced, and its electrolytic nature, stability, and octahedral structural properties were determined by elemental, IR, UV-Vis spectral, conductivity, and thermal studies (TGA-DTA). From XRD results, the practical size of Schiff base and its complex were in the nano range with crystallinity structure. To evaluate the antibacterial activity, the free ligand and its complex were assessed in vitro against Pseudomonas aeruginosa, Escherichia coli, and Staphylococcus aureus. These results show that the metal complex has stronger antibacterial action than the Schiff base ligand.

Anion-pairing effect in Cd(II) coordination with a tetrabenzotetraza-crown macrocyclic ligand

Three new complexes of a tetrabenzotetraza-crown ether macrocyclic ligand (L) with Cd(II) chloride (1), iodide (2), and acetate (3) salts were synthesized and characterized by FT-IR, 1H NMR spectroscopy, elemental microanalysis, and single crystal X-ray diffraction. Complex 1 has the formula [Cd(L)Cl]2 [CdCl4] with two square pyramidal [Cd(L)Cl]+ subunits interconnected through the CdCl42− counter anion. Meanwhile, the reaction with CdI2 produces the discrete complex [Cd(L)I]I (2) with an octahedral geometry about the Cd(II) center. A distorted six-coordinated asymmetric unit was observed for [Cd(L)OAc]2(OAc·H2O)2 (3), wherein two [Cd(L)OAc]+ subunits are held together by a flat (OAc·H2O)2 acetate-water cluster. Hirshfeld Surface calculations were applied to confirm the dominant interactions in 1–3, namely π–π, and X⋯H/H⋯X (X-H, C, O, and halogen) interactions as the main factors for their structural differences. At the same time, the structure of [Cd(L)L′]+ (L′ = Cl, I, and OAc) core remained almost unchanged. The Cd(II) coordination with L in the presence of different Cd(II) salts was followed by 1H NMR spectroscopy. All three Cd(II) salt displays 1:1 stoichiometry, with binding constants in the order CdCl2 < CdI2 < Cd(OAc)2.

Synthesis, conformational analysis and host-guest chemistry of an ester-containing tub[4]arene with a conformational ensemble

Ester tub[4]arene, a conformationally adaptive macrocycle with interconvertible cavities, has been synthesized and characterized. Its conformational complexity was analyzed, and its binding ability to organic cations was studied by 1H NMR spectroscopy and UV–vis spectroscopy. The conformational conversion of the host can be achieved by binding a suitable guest. The binding performance of such adaptable receptors may have significant implications for the molecular recognition processes occurring in natural settings.

17O NMR spectroscopy protocol for the determination of water content in liquids produced by pyrolysis and hydrothermal liquefaction

BackgroundThere is an urgent need to replace fossil-based fuels and chemicals with bio-based, renewable alternatives. Water content is a critical parameter in these liquid products since water affects their quality and properties. However, currently existing methods for bio-oil water content determination have limitations and thus, there is a need to find methods that are versatile, work for a wide water content and sample consistency range repeatably and reliably and are safe for the user and the environment. ResultsIn this research, a17O NMR spectroscopy protocol for water content determination of pyrolysis and hydrothermal liquefaction (HTL) liquids was developed and compared with the standard method Karl Fischer (KF) titration. The approach showed linearity over a wide concentration range, and the changes to the measurement parameters caused only minor effects to the results (≤0.8 percentage points) indicating robustness. The method is also accurate since the absolute differences between experimental and theoretical water contents varied from 0.08 % to 2.09 %. Additionally, the precision of the method, based on the relative standard deviations (RSD) of the three replicate measurements of pyrolysis and HTL samples, was good (RSD <1.82 %). The method was applied to samples containing 1–98 wt% water. Overall, the 17O NMR spectroscopy and KF titration results were well aligned with each other suggesting that the 17O NMR spectroscopy is a potential alternative for the conventional KF titration. SignificanceThis is the first study on the use of 17O NMR spectroscopy protocol for water content quantification. The results indicate that the protocol is an accurate, linear, and precise technique for water content determination of a wide range of samples. Furthermore, the method does not require hazardous chemicals or calibration standards, and the sample preparation is straightforward. The non-destructiveness of the method also enables further studies on the sample, e.g. by 1H NMR spectroscopy.

Pyrazine bound, zinc 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin: Synthesis, crystal structure and computational studies

This work describes the synthesis, characterization, crystal structure, and computational analyses of the zinc porphyrin [ZnT(4-Cl)PP], 1 and its pyrazine bound analogue, [ZnT(4-Cl)PP(pyz)], 2, (where T(4-Cl)PP stands for 5,10,15,20-tetrakis-(4-chlorophenyl)porphyrin and pyz represents pyrazine). Both compounds were structurally characterized by UV–visible spectroscopy, infrared spectroscopy, 1HNMR spectroscopy, 13CNMR spectroscopy and single crystal XRD. The crystal structure of the 2 consists of a zinc porphyrin with an axial pyrazine ligand forming a penta-coordinated complex with Zn1-N5(pyz) distance 2.228(3) Å. To investigate the key insights into their photophysical properties, fluorescence emission spectral analysis of the synthesized compounds has been studied. Theoretical calculations like optimization of geometry, the energy of frontier orbitals, Hirshfeld surface analysis and simulation of electronic spectra were performed which supports the experimental results.

Naked eye Fe(III) recognition and anticancer efficacy evaluation via diazenyl-propargyl appended imine functionalized moiety

The study delves into the synthesis of diazenyl-propargyl appended imine functionalized moiety (4) emphasizing its structural dynamic, Fe(III) sensitivity, and anticancer potential. The synthesized compound was characterized via NMR (1H,13C), TGA, mass spectrometry, and single-crystal X-ray crystallography. The color transition of the compound from yellow to red demonstrates naked-eye sensing for Fe (III), validated by UV–visible spectroscopy. The limit of detection (LOD) and Association Constant (Ka) were calculated from the linear calibration curve and the B–H plot come out to be 28.71 nM and 2.17 × 105 M−1, respectively. As per Job’s plot Fe(III) binds to probe (4) in 1:1 stoichiometry. The interaction of probe (4) with Fe(III) has been examined through VSM (vibrating spectrum magnetism) study, FT-IR, 1H NMR and mass spectrometry. The pharmacokinetic properties of the synthesized compound were assessed, emphasizing absorption, distribution, metabolism, excretion and toxicity. The cytotoxicity assay using SAF-1 cell line indicated that the compound is nontoxic. Also compound (4) showed positive response on cervical cancer cells line and this anti-cancer potential has been further explored through molecular docking analysis.

Structure-property correlations study in biochar-enhanced polyamide composites for sustainable materials development

This study explores the synthesis and characterization of polyamide/biochar composites via in situ polymerization of 12-aminolauric acid with varying biochar concentrations. The motivation behind this research is to enhance the properties of polyamide 12 (PA12) by integrating biochar, a sustainable material derived from biomass, to improve both performance and environmental impact. A detailed structure-property correlation analysis was conducted to assess the effects of biochar on PA12's morphology, mechanical behavior, crystallinity, thermal stability, viscoelastic performance, and environmental sustainability. Key findings include successful PA12 synthesis, confirmed by FTIR and 1H NMR spectroscopy. Increased biochar content led to a decrease in molecular weight and an increase in crystallinity from 27 % to 38 %, suggesting enhanced nucleation effects. SEM analysis showed excellent dispersion and compatibility of biochar within the PA12 matrix, leading to significant improvements in tensile strength (from 38 ± 1 MPa to 54 ± 2 MPa) and modulus (from 745 ± 30 MPa to 2055 ± 65 MPa). Rheological tests demonstrated shear-thinning behavior, facilitating effective extrusion-based 3D printing of a complex object with 50 wt% biochar. A life cycle assessment revealed substantial environmental benefits, including a net reduction of 1.83 kg·CO₂ equiv.·kg⁻1 due to the use of biochar derived from wood pyrolysis. These findings highlight the potential of PA12/biochar composites as environmentally sustainable structural materials, combining enhanced functional properties with significant ecological advantages.

Metal ion complexes of 2-thioxoimidazolidine-4-one derivatives mixed ligand synthesis, characterization, in-vitro biological activities and in-silico studies

A series of complexes of [Mn (III), Co(II), Cu(II), and Cd(II)] were synthesized with two new 2-thioxoimidazolidin-4-one derivates ligands. These ligands were characterized using an elemental analyzer (CHNS), 1H NMR spectroscopy, FT-IR spectroscopy, and UV–Vis spectroscopy. The synthesized complexes were characterized by magnetic susceptibility measurements, electrical conductance analysis, and atomic absorption spectroscopy. The biological activity of the ligands and complexes were determined against E. coli, B. subtilis, A. niger, and P. chrysogenum. To determine the influence of different metal-ion concentrations on microbial growth, we used molecular docking to evaluate antibacterial activity targeting antimicrobial sites. Our findings indicate that the metal ion complexes exhibited varying degrees of antimicrobial activity, affecting the growth of the tested organisms.

Comparative study of metal-organic frameworks synthesized via imide condensation and coordination assembly.

A series of metal-organic frameworks (1-XDI) have been synthesized by imide condensation reactions between an amine-functionalized pentanuclear zinc cluster, Zn4Cl5(bt-NH2)6, (bt-NH2 = 5-aminobenzotriazolate), and organic dianhydrides (pyromellitic dianhydride (PMDA), naphthalenetetracarboxylic dianhydride (NDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (HFIPA)). The properties of the 1-XDI MOFs have been compared with analogues (2-XDI) prepared using traditional coordination assembly. The resulting materials have been characterized by ATR-IR spectroscopy, acid-digested 1H NMR spectroscopy, elemental analysis, and gas adsorption measurements. N2 adsorption isotherm data reveal modest porosities and BET surface areas (30-552 m2 g-1). All of the new 1-XDI and 2-XDI MOFs show selective adsorption of C2H2 over CO2 while 2-PMDI and 2-BPDI exhibit high selectivity toward C3H6/C3H8 separation. This study establishes imide condensation of preformed metal-organic clusters with organic linkers as a viable route for MOF design.

Design, synthesis, pharmacophore modeling, and molecular docking of some novel chloroacetamide derivatives as herbicidal agents

BackgroundThe discovery of new lead compounds with desired properties and biological activity is an excellent challenge in pesticide chemistry. Chloroacetamide are an important class of synthetic herbicides.ResultsTo explore the herbicidal activity of chloroacetamides, several new chloroacetamide derivatives have been designed, and synthesized. The compounds have been described by forming Schiff bases followed by chloroacetylation of imines. The herbicidal activity as a chlorophyll inhibition was evaluated against two broadleaf weeds (Chenopodium album and Anagallis arvensis) and two grass weeds (Lolium temulentum and Echinochloa crus-galli) in comparison with acetochlor as a standard herbicide. 1H-NMR, 13C-NMR and mass spectroscopic analyses confirmed the chemical structures of the synthesized compounds. Several compounds have demonstrated highly potent herbicidal activity compared to the standard herbicide acetochlor. Some of them have been described as the most effective against weeds tested, such as compounds 5b and 18b. Molecular docking to the active sites of Very Long Chain Fatty Acid Synthase (VLCFAS) has indicated that most compounds are low-energy binding agents and show high affinity for the active pocket.ConclusionNovel herbicides may be discovered by combining chloroacetamide derivatives with these existing lead structures.Graphical

The Impact of Varying Pasture Levels on the Metabolomic Profile of Bovine Ruminal Fluid.

A pasture or concentrate-based dietary regime impacts a variety of factors including both ruminal health and function, and consequently milk production and quality. The objective of this study was to examine the effect of feeding differing pasture levels on the metabolite composition of bovine ruminal fluid. Ruminal fluid was obtained from rumen-cannulated spring-calving cows (N = 9, Holstein-Friesian breed, average lactation number = 5) fed one of three diets across a full lactation season. Group 1 (pasture) consumed perennial ryegrass supplemented with 5% concentrates; group 2 received a total mixed ration (TMR) diet; and group 3 received a partial mixed ration (PMR) diet which included pasture and a TMR. Samples were taken at two timepoints: morning and evening. Metabolomic analysis was performed using nuclear magnetic resonance (1H-NMR) spectroscopy. Statistical analysis revealed significant changes across the dietary regimes in both morning and evening samples, with distinct alterations in the metabolite composition of ruminal fluid from pasture-fed cows (FDR-adjusted p-value < 0.05). Acetate and butyrate were significantly higher in samples derived from a pasture-based diet whereas sugar-related metabolites were higher in concentrate-based samples. Furthermore, a distinct diurnal impact on the metabolite profile was evident. This work lays the foundation for understanding the complex interaction between dietary regime and ruminal health.

Aza-Diarylethenes Undergoing Both Photochemically and Thermally Reversible Electrocyclic Reactions.

Exploring novel molecular photoswitches plays a crucial role in the field of photo-functional materials chemistry. In this study, we synthesized aza-diarylethenes with benzothiophene-S,S-dioxide as apart of hexatriene structureand investigated their photochromic properties. Unlike previously reported aza-diarylethenes, which exhibit fast thermally reversible photochromism, the compounds synthesized here exhibited pseudo-photochemically reversible photochromism. Due to their thermal stability, we successfully isolated the colored isomer. X-ray crystallographic analysis revealed for the first time that the colored isomer adopts a closed-ring structure with a bond between carbon and nitrogen atoms. Remarkably, these aza-diarylethenes exhibited not only photochemical ring-closing and ring-opening reactions but also thermal ring-closing and ring-opening reactions, driven by a thermal equilibrium between the open- and closed-ring isomers. This behavior, unprecedented for common diarylethenes, was elucidated through kinetic analysis, revealing an energy-level diagram for the thermal equilibrium between these isomers. Furthermore, 1H NMR spectroscopy revealed that both photochemically and thermally generated closed-ring isomers adopt the same structure, which was well explained based on the reaction mechanism of photochemical and thermal ring-closing reactions. These findings not only advance the field of aza-diarylethenes but also inspire future research in the development of new photoswitches.

Aromatic (Co)polycarbonates bearing pendant norbornenyl groups: Synthesis, characterization and post-polymerization modification

A homo- and three co-polycarbonates (PC-NBs) bearing pendant norbornenyl groups were synthesized via solution polycondensation of triphosgene with 4, 4'-(bicyclo (2.2.1) hept-5-en-2 yl methylene) bis (2-methoxyphenol) (BPA-NB) or various mol % compositions of BPA-NB and bisphenol-A, respectively. 1H-NMR spectroscopy confirmed the chemical structure and composition of PC-NBs. Inherent viscosity and number-average molecular weight (Mn) values of PC-NBs were in the range 0.44 – 0.64 dL g−1 and 21,800 – 34,100 g mol−1, respectively, indicating the formation of polymers of medium to reasonably high molecular weights. Tough, transparent, and flexible films of PC-NBs could be cast from chloroform solution. X-Ray diffraction studies indicated the amorphous nature of PC-NBs. Glass transition temperature (Tg) values, determined by DSC analysis, of PC-NBs were in the range 154 – 175°C and Tg values increased with the increase in mol % of BPA-NB. The post-polymerization modification of a representative PC-NB was demonstrated using 3,6-diphenyl-1,2,4,5-tetrazine via tetrazine-ene reaction.

An Efficient Metal-Free Methodology for the Synthesis of Hydrazo-Linked 5-(4-aryl)-1H-1,2,4-Triazoles

Hydrazo compounds have displayed significant roles in both biological and physical aspects, such as spinamycin as a potent growth inhibitor against fungi and rat sarcoma cells, hydrazo tocopherol as a component of vitamin E, and electron-rich hydrazo-linked triazines as energetic materials. In this study, a metal-free approach was proposed for the synthesis of hydrazo-linked 5-(4- aryl)-1H-1,2,4-triazoles. The methods for the synthesis of 5-(4-aryl)-1H-1,2,4-triazoles initiated by the reaction of aldehyde with semicarbazide. The resulted compound, 5-(4-aryl)-1H-1,2,4-triazol-3- ol, upon reaction with phosphorous oxychloride yielded 3-chloro-5-(4-aryl)-1H-1,2,4-triazoles. These synthesized compounds upon fusión with various aryl and hetero aryl substituted hydrazines provided desired hydrazo moieties. Synthesized hydrazo compounds were characterized by spectroscopic techniques, viz. 1H-NMR, FT-IR and mass spectrometry. In this study, a series of novel hydrazo- linked 5-(4-aryl)-1H-1,2,4-triazoles were synthesized. The methodology proposed in this study eliminates the use of complicated procedures and heavy metals.

Pharmacological investigation of new niclosamide-based isatin hybrids as antiproliferative, antioxidant, and apoptosis inducers

A group of Niclosamide-linked isatin hybrids (Xo, X1, and X2) was created and examined using IR, 1HNMR, 13C NMR, and mass spectrometry. These hybrids' cytotoxicity, antioxidant, cell cycle analysis, and apoptosis-inducing capabilities were identified. Using the SRB assay, their cytotoxicity against the human HCT-116, MCF-7, and HEPG-2 cancer cell lines, as well as VERO (African Green Monkey Kidney), was evaluated. Compound X1 was the most effective compound. In HCT-116 cells, compound X1 produced cell cycle arrest in the G1 phase, promoted cell death, and induced apoptosis through mitochondrial membrane potential breakdown in comparison to niclosamide and the control. Niclosamide and compound X1 reduced reactive oxygen species generation and modulated the gene expression of BAX, Bcl-2, Bcl-xL, and PAR-4 in comparison to the control. Docking modeling indicated their probable binding modalities with the XIAP BIR2 domain, which selectively binds caspase-3/7, and highlighted their structural drivers of activity for further optimization investigations. Computational in silico modeling of the new hybrids revealed that they presented acceptable physicochemical values as well as drug-like characteristics, which may introduce them as drug-like candidates. The study proved that compound X1 might be a novel candidate for the development of anticancer agents as it presents antiproliferative activity mediated by apoptosis.

Double Type Detection of Triiodide and Iodide Ions Using a Manganese(III) Porphyrin as Sensitive Compound.

A paramagnetic A3B-type Mn(III)-porphyrin was synthesized and characterized by physical-chemical methods (UV-Vis, FT-IR, 1H-NMR spectroscopy). The obtained compound was tested as a sensitive material for the spectrophotometric and potentiometric detection of iodine species. Using UV-Vis spectroscopy, the triiodide anions could be detected with high precision in the concentration interval of 1.02 × 10-5 to 2.3 × 10-5 M, with an LOD of 9.44 × 10-6 M. The PVC-based electrode using DOP as a plasticizer showed a sensitivity toward iodide in a wide concentration range of 1.0 × 10-5 to 1.0 × 10-1 M, with an LOD of 8.0 × 10-6 M. Both methods are simple, low-cost, and efficient for the detection of iodine species in synthetic samples and pharmaceuticals.