Modeling of Michael addition of pyrazole to cinnamaldehyde in the presence of six thiourea catalysts has been done at the DFT (B3LYP/6-31+G(d,p)) level. Four catalysts incorporating 2-pyridyl moiety are found to exhibit bifunctional dual activation by encapsulating pyrazole molecule in the cavity of cinnamaldehyde-catalyst complex thereby mimicking biosystem to bring the two reactants closer and also narrowing down the HOMO-LUMO gap. Guided by the theoretical results, four new N-bis(3,5-trifluoromethyl)phenyl-N′-2-pyridylthiourea catalysts were synthesized and well characterized on the basis of IR, 1H and 13C NMR and HRMS studies. X-ray crystal structure of one catalyst could also be done. On determining comparative catalytic efficacies of these catalysts experimentally for the model reaction of pyrazole with cinnamaldehyde, the catalyst N-bis(3,5-trifluoromethyl)phenyl-N′-2-(5-chloropyridyl)thiourea was found to be most effective, which is in accordance with the theoretical modeling results.
在DFT （B3LYP/6-31+G(d,p)）水平上模拟了六种硫脲催化剂存在下吡唑对肉桂醛的Michael加成反应。四种含2-吡啶基的催化剂通过将吡唑分子包封在肉桂醛-催化剂配合物的空腔中，从而模拟生物系统，使两种反应物更接近，并缩小了HOMO-LUMO间隙，从而表现出双功能双活化。在理论结果的指导下，合成了4种新型n -双（3,5-三氟甲基）苯基- n ' -2-吡啶硫脲催化剂，并通过IR、1H、13C NMR和HRMS对催化剂进行了表征。其中一种催化剂的x射线晶体结构也可以得到。通过实验比较这些催化剂对吡唑与肉桂醛模型反应的催化效果，发现n -双（3,5-三氟甲基）苯基- n ' -2-（5-氯吡啶基）硫脲催化剂的催化效果最好，这与理论模拟结果一致。
{"title":"Modeling and synthesis of bifunctional dual activation thiourea organocatalysts for Michael addition of pyrazole","authors":"Savita Sharma , Vandana Sharma , Sanjay Mandal , Raj K. Bansal","doi":"10.1016/j.tgchem.2025.100081","DOIUrl":"10.1016/j.tgchem.2025.100081","url":null,"abstract":"<div><div>Modeling of Michael addition of pyrazole to cinnamaldehyde in the presence of six thiourea catalysts has been done at the DFT (B3LYP/6-31+G(d,p)) level. Four catalysts incorporating 2-pyridyl moiety are found to exhibit bifunctional dual activation by encapsulating pyrazole molecule in the cavity of cinnamaldehyde-catalyst complex thereby mimicking biosystem to bring the two reactants closer and also narrowing down the HOMO-LUMO gap. Guided by the theoretical results, four new N-bis(3,5-trifluoromethyl)phenyl-N′-2-pyridylthiourea catalysts were synthesized and well characterized on the basis of IR, <sup>1</sup>H and <sup>13</sup>C NMR and HRMS studies. X-ray crystal structure of one catalyst could also be done. On determining comparative catalytic efficacies of these catalysts experimentally for the model reaction of pyrazole with cinnamaldehyde, the catalyst N-bis(3,5-trifluoromethyl)phenyl-N′-2-(5-chloropyridyl)thiourea was found to be most effective, which is in accordance with the theoretical modeling results.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"6 ","pages":"Article 100081"},"PeriodicalIF":0.0,"publicationDate":"2025-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144605552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Compounds containing the 1-chloropyrrolo[1,2-a]quinoxaline framework were assessed against MtbCM (chorismate mutase) for the identification of possible anti-tubercular entities. These compounds were synthesized via the sonochemical chlorination of pyrrolo[1,2-a]quinoxalines using N-chlorosaccharin. The regioselective C-1 chlorination, mild and eco-friendly conditions, and decreased reaction time are the key aspects of the present ultrasound-assisted method, an application of which is also demonstrated. The molecular docking of synthesized compounds into the target protein MtbCM revealed that they were oriented in the loop region of MtbCM and mostly interacted with the residues in the periphery of the loop via hydrophobic interactions e.g. (i) pi-sigma with LEU130 and LEU65, (ii) pi-anion with ASP69 and (iii) pi-cation with ARG134. Furthermore, similar molecular alignment of -Cl group displaying a hydrophobic interaction with PRO66 was noted in case of majority of these compounds. The compound 3b, 3f, 3g and 3k showed better binding affinities with the order 3b > 3f > 3g > 3k indicating 3b as the best among them. This observation correlated the outcome of in vitro assay using MtbCM when 3b, 3f and 3g showed >50 % inhibition at 30 μM. The Structure-Activity-Relationship (SAR) suggested that the C-4 aryl/heteroaryl group seemed to be vital for the activity. Indeed, a p-substituent on the C-4 phenyl ring was found to be favorable for activities. The role of Cl group was also assessed via in vitro testing of compounds with and without –Cl group. With the IC50 value 12.34 ± 0.76 μM for MtbCM, the compound 3b was also expected to exhibit acceptable pharmacokinetic properties.
{"title":"An ultrasound based greener approach to 1-chloropyrrolo[1,2-a]quinoxalines as potential anti-tubercular agents","authors":"Jyothi Shivanoori , Mallesham Baldha , Sunder Kumar Kolli , Ravikumar Kapavarapu , Manojit Pal","doi":"10.1016/j.tgchem.2025.100080","DOIUrl":"10.1016/j.tgchem.2025.100080","url":null,"abstract":"<div><div>Compounds containing the 1-chloropyrrolo[1,2-<em>a</em>]quinoxaline framework were assessed against <em>Mtb</em>CM (chorismate mutase) for the identification of possible anti-tubercular entities. These compounds were synthesized <em>via</em> the sonochemical chlorination of pyrrolo[1,2-<em>a</em>]quinoxalines using <em>N</em>-chlorosaccharin. The regioselective C-1 chlorination, mild and eco-friendly conditions, and decreased reaction time are the key aspects of the present ultrasound-assisted method, an application of which is also demonstrated. The molecular docking of synthesized compounds into the target protein <em>MtbCM</em> revealed that they were oriented in the loop region of <em>Mtb</em>CM and mostly interacted with the residues in the periphery of the loop <em>via</em> hydrophobic interactions e.g. (i) pi-sigma with LEU130 and LEU65, (ii) pi-anion with ASP69 and (iii) pi-cation with ARG134. Furthermore, similar molecular alignment of -Cl group displaying a hydrophobic interaction with PRO66 was noted in case of majority of these compounds. The compound <strong>3b</strong>, <strong>3f</strong>, <strong>3g</strong> and <strong>3k</strong> showed better binding affinities with the order <strong>3b > 3f > 3g</strong> > <strong>3k</strong> indicating <strong>3b</strong> as the best among them. This observation correlated the outcome of <em>in vitro</em> assay using <em>Mtb</em>CM when <strong>3b</strong>, <strong>3f</strong> and <strong>3g</strong> showed >50 % inhibition at 30 μM. The Structure-Activity-Relationship (SAR) suggested that the C-4 aryl/heteroaryl group seemed to be vital for the activity. Indeed, a <em>p</em>-substituent on the C-4 phenyl ring was found to be favorable for activities. The role of Cl group was also assessed <em>via in vitro</em> testing of compounds with and without –Cl group. With the IC<sub>50</sub> value 12.34 ± 0.76 μM for <em>Mtb</em>CM, the compound <strong>3b</strong> was also expected to exhibit acceptable pharmacokinetic properties.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100080"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144195313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An efficient, photo-catalytic synthesis of thioamidoguanidine was developed through oxidative sulfurization of thioureas. The protocol involves the use of Ru(bpy)3Cl2 (bpy = 2,2′-bipyridine)as a photo-catalyst, carbon tetrabromide (CBr4) as the oxidizing reagent, and visible light as the source of energy at room temperature. Present reaction offers a practical, base-free, economically cheap reagent, an environmentally benign and safer approach for a variety of anti-Hugelchoff products.
{"title":"Visible light photoredox catalyzed controlled oxidative desulfurization of thioureas using CBr4: A new route for the synthesis of thioamidoguanidine","authors":"Babita Yadav , Arvind Kumar Yadav , Garima , Atul Kumar Singh , Vishnu Prabhakar Srivastava , Santosh K. Srivastava","doi":"10.1016/j.tgchem.2025.100079","DOIUrl":"10.1016/j.tgchem.2025.100079","url":null,"abstract":"<div><div>An efficient, photo-catalytic synthesis of thioamidoguanidine was developed through oxidative sulfurization of thioureas. The protocol involves the use of Ru(bpy)<sub>3</sub>Cl<sub>2</sub> (bpy = 2,2′-bipyridine)as a photo-catalyst, carbon tetrabromide (CBr<sub>4</sub>) as the oxidizing reagent, and visible light as the source of energy at room temperature. Present reaction offers a practical, base-free, economically cheap reagent, an environmentally benign and safer approach for a variety of anti-Hugelchoff products.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100079"},"PeriodicalIF":0.0,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144134721","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-12DOI: 10.1016/j.tgchem.2025.100078
R. Kavitha , M. Srinivas , Prashantha Karunakar , G.R. Rekhashree , R. Priyanka , K.G. Shilpashree , M.S. Kavya , S.M. Basavarajaiah
The extensive use of nanocomposites in the field of medicine and pharmaceuticals stems from their physicochemical properties and due to their potential therapeutic application. Further, nanopharmaceutics take a significant role in designing smart drug-release and controlled drug delivery, where the drug is efficiently reached towards the target sites within a predictable and limited timescale. The scope of present research work is to synthesis an ecofriendly silver nanocomposite (Ag/Ag2O) by using alcoholic fruit extract of Pheonix slyvestris and its efficiency was evaluated for anticancer activity. PXRD results and HRTEM images confirmed that Ag/Ag2O was crystalline in nature with diverse morphology and possessed an average particle size of 23–50 nm. Surface plasmon resonance of Ag/Ag2O was observed at 465–500 nm in UV-DRS. The PL spectrum of Ag/Ag2O NPs shows two asymmetric peaks confirming the formation of Ag/Ag2O heterocomposite. The cytotoxicity study Ag/Ag2Osynthesized via green chemistry was performed using the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyltetrazolium bromide) assay against breast cancer cell line (MCF7) with an IC5021.61 μg/mL. The results of the cytotoxicity tests showed a concentration dependent outcome against tumor cells and a correlation between dosage and effectiveness against tested cancer cell line. DFT studies revealed the sensing response of Ag/Ag2O composite towards doxorubicin drug confirmed by relative work function changes. Molecular docking and dynamics simulation resulted that the Ag/Ag2O illustrates to be an excellent lead molecule. In conclusion, the present research work demonstrated that Ag/Ag2O synthesized from alcoholic fruit extract of Pheonix slyvestris may be an impending remedial drug for breast cancer management.
{"title":"Unveiling of bio-inspired synthesis, characterization, DFT calculations, molecular modeling of silver (Ag/Ag2O) nanocomposite: A promising sustainable material against human breast cancer","authors":"R. Kavitha , M. Srinivas , Prashantha Karunakar , G.R. Rekhashree , R. Priyanka , K.G. Shilpashree , M.S. Kavya , S.M. Basavarajaiah","doi":"10.1016/j.tgchem.2025.100078","DOIUrl":"10.1016/j.tgchem.2025.100078","url":null,"abstract":"<div><div>The extensive use of nanocomposites in the field of medicine and pharmaceuticals stems from their physicochemical properties and due to their potential therapeutic application. Further, nanopharmaceutics take a significant role in designing smart drug-release and controlled drug delivery, where the drug is efficiently reached towards the target sites within a predictable and limited timescale. The scope of present research work is to synthesis an ecofriendly silver nanocomposite (Ag/Ag<sub>2</sub>O) by using alcoholic fruit extract of <em>Pheonix slyvestris</em> and its efficiency was evaluated for anticancer activity. PXRD results and HRTEM images confirmed that Ag/Ag<sub>2</sub>O was crystalline in nature with diverse morphology and possessed an average particle size of 23–50 nm. Surface plasmon resonance of Ag/Ag<sub>2</sub>O was observed at 465–500 nm in UV-DRS. The PL spectrum of Ag/Ag<sub>2</sub>O NPs shows two asymmetric peaks confirming the formation of Ag/Ag<sub>2</sub>O heterocomposite. The cytotoxicity study Ag/Ag<sub>2</sub>Osynthesized via green chemistry was performed using the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyltetrazolium bromide) assay against breast cancer cell line (MCF7) with an IC<sub>50</sub>21.61 μg/mL. The results of the cytotoxicity tests showed a concentration dependent outcome against tumor cells and a correlation between dosage and effectiveness against tested cancer cell line. DFT studies revealed the sensing response of Ag/Ag<sub>2</sub>O composite towards doxorubicin drug confirmed by relative work function changes. Molecular docking and dynamics simulation resulted that the Ag/Ag<sub>2</sub>O illustrates to be an excellent lead molecule. In conclusion, the present research work demonstrated that Ag/Ag<sub>2</sub>O synthesized from alcoholic fruit extract of <em>Pheonix slyvestris</em> may be an impending remedial drug for breast cancer management.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100078"},"PeriodicalIF":0.0,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-10DOI: 10.1016/j.tgchem.2025.100077
A. Harshavardhan , V.B. Nagaveni , H. Madhu
This study presents a comparative investigation of cerium oxide (CeO2) and copper oxide (CuO) nanoparticles synthesized via the solution combustion method (SCM) using pomegranate peel as a green fuel. The synthesized materials were systematically characterized for their structural, morphological, optical, and electrochemical properties using XRD, SEM, UV–Vis spectroscopy, FTIR, and CV techniques. Optical studies were analyzed to understand their functional behaviour, including transmittance, refractive index, dielectric constant, optical conductivity, and absorption coefficient.
The photocatalytic potential of CeO2 and CuO was evaluated for the degradation of malachite green under UV light, achieving degradation efficiencies of 97.4 % and 91.56 %, respectively, following first-order kinetics. Additional photocatalytic performance parameters such as half-life (T1/2), total organic carbon (TOC) removal, pH dependence, scavenger effects, and recyclability were systematically studied. Electrochemical investigations were conducted using a nickel mesh electrode, revealing redox behaviour in 1 M NaOH through cyclic voltammetry (CV) with specific capacitances of 95 F/g (CeO2) and 64 F/g (CuO). Diffusion coefficients were determined as 4.365 × 10−5 cm2/s for CeO2 and 3.137 × 10−5 cm2/s for CuO. Furthermore, via CV analysis, CeO2 and CuO were explored as electrochemical sensors for heavy metal detection, demonstrating sensitivity towards mercury (Hg) and cadmium (Cd) in the 1–5 mM range.
This work highlights the dual functionality of CeO2 and CuO nanoparticles as effective photocatalysts and electrochemical sensors, offering promising applications in environmental remediation and heavy metal detection.
{"title":"Optical, dye degradation, and electrochemical sensor studies of CeO2 and CuO nanoparticles by pomegranate peel","authors":"A. Harshavardhan , V.B. Nagaveni , H. Madhu","doi":"10.1016/j.tgchem.2025.100077","DOIUrl":"10.1016/j.tgchem.2025.100077","url":null,"abstract":"<div><div>This study presents a comparative investigation of cerium oxide (CeO<sub>2</sub>) and copper oxide (CuO) nanoparticles synthesized via the solution combustion method (SCM) using pomegranate peel as a green fuel. The synthesized materials were systematically characterized for their structural, morphological, optical, and electrochemical properties using XRD, SEM, UV–Vis spectroscopy, FTIR, and CV techniques. Optical studies were analyzed to understand their functional behaviour, including transmittance, refractive index, dielectric constant, optical conductivity, and absorption coefficient.</div><div>The photocatalytic potential of CeO<sub>2</sub> and CuO was evaluated for the degradation of malachite green under UV light, achieving degradation efficiencies of 97.4 % and 91.56 %, respectively, following first-order kinetics. Additional photocatalytic performance parameters such as half-life (T<sub>1</sub>/<sub>2</sub>), total organic carbon (TOC) removal, pH dependence, scavenger effects, and recyclability were systematically studied. Electrochemical investigations were conducted using a nickel mesh electrode, revealing redox behaviour in 1 M NaOH through cyclic voltammetry (CV) with specific capacitances of 95 F/g (CeO<sub>2</sub>) and 64 F/g (CuO). Diffusion coefficients were determined as 4.365 × 10<sup>−5</sup> cm<sup>2</sup>/s for CeO<sub>2</sub> and 3.137 × 10<sup>−5</sup> cm<sup>2</sup>/s for CuO. Furthermore, via CV analysis, CeO<sub>2</sub> and CuO were explored as electrochemical sensors for heavy metal detection, demonstrating sensitivity towards mercury (Hg) and cadmium (Cd) in the 1–5 mM range.</div><div>This work highlights the dual functionality of CeO<sub>2</sub> and CuO nanoparticles as effective photocatalysts and electrochemical sensors, offering promising applications in environmental remediation and heavy metal detection.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100077"},"PeriodicalIF":0.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-02DOI: 10.1016/j.tgchem.2025.100076
Barnabás Zsignár-Nagy , Viktória Kümmel , Tamás Gazdag , Péter J. Mayer , Zsófia Bokor , Tamás Holczbauer , Gábor London
A photoinduced electrocyclization followed by aerobic oxidation of 1,2-dithienylarene derivatives is described as a greener alternative to direct aryl-aryl couplings. The formation of the naphthodithiophene type products was monitored by UV–vis spectroscopy. Naphthodithiophenes with different structural features and electronic characters were accessed. Oxidative cyclization using the combination of BF3·Et2O and DDQ was a complementary approach to confirm the formation of the desired products. The method was also applicable to 2,3-dithienylbiphenylene having a backbone with antiaromatic character.
{"title":"Photoinduced oxidative cyclization of dithienylarenes","authors":"Barnabás Zsignár-Nagy , Viktória Kümmel , Tamás Gazdag , Péter J. Mayer , Zsófia Bokor , Tamás Holczbauer , Gábor London","doi":"10.1016/j.tgchem.2025.100076","DOIUrl":"10.1016/j.tgchem.2025.100076","url":null,"abstract":"<div><div>A photoinduced electrocyclization followed by aerobic oxidation of 1,2-dithienylarene derivatives is described as a greener alternative to direct aryl-aryl couplings. The formation of the naphthodithiophene type products was monitored by UV–vis spectroscopy. Naphthodithiophenes with different structural features and electronic characters were accessed. Oxidative cyclization using the combination of BF<sub>3</sub>·Et<sub>2</sub>O and DDQ was a complementary approach to confirm the formation of the desired products. The method was also applicable to 2,3-dithienylbiphenylene having a backbone with antiaromatic character.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100076"},"PeriodicalIF":0.0,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143800673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-26DOI: 10.1016/j.tgchem.2025.100075
Luisa Damaris Ramos , Alfonso Enrique Ramírez, Cristian David Miranda
The transformation of coffee husks into solid acid catalysts (eco-catalysts) was studied. The synthesis of the materials consisted of the elaboration of carbonaceous supports by thermal means [graphitic carbon (Cp) and biochar (Cc)], followed by functionalization with sulfonic groups, by means of two techniques: i) in situ diazotization with sulfanilic acid (SD) or ii) direct sulfonation with sulfuric acid (SA). The density of acid sites (-SO3H) present in the materials was determined by elemental analysis and additionally characterizations such as TGA, XRD, TEM and FTIR spectroscopy were performed. The catalytic properties of eco-catalysts in the glycerol acetylation reaction were studied and compared with a commercial sulfonic resin, i.e. Amberlyst® 15. It was found that all of them were more active compared to Amberlyst ® 15. CpSA showed the highest conversion and selectivity towards triacetin, the product of interest.
{"title":"Acidic eco-catalysts derived from coffee husks in the acetylation of glycerol","authors":"Luisa Damaris Ramos , Alfonso Enrique Ramírez, Cristian David Miranda","doi":"10.1016/j.tgchem.2025.100075","DOIUrl":"10.1016/j.tgchem.2025.100075","url":null,"abstract":"<div><div>The transformation of coffee husks into solid acid catalysts (eco-catalysts) was studied. The synthesis of the materials consisted of the elaboration of carbonaceous supports by thermal means [graphitic carbon (Cp) and biochar (<em>Cc</em>)], followed by functionalization with sulfonic groups, by means of two techniques: i) in situ diazotization with sulfanilic acid (S<sub>D</sub>) or ii) direct sulfonation with sulfuric acid (S<sub>A</sub>). The density of acid sites (-SO<sub>3</sub>H) present in the materials was determined by elemental analysis and additionally characterizations such as TGA, XRD, TEM and FTIR spectroscopy were performed. The catalytic properties of eco-catalysts in the glycerol acetylation reaction were studied and compared with a commercial sulfonic resin, i.e. Amberlyst® 15. It was found that all of them were more active compared to Amberlyst ® 15. CpS<sub>A</sub> showed the highest conversion and selectivity towards triacetin, the product of interest.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100075"},"PeriodicalIF":0.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-25DOI: 10.1016/j.tgchem.2025.100074
Madhuri A. Balpande , Manish M. Katiya , Madhukar G. Dhonde , Jayant M. Gajbhiye
A base catalyzed the transesterification reaction, resulting in a 98 % yield during biodiesel (fatty acid methyl ester - FAME) synthesis. The optimization reaction protocol requires maximum agitation of 600 rpm at room temperature for 20min with a 10mol% KOH as a base catalyst and 1:8 ratios of sunflower oil and methanol to complete the reaction. This study examines the viability of using vegetable oil through transesterification to produce biodiesel on a commercial scale, with the goal of serving as a fuel substitute for diesel engines. We explored well-established spectroscopic techniques, including Infra-Red, 1H, 13C Nuclear Magnetic Resonance, Gas Chromatography Mass Spectra, and High-Resolution Mass Spectra, to investigate the synthesized FAME in accordance with the ASTM specification. The novelty of the current study outlines the significance of synthesizing FAME through catalytic transesterification, examines its physicochemical parameters, and green chemistry matrices have shown that biodiesel is a beneficial fuel, which led to less reaction waste, better environmental compatibility, and long-term use of the current protocol. In addition to exploring biodiesel's fuel applications; we are also looking into its possible uses as a biodetergent for other purposes and a biolubricant for diesel engines. The study highlights the simple, efficient development of current biodiesel, with its sustainability, and its potential contribution to renewable energy goals. It also explores the environmental impact of transitioning to biobased alternatives and its potential applications in industries like cosmetics and automobiles. Therefore, this investigation aims to explore and combine the unique advantages associated with varying ratios of additives in FAME, with the goal of replacing as much diesel as possible. We created and experimented with blends including 10, 20, and 30 % ethanol or iso-octane in FAME; nevertheless, the blend containing 30 % ethanol works better as a diesel substitute.
{"title":"Synthesis of biodiesel and prepared its blend: An ecofriendly, clean, alternative, and sustainable energy source","authors":"Madhuri A. Balpande , Manish M. Katiya , Madhukar G. Dhonde , Jayant M. Gajbhiye","doi":"10.1016/j.tgchem.2025.100074","DOIUrl":"10.1016/j.tgchem.2025.100074","url":null,"abstract":"<div><div>A base catalyzed the transesterification reaction, resulting in a 98 % yield during biodiesel (fatty acid methyl ester - FAME) synthesis. The optimization reaction protocol requires maximum agitation of 600 rpm at room temperature for 20min with a 10mol% KOH as a base catalyst and 1:8 ratios of sunflower oil and methanol to complete the reaction. This study examines the viability of using vegetable oil through transesterification to produce biodiesel on a commercial scale, with the goal of serving as a fuel substitute for diesel engines. We explored well-established spectroscopic techniques, including Infra-Red, <sup>1</sup>H, <sup>13</sup>C Nuclear Magnetic Resonance, Gas Chromatography Mass Spectra, and High-Resolution Mass Spectra, to investigate the synthesized FAME in accordance with the ASTM specification. The novelty of the current study outlines the significance of synthesizing FAME through catalytic transesterification, examines its physicochemical parameters, and green chemistry matrices have shown that biodiesel is a beneficial fuel, which led to less reaction waste, better environmental compatibility, and long-term use of the current protocol. In addition to exploring biodiesel's fuel applications; we are also looking into its possible uses as a biodetergent for other purposes and a biolubricant for diesel engines. The study highlights the simple, efficient development of current biodiesel, with its sustainability, and its potential contribution to renewable energy goals. It also explores the environmental impact of transitioning to biobased alternatives and its potential applications in industries like cosmetics and automobiles. Therefore, this investigation aims to explore and combine the unique advantages associated with varying ratios of additives in FAME, with the goal of replacing as much diesel as possible. We created and experimented with blends including 10, 20, and 30 % ethanol or iso-octane in FAME; nevertheless, the blend containing 30 % ethanol works better as a diesel substitute.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100074"},"PeriodicalIF":0.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143715125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-12DOI: 10.1016/j.tgchem.2025.100073
Shajahan Rubina , Kareem A. Feby , Saithalavi Anas
Photodegradation of organic pollutants in wastewater is an ideal process for reducing environmental pollution, as it harnesses light energy to break down harmful compounds into safer byproducts. Supported catalysts play a crucial role in this process as they increase the stability and reusability of the photocatalysts, enhance light absorption, and improve degradation efficiency by providing a larger surface area for the reaction. This certainly improves the sustainability and effectiveness of the contaminated water treatment. This review article provides a comprehensive overview of various polymer-supported Fenton catalysts for the photodegradation of organic compounds in wastewater treatment. The discussion is structured based on the type of polymer such as polystyrene, polyacrylonitrile, resins, Nafion and other miscellaneous polymers employed as suitable solid support for Fenton catalysts. Key aspects of each category of these supported catalysts are explored, including their preparation methods, structural characteristics, and catalytic performance in degrading pollutants under different conditions. The review also focuses on the recent challenges and gaps in this area of research in terms of catalyst stability, reusability, and efficiency under varying environmental conditions. By consolidating the existing knowledge on the title topic, this article serves as a valuable resource for researchers and practitioners, offering insights into the potential of polymer-supported Fenton catalysts and directing toward more effective and sustainable photocatalytic systems for wastewater treatment.
{"title":"Advances in photodegradation of organic pollutants using polymer supported Fenton catalysts","authors":"Shajahan Rubina , Kareem A. Feby , Saithalavi Anas","doi":"10.1016/j.tgchem.2025.100073","DOIUrl":"10.1016/j.tgchem.2025.100073","url":null,"abstract":"<div><div>Photodegradation of organic pollutants in wastewater is an ideal process for reducing environmental pollution, as it harnesses light energy to break down harmful compounds into safer byproducts. Supported catalysts play a crucial role in this process as they increase the stability and reusability of the photocatalysts, enhance light absorption, and improve degradation efficiency by providing a larger surface area for the reaction. This certainly improves the sustainability and effectiveness of the contaminated water treatment. This review article provides a comprehensive overview of various polymer-supported Fenton catalysts for the photodegradation of organic compounds in wastewater treatment. The discussion is structured based on the type of polymer such as polystyrene, polyacrylonitrile, resins, Nafion and other miscellaneous polymers employed as suitable solid support for Fenton catalysts. Key aspects of each category of these supported catalysts are explored, including their preparation methods, structural characteristics, and catalytic performance in degrading pollutants under different conditions. The review also focuses on the recent challenges and gaps in this area of research in terms of catalyst stability, reusability, and efficiency under varying environmental conditions. By consolidating the existing knowledge on the title topic, this article serves as a valuable resource for researchers and practitioners, offering insights into the potential of polymer-supported Fenton catalysts and directing toward more effective and sustainable photocatalytic systems for wastewater treatment.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100073"},"PeriodicalIF":0.0,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-05DOI: 10.1016/j.tgchem.2025.100072
Aashna Perwin, Nasreen Mazumdar
In the development of bioactive materials centered around salicylaldehyde, we synthesized O-alkyl/aryl derivatives through the etherification of the phenolic group. Salicylaldehyde underwent a copper-catalyzed reaction with various halides under basic conditions, yielding 2-(3-chloropyrazin-2-yl)oxy benzaldehyde, 2-(6-chloropyrimidin-4-yl)oxy benzaldehyde, and 3-(2-formylphenoxy)-2-hydroxypropyl methacrylate. Meanwhile, 2-(2-formylphenoxy)ethyl methacrylate was synthesized via a sonication-assisted Mitsunobu reaction, affording high yields of ether derivatives. Structural elucidation was achieved using standard analytical techniques, such as 1H NMR, 13C NMR, FT-IR and LC-MS. The free radical homopolymerization of 3-(2-formylphenoxy)-2-hydroxypropyl methacrylate using benzoyl peroxide as an initiator was successfully achieved. The resulting polymer exhibited enhanced thermal stability, as confirmed by solid-state 13C NMR, FT-IR, TGA, DSC, and SEM analyses, with a higher glass transition temperature than the reported poly(glycidyl methacrylate). This increase in Tg is attributed to the enhanced rigidity introduced by the aromatic ring in the homopolymer. This study highlights the successful synthesis of various O-alkyl/aryl salicylaldehyde derivatives using different techniques and functionalities, followed by the effective polymerization of one of the monomers, 3-(2-formylphenoxy)-2-hydroxypropyl methacrylate.
{"title":"Advanced approach to O-alkyl/aryl salicylaldehyde derivatives: Synthesis, characterization, and free-radical homopolymerization for improved thermal stability","authors":"Aashna Perwin, Nasreen Mazumdar","doi":"10.1016/j.tgchem.2025.100072","DOIUrl":"10.1016/j.tgchem.2025.100072","url":null,"abstract":"<div><div>In the development of bioactive materials centered around salicylaldehyde, we synthesized O-alkyl/aryl derivatives through the etherification of the phenolic group. Salicylaldehyde underwent a copper-catalyzed reaction with various halides under basic conditions, yielding 2-(3-chloropyrazin-2-yl)oxy benzaldehyde, 2-(6-chloropyrimidin-4-yl)oxy benzaldehyde, and 3-(2-formylphenoxy)-2-hydroxypropyl methacrylate. Meanwhile, 2-(2-formylphenoxy)ethyl methacrylate was synthesized via a sonication-assisted Mitsunobu reaction, affording high yields of ether derivatives. Structural elucidation was achieved using standard analytical techniques, such as <sup>1</sup>H NMR, <sup>13</sup>C NMR, FT-IR and LC-MS. The free radical homopolymerization of 3-(2-formylphenoxy)-2-hydroxypropyl methacrylate using benzoyl peroxide as an initiator was successfully achieved. The resulting polymer exhibited enhanced thermal stability, as confirmed by solid-state <sup>13</sup>C NMR, FT-IR, TGA, DSC, and SEM analyses, with a higher glass transition temperature than the reported poly(glycidyl methacrylate). This increase in <em>T</em><sub><em>g</em></sub> is attributed to the enhanced rigidity introduced by the aromatic ring in the homopolymer. This study highlights the successful synthesis of various O-alkyl/aryl salicylaldehyde derivatives using different techniques and functionalities, followed by the effective polymerization of one of the monomers, 3-(2-formylphenoxy)-2-hydroxypropyl methacrylate.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100072"},"PeriodicalIF":0.0,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143550885","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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