Pub Date : 2023-04-03DOI: 10.1007/s12039-023-02148-3
Moupriya Das, Deb Shankar Ray
We explore the critical and scaling behavior of delayed bifurcations in systems with dynamic disorder well-known in kinetics when the control parameter in the rate is made to sweep stochastically across the critical point. The analysis is based on an extended Hamiltonian system that includes noise as an additional degree of freedom conjugate to the relevant dynamical variable. Appropriate quantifiers for measuring the time delay in reaching the bifurcation point have been introduced. We show that the time delay (i.e., the time difference between the static and dynamic bifurcation times) exhibits a power law decay with the deviation of the control parameter from its critical value, the decay constant being close to unity and is independent of the nature of bifurcations. The characteristic time to reach the zero solution state decreases algebraically with the deviation of the dynamical variable from its critical value and the decay exponent scales as the highest power of nonlinearity characterizing the nature of bifurcations.
Graphical abstract
Bifurcations are essential features of various chemical kinetics; biological and ecological evolution. Critical and scaling behavior of delayed bifurcations in such systems with dynamic disorder has been explored when the control parameter in the rate is varied stochastically across the critical point.
{"title":"Critical and scaling behavior of delayed bifurcations in nonlinear systems with dynamic disorder","authors":"Moupriya Das, Deb Shankar Ray","doi":"10.1007/s12039-023-02148-3","DOIUrl":"10.1007/s12039-023-02148-3","url":null,"abstract":"<div><p>We explore the critical and scaling behavior of delayed bifurcations in systems with dynamic disorder well-known in kinetics when the control parameter in the rate is made to sweep stochastically across the critical point. The analysis is based on an extended Hamiltonian system that includes noise as an additional degree of freedom conjugate to the relevant dynamical variable. Appropriate quantifiers for measuring the time delay in reaching the bifurcation point have been introduced. We show that the time delay (<i>i.e.,</i> the time difference between the static and dynamic bifurcation times) exhibits a power law decay with the deviation of the control parameter from its critical value, the decay constant being close to unity and is independent of the nature of bifurcations. The characteristic time to reach the zero solution state decreases algebraically with the deviation of the dynamical variable from its critical value and the decay exponent scales as the highest power of nonlinearity characterizing the nature of bifurcations.</p><h3>Graphical abstract</h3><p>\u0000Bifurcations are essential features of various chemical kinetics; biological and ecological evolution. Critical and scaling behavior of delayed bifurcations in such systems with dynamic disorder has been explored\u0000when the control parameter in the rate is varied stochastically across the critical point.</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s12039-023-02148-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4108985","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-03-29DOI: 10.1007/s12039-023-02146-5
Anjani Nandan Pandey, Tetsuya Taketsugu, Raman K Singh
Different decouplings of the Electron Propagator Theory (EPT) have been applied to many organic/inorganic compounds to get their vertical ionization potentials, while its potential in metal clusters is yet to be explored. In this study, we focus on assessing the reliability of this method for copper clusters, Cun (n = 1-13), as a case study. Furthermore, the wave function methods such as Hartree-Fock theory, Moller-Plesset perturbation theory, coupled-cluster theory, and long-range corrected density functional theory (LC-DFT) methods were also employed using the direct method (orbital eigenvalues) and indirect methods for comparison. The results show that outer-valance green function (OVGF) decoupling of the EPT methods gives a mean signed error (MSE) of 0.14 eV for the vertical ionization energies, which are lowest followed by partial third-order (P3) and modified partial third-order (P3+) methods. We presumed that the predicted vertical electron affinity using the EPT methods would be helpful for the experimentalists in the coming years. Therefore, electron propagator theory is reliable and should be explored extensively to get vertical ionization potentials and vertical electron affinities of other precious and non-precious metal clusters.
Graphical abstract
Different decouplings of the Electron Propagator Theory (EPT) have been applied to many organic/inorganic compounds to get their vertical ionization potentials, while its potential in metal clusters is yet to be explored. In this study, we focus on assessing the reliability of this method for copper clusters as a case study. It was found that the EPT is reliable, and this study encourages exploration of its untapped potential in other transition metal clusters.
{"title":"Theoretical investigation of copper clusters using the electron propagator theory","authors":"Anjani Nandan Pandey, Tetsuya Taketsugu, Raman K Singh","doi":"10.1007/s12039-023-02146-5","DOIUrl":"10.1007/s12039-023-02146-5","url":null,"abstract":"<div><p>Different decouplings of the Electron Propagator Theory (EPT) have been applied to many organic/inorganic compounds to get their vertical ionization potentials, while its potential in metal clusters is yet to be explored. In this study, we focus on assessing the reliability of this method for copper clusters, Cu<sub>n</sub> (n = 1-13), as a case study. Furthermore, the wave function methods such as Hartree-Fock theory, Moller-Plesset perturbation theory, coupled-cluster theory, and long-range corrected density functional theory (LC-DFT) methods were also employed using the direct method (orbital eigenvalues) and indirect methods for comparison. The results show that outer-valance green function (OVGF) decoupling of the EPT methods gives a mean signed error (MSE) of 0.14 eV for the vertical ionization energies, which are lowest followed by partial third-order (P3) and modified partial third-order (P3+) methods. We presumed that the predicted vertical electron affinity using the EPT methods would be helpful for the experimentalists in the coming years. Therefore, electron propagator theory is reliable and should be explored extensively to get vertical ionization potentials and vertical electron affinities of other precious and non-precious metal clusters.</p><h3>Graphical abstract</h3><p>Different decouplings of the Electron Propagator Theory (EPT) have been applied to many organic/inorganic compounds to get their vertical ionization potentials, while its potential in metal clusters is yet to be explored. In this study, we focus on assessing the reliability of this method for copper clusters as a case study. It was found that the EPT is reliable, and this study encourages exploration of its untapped potential in other transition metal clusters.\u0000</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5124831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Epoxy thermoset polymer materials (P1, P2, and P3) using resorcinol diglycidyl ether (RE) with different primary amines having aliphatic and aromatic backbones were prepared without using any transition metal-based catalyst and solvent. The polymerization was carried out with comonomers in the presence of non-nucleophilic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and CO2 gas through bulk copolymerization within 10-15 min at 100 °C yielding the cross-linked polymer. This cross-linking reaction can capture CO2 while forming a thermoset. The ring-strain-induced reactivity of oxiranes and the proton-removing ability of the sterically hindered non-nucleophilic base have driven the copolymerization reactions. Considering the fast pace in which the reaction occurred and the material’s hardness, the method reported here has the potential for large-scale industrial application. The resultant epoxy thermosets showed high glass transition temperature (Tg) in the range of 67–106 °C and possessed hardness up to 24.26 HV in the Vickers microhardness scale.
Graphical abstract
Epoxy thermoset polymer materials are prepared from resorcinol diglycidyl ether (RE) reactions with different primary amines. These materials capture carbon dioxide rapidly during the cross-linking reactions yielding highly abrasive materials as determined by the Vickers microhardness tester.
{"title":"Rapid capture of flow carbon dioxide by hard Epoxy thermosets with the high glass transition temperature","authors":"Venkateswara Rao Velpuri, Seelam Kumari, Krishnamurthi Muralidharan","doi":"10.1007/s12039-023-02139-4","DOIUrl":"10.1007/s12039-023-02139-4","url":null,"abstract":"<div><p>Epoxy thermoset polymer materials (<b>P1</b>, <b>P2</b>, and <b>P3</b>) using resorcinol diglycidyl ether (RE) with different primary amines having aliphatic and aromatic backbones were prepared without using any transition metal-based catalyst and solvent. The polymerization was carried out with comonomers in the presence of non-nucleophilic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and CO<sub>2</sub> gas through bulk copolymerization within 10-15 min at 100 °C yielding the cross-linked polymer. This cross-linking reaction can capture CO<sub>2</sub> while forming a thermoset. The ring-strain-induced reactivity of oxiranes and the proton-removing ability of the sterically hindered non-nucleophilic base have driven the copolymerization reactions. Considering the fast pace in which the reaction occurred and the material’s hardness, the method reported here has the potential for large-scale industrial application. The resultant epoxy thermosets showed high glass transition temperature (Tg) in the range of 67–106 °C and possessed hardness up to 24.26 HV in the Vickers microhardness scale.</p><h3>Graphical abstract</h3><p>Epoxy thermoset polymer materials are prepared from resorcinol diglycidyl ether (RE) reactions with different primary amines. These materials capture carbon dioxide rapidly during the cross-linking reactions yielding highly abrasive materials as determined by the Vickers microhardness tester.\u0000</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s12039-023-02139-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5090997","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this work, we have systematically reviewed the till date disclosed routes pertaining to the synthesis of Parvaquone. Prior art search gave us around nineteen synthetic routes, involving invention and innovation towards the starting material selection and process path to synthesize Parvaquone. Interestingly, 2-hydroxy naphthalene-1,4-dione has been the predominant raw material used for the synthesis of Parvaquone. Every process was executed to attain higher atom economy, process economy, and better purity of the product. In most of the works, a significant focus was given on choosing cheap and easy-to-obtain raw materials/reagents. In the past six years, we have noticed the disclosure of mainly single and two-step processes with simple and mild reaction conditions for the preparation of Parvaquone. Only a few researchers had given an importance for the recovery and reuse of high-cost raw materials/reagents/solvents along with effluent management. If these aspects were collectively considered during the process development of drug, then the disclosed synthetic routes would become well accomplished for large-scale manufacturing.
{"title":"A comprehensive review of the disclosed approaches for the synthesis of Parvaquone, an anti-protozoan drug","authors":"Sanjay Sukumar Saralaya, Shashiprabha, Shridhara Kanakamajalu","doi":"10.1007/s12039-023-02145-6","DOIUrl":"10.1007/s12039-023-02145-6","url":null,"abstract":"<p>In this work, we have systematically reviewed the till date disclosed routes pertaining to the synthesis of Parvaquone. Prior art search gave us around nineteen synthetic routes, involving invention and innovation towards the starting material selection and process path to synthesize Parvaquone. Interestingly, 2-hydroxy naphthalene-1,4-dione has been the predominant raw material used for the synthesis of Parvaquone. Every process was executed to attain higher atom economy, process economy, and better purity of the product. In most of the works, a significant focus was given on choosing cheap and easy-to-obtain raw materials/reagents. In the past six years, we have noticed the disclosure of mainly single and two-step processes with simple and mild reaction conditions for the preparation of Parvaquone. Only a few researchers had given an importance for the recovery and reuse of high-cost raw materials/reagents/solvents along with effluent management. If these aspects were collectively considered during the process development of drug, then the disclosed synthetic routes would become well accomplished for large-scale manufacturing.</p>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s12039-023-02145-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5090748","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-03-25DOI: 10.1007/s12039-023-02149-2
Asha Matta, Leela Sai Lokesh Janardhanam, Venkata Vamsi Krishna Venuganti
The matrix-forming microneedle-based drug delivery system has the potential to localize drug dosage to the application site and limit systemic effects. Here, we report the development of sodium carboxymethyl cellulose, sodium alginate, and PEG 400 composite dissolvable microneedle patch for insertion in the buccal mucosa. The patch with pyramidal-shaped microneedles in 20 x 20 array format was fabricated by micromolding technique. The chemotherapeutic agent, 5-fluorouracil (5FU)-loaded microneedle patch, was characterized for physical and mechanical properties using a stereomicroscope, scanning electron microscope, and texture analyzer. Confocal laser scanning microscopy showed that microneedles were able to penetrate up to a depth of 120 µm inside the excised porcine buccal mucosa. The microneedles dissolved within 30s and 20 min after insertion in phosphate buffer and the excised buccal mucosa. 5FU permeation studies in the excised porcine buccal mucosa revealed a 1.8-fold greater flux after applying a microneedle patch compared with the 5FU solution. Applying a microneedle patch in the rat buccal mucosa for 30 min resulted in an accumulation of 330 µg/g of 5FU in the buccal tissue. In contrast, intravenous administration showed 5FU concentration below the detection limit in buccal tissue. In conclusion, a dissolvable microneedle patch can be developed for localized delivery of 5FU to treat oral carcinoma.
Graphical abstract
The pyramidal-shaped dissolvable polymeric microneedle patch loaded with 5-fluorouracil was fabricated through the micromolding technique. The microneedles demonstrated sufficient mechanical strength to penetrate buccal mucosa up to 120 µm. The microneedles dissolved after application into the buccal mucosa releasing 5-fluorouracil for localized drug delivery.
{"title":"Dissolvable layered microneedle patch containing 5-fluorouracil for localized treatment of oral carcinoma","authors":"Asha Matta, Leela Sai Lokesh Janardhanam, Venkata Vamsi Krishna Venuganti","doi":"10.1007/s12039-023-02149-2","DOIUrl":"10.1007/s12039-023-02149-2","url":null,"abstract":"<div><p>The matrix-forming microneedle-based drug delivery system has the potential to localize drug dosage to the application site and limit systemic effects. Here, we report the development of sodium carboxymethyl cellulose, sodium alginate, and PEG 400 composite dissolvable microneedle patch for insertion in the buccal mucosa. The patch with pyramidal-shaped microneedles in 20 x 20 array format was fabricated by micromolding technique. The chemotherapeutic agent, 5-fluorouracil (5FU)-loaded microneedle patch, was characterized for physical and mechanical properties using a stereomicroscope, scanning electron microscope, and texture analyzer. Confocal laser scanning microscopy showed that microneedles were able to penetrate up to a depth of 120 µm inside the excised porcine buccal mucosa. The microneedles dissolved within 30s and 20 min after insertion in phosphate buffer and the excised buccal mucosa. 5FU permeation studies in the excised porcine buccal mucosa revealed a 1.8-fold greater flux after applying a microneedle patch compared with the 5FU solution. Applying a microneedle patch in the rat buccal mucosa for 30 min resulted in an accumulation of 330 µg/g of 5FU in the buccal tissue. In contrast, intravenous administration showed 5FU concentration below the detection limit in buccal tissue. In conclusion, a dissolvable microneedle patch can be developed for localized delivery of 5FU to treat oral carcinoma.</p><h3>Graphical abstract</h3><p>The pyramidal-shaped dissolvable polymeric microneedle patch loaded with 5-fluorouracil was fabricated through the micromolding technique. The microneedles demonstrated sufficient mechanical strength to penetrate buccal mucosa up to 120 µm. The microneedles dissolved after application into the buccal mucosa releasing 5-fluorouracil for localized drug delivery.\u0000</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4974281","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-03-25DOI: 10.1007/s12039-023-02144-7
Madhuri P Rao, Anu Chauhan, Lucia Pintilie, Sudheer Kumar Singh, Madhu Ganesh
A chemoselective chlorination of nitroolefin was accomplished, and the resulting monochlorinated nitroolefin underwent [3+2]-cycloadditions with in-situ generated azomethine-ylide to afford spiro pyrrolidine-oxindoles. All the compounds were tested against exponentially growing Mycobacterium tuberculosis H37Ra (Mtb-Ra) cells. Two of the compounds exhibited 90% inhibition at 3.125 µM and 6.25 µM concentrations, respectively. The ex vivo activity assay in macrophage J774A.1 cell line showed one log Colony Forming Unit (CFU) reduction for both compounds after 24 h and approximately 2 log reduction after 48 h, suggesting almost 99% killing of Mtb-Ra after 48 h of exposure in macrophages. Although the cytotoxicity studies with both compounds showed low toxicity at MIC values for both compounds, given the efficient killing of Mtb-Ra in macrophages, the present group of compounds is interesting, and further work is in progress to reduce the toxicity of these compounds for further activity studies.
Graphical abstract
SYNOPSIS. Chemoselective chlorination of nitroolefins using iodobenzene dichloride (IBDC) was carried out to obtain monochlorinated nitroolefins. This was further demonstrated for [3+2]-cycloadditions with azomethine ylide and isatin to synthesize spiropyrrolidine oxindoles. This work also presents that two of the synthesized compounds was able to exhibit good activity against Mycobacterium tuberculosis H37Ra (Mtb-Ra) cells.
{"title":"Concise route to stereoselective chlorobenzene-based spiropyrrolidine oxindoles for pursuit as antitubercular agents","authors":"Madhuri P Rao, Anu Chauhan, Lucia Pintilie, Sudheer Kumar Singh, Madhu Ganesh","doi":"10.1007/s12039-023-02144-7","DOIUrl":"10.1007/s12039-023-02144-7","url":null,"abstract":"<div><p>A chemoselective chlorination of nitroolefin was accomplished, and the resulting monochlorinated nitroolefin underwent [3+2]-cycloadditions with <i>in-situ</i> generated azomethine-ylide to afford spiro pyrrolidine-oxindoles. All the compounds were tested against exponentially growing <i>Mycobacterium tuberculosis</i> H37Ra (<i>Mtb-</i>Ra) cells. Two of the compounds exhibited 90% inhibition at 3.125 <i>µ</i>M and 6.25 <i>µ</i>M concentrations, respectively. The <i>ex vivo</i> activity assay in macrophage J774A.1 cell line showed one log Colony Forming Unit (CFU) reduction for both compounds after 24 h and approximately 2 log reduction after 48 h, suggesting almost 99% killing of <i>Mtb</i>-Ra after 48 h of exposure in macrophages. Although the cytotoxicity studies with both compounds showed low toxicity at MIC values for both compounds, given the efficient killing of <i>Mtb</i>-Ra in macrophages, the present group of compounds is interesting, and further work is in progress to reduce the toxicity of these compounds for further activity studies.</p><h3>Graphical abstract</h3><p><b>SYNOPSIS.</b> Chemoselective chlorination of nitroolefins using iodobenzene dichloride (IBDC) was carried out to obtain monochlorinated nitroolefins. This was further demonstrated for [3+2]-cycloadditions with azomethine ylide and isatin to synthesize spiropyrrolidine oxindoles. This work also presents that two of the synthesized compounds was able to exhibit good activity against <i>Mycobacterium tuberculosis</i> H37Ra (<i>Mtb-</i>Ra) cells.\u0000</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5357642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Artificial intelligence (AI) and machine learning (ML) methods have touched practically all aspects of our life. Their utility ranges from separating different quality agricultural produce to facial recognition to guiding us through most steps in our day-to-day life. In this perspective article, we demonstrate the utility of artificial neural network (ANN) method in fitting potential energy curves and surfaces and point out the potential applications to predicting and analyzing dynamical observables. Although the regression methods seem to be successful in fitting potential energy surfaces using limited ab initio data, the ANN method yields accurate fits of surfaces when enough number of ab initio points on the potential energy surface become available. The possibility of utilizing the ANN method for fitting excitation function data is pointed out and the implications are discussed.
Graphical abstract
This perspective article illustrates how the artificial neural network can be used to interpolate accurately potential energy curves and surfaces for molecular systems and how the method can be extended to systems with avoided crossing of potential energy curves and to multidimensional excitation function data.
{"title":"Artificial neural networks and their utility in fitting potential energy curves and surfaces and related problems","authors":"Rupayan Biswas, Upakarasamy Lourderaj, Narayanasami Sathyamurthy","doi":"10.1007/s12039-023-02136-7","DOIUrl":"10.1007/s12039-023-02136-7","url":null,"abstract":"<div><p>Artificial intelligence (AI) and machine learning (ML) methods have touched practically all aspects of our life. Their utility ranges from separating different quality agricultural produce to facial recognition to guiding us through most steps in our day-to-day life. In this perspective article, we demonstrate the utility of artificial neural network (ANN) method in fitting potential energy curves and surfaces and point out the potential applications to predicting and analyzing dynamical observables. Although the regression methods seem to be successful in fitting potential energy surfaces using limited <i>ab initio</i> data, the ANN method yields accurate fits of surfaces when enough number of <i>ab initio</i> points on the potential energy surface become available. The possibility of utilizing the ANN method for fitting excitation function data is pointed out and the implications are discussed.</p><h3>Graphical abstract</h3><p>This perspective article illustrates how the artificial neural network can be used to interpolate accurately potential energy curves and surfaces for molecular systems and how the method can be extended to systems with avoided crossing of potential energy curves and to multidimensional excitation function data.</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4975398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-03-25DOI: 10.1007/s12039-023-02147-4
Gagandeep Kaur, Pawan Kumar
1,3,5-tris-(4 formyl phenyl) benzene and p-Phenylenediamine based covalent organic framework (COF) i.e., National University of Singapore-15 (NUS-15) have been synthesized using the solvothermal method at room temperature. Importantly, synthesized NUS-15 has been analysed using powdered X-ray diffraction (PXRD), Field emission scanning electron microscopy (FE-SEM), Infrared and UV-Visible spectroscopy techniques. Afterward, the optical properties of NUS-15 (excitation wavelength = 298 nm, emission wavelength = 404 nm) were confirmed through a photoluminescence spectrophotometer. Later on, biofunctionalization of NUS-15 was performed with Anti-BSA using coordination chemistry and confirmed through various analysis techniques. Based on optical properties, NUS-15-based Bioconjugate i.e., Anti-BSA@ NUS-15, has been utilized for selective sensing applications and noted 0.366 ppm detection limit for BSA. Our results imply that NUS-15 might be applied in future biomedical applications.
Graphical abstract
Synopsis. In this work, a covalent organic framework i.e., NUS-15 was synthesised and characterised for Anti-BSA tagged through simple coordination chemistry. Later, Anti BSA-tagged NUS-15 was explored for selective BSA sensing in a certain range using a photoluminescence spectrophotometer. Our results confirm 1.11 ppm (limit of quantification) and 0.366 ppm (limited of detection) during BSA detection.
{"title":"Imine linked AntiBSA@NUS-15 for molecular sensing applications","authors":"Gagandeep Kaur, Pawan Kumar","doi":"10.1007/s12039-023-02147-4","DOIUrl":"10.1007/s12039-023-02147-4","url":null,"abstract":"<div><p>1,3,5-tris-(4 formyl phenyl) benzene and p-Phenylenediamine based covalent organic framework (COF) <i>i.e.,</i> National University of Singapore-15 (NUS-15) have been synthesized using the solvothermal method at room temperature. Importantly, synthesized NUS-15 has been analysed using powdered X-ray diffraction (PXRD), Field emission scanning electron microscopy (FE-SEM), Infrared and UV-Visible spectroscopy techniques. Afterward, the optical properties of NUS-15 (excitation wavelength = 298 nm, emission wavelength = 404 nm) were confirmed through a photoluminescence spectrophotometer. Later on, biofunctionalization of NUS-15 was performed with Anti-BSA using coordination chemistry and confirmed through various analysis techniques. Based on optical properties, NUS-15-based Bioconjugate <i>i.e.,</i> Anti-BSA@ NUS-15, has been utilized for selective sensing applications and noted 0.366 ppm detection limit for BSA. Our results imply that NUS-15 might be applied in future biomedical applications.</p><h3>Graphical abstract</h3><p>Synopsis. In this work, a covalent organic framework <i>i.e.,</i> NUS-15 was synthesised and characterised for Anti-BSA tagged through simple coordination chemistry. Later, Anti BSA-tagged NUS-15 was explored for selective BSA sensing in a certain range using a photoluminescence spectrophotometer. Our results confirm 1.11 ppm (limit of quantification) and 0.366 ppm (limited of detection) during BSA detection.\u0000</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4975392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
More than 47,000 articles have been published in the area of Metal-Organic Framework since its seminal discovery in 1995, exemplifying the intense research carried out in this short span of time. Among other applications, gas adsorption and storage are perceived as central to the MOFs research, and more than 10,000 MOFs structures are reported to date to utilize them for various gas storage/separation applications. Molecular modeling, particularly based on density functional theory, played a key role in (i) understanding the nature of interactions between the gas and the MOFs geometry (ii) establishing various binding pockets and relative binding energies, and (iii) offering design clues to improve the gas uptake capacity of existing MOF architectures. In this review, we have looked at various MOFs that are studied thoroughly using DFT/periodic DFT (pDFT) methods for CO2, H2, O2, and CH4 gases to provide a birds-eye-view on how various exchange-correlation functionals perform in estimating the binding energy for various gases and how factors such as nature of the (i) metal ion, (ii) linkers, (iii) ligand, (iv) spin state and (v) spin-couplings play a role in this process with selected examples. While there is still room for improvement, the rewards offered by the molecular modelling of MOFs were already substantial that we advocate experimental and theoretical studies to go hand-in-hand to undercut the trial-and-error approach that is often perceived in the selection of MOFs and gas partners in this area.
Graphical abstract
The importance of density functional theory-based molecular modeling studies in offering design clues to improve the gas adsorption and storage capacity of existing MOF architectures is discussed here. The use of DFT-based investigation in conjunction with experimental synthesis is an imperative tool in designing new-generation MOFs with enhanced uptake capacity.
{"title":"Role of molecular modelling in the development of metal-organic framework for gas adsorption applications","authors":"Reshma Jose, Garima Bangar, Sourav Pal, Gopalan Rajaraman","doi":"10.1007/s12039-022-02130-5","DOIUrl":"10.1007/s12039-022-02130-5","url":null,"abstract":"<div><p>More than 47,000 articles have been published in the area of Metal-Organic Framework since its seminal discovery in 1995, exemplifying the intense research carried out in this short span of time. Among other applications, gas adsorption and storage are perceived as central to the MOFs research, and more than 10,000 MOFs structures are reported to date to utilize them for various gas storage/separation applications. Molecular modeling, particularly based on density functional theory, played a key role in (i) understanding the nature of interactions between the gas and the MOFs geometry (ii) establishing various binding pockets and relative binding energies, and (iii) offering design clues to improve the gas uptake capacity of existing MOF architectures. In this review, we have looked at various MOFs that are studied thoroughly using DFT/periodic DFT (pDFT) methods for CO<sub>2</sub>, H<sub>2</sub>, O<sub>2</sub>, and CH<sub>4</sub> gases to provide a birds-eye-view on how various exchange-correlation functionals perform in estimating the binding energy for various gases and how factors such as nature of the (i) metal ion, (ii) linkers, (iii) ligand, (iv) spin state and (v) spin-couplings play a role in this process with selected examples. While there is still room for improvement, the rewards offered by the molecular modelling of MOFs were already substantial that we advocate experimental and theoretical studies to go hand-in-hand to undercut the trial-and-error approach that is often perceived in the selection of MOFs and gas partners in this area.</p><h3>Graphical abstract</h3><p>The importance of density functional theory-based molecular modeling studies in offering design clues to improve the gas adsorption and storage capacity of existing MOF architectures is discussed here. The use of DFT-based investigation in conjunction with experimental synthesis is an imperative tool in designing new-generation MOFs with enhanced uptake capacity.\u0000</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 2","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s12039-022-02130-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4581473","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-02-27DOI: 10.1007/s12039-023-02138-5
Jun He, Meng Yuan, Haodong Ren, Tao Song, Yihan Zhang
The environmentally friendly preparation of sulfur-free expanded graphite (EG) remains a great challenge. A large amount of strong acids and strong oxidants were used to prepare expandable graphite, resulting in environmental pollution problems. Herein, a novel and green preparation method for EG has been developed. Sulfur-free EG was fabricated using natural flake graphite (NFG), sodium perchlorate (NaClO4), and oxalic acid (C2H2O4) as raw materials. The electrochemical oxidation method was applied to prepare sulfur-free expandable graphite, and microwave irradiation technology was adopted to prepare sulfur-free EG. Sulfur-free expandable graphite was heated to generate sulfur-free EG through microwave irradiation technology. The optimum weight ratio was as follows: NFG:NaClO4:C2H2O4 = 1.5:10:2. The anodic oxidation occurred under a constant current density of 47 mA/cm2, and the intercalation reaction lasted for 60 min at ambient temperature. The largest expanded volume (EV) of sulfur-free EG was 290 mL/g. The FTIR spectrum proved that the ClO4− and COO− groups had entered the graphite layers. The SEM images showed that the graphite layers were completely opened, and the pore structure was clearly observed. The sulfur-free EG prepared by the method does not cause environmental pollution and has broad application prospects.
Graphical abstract
Natural flake graphite is composed of carbon atoms and has a layered structure. Oxidant oxidizes the edges of the graphite layer, causing the interplanar spacing to increase, and the intercalation agent molecules could enter the layers. The expandable graphite was synthesized, and microwave irradiation technology was adopted to prepare expanded graphite.
{"title":"The electrochemical preparation and characterization of sulfur-free expanded graphite","authors":"Jun He, Meng Yuan, Haodong Ren, Tao Song, Yihan Zhang","doi":"10.1007/s12039-023-02138-5","DOIUrl":"10.1007/s12039-023-02138-5","url":null,"abstract":"<div><p>The environmentally friendly preparation of sulfur-free expanded graphite (EG) remains a great challenge. A large amount of strong acids and strong oxidants were used to prepare expandable graphite, resulting in environmental pollution problems. Herein, a novel and green preparation method for EG has been developed. Sulfur-free EG was fabricated using natural flake graphite (NFG), sodium perchlorate (NaClO<sub>4</sub>), and oxalic acid (C<sub>2</sub>H<sub>2</sub>O<sub>4</sub>) as raw materials. The electrochemical oxidation method was applied to prepare sulfur-free expandable graphite, and microwave irradiation technology was adopted to prepare sulfur-free EG. Sulfur-free expandable graphite was heated to generate sulfur-free EG through microwave irradiation technology. The optimum weight ratio was as follows: NFG:NaClO<sub>4</sub>:C<sub>2</sub>H<sub>2</sub>O<sub>4</sub> = 1.5:10:2. The anodic oxidation occurred under a constant current density of 47 mA/cm<sup>2</sup>, and the intercalation reaction lasted for 60 min at ambient temperature. The largest expanded volume (EV) of sulfur-free EG was 290 mL/g. The FTIR spectrum proved that the ClO<sub>4</sub><sup>−</sup> and COO<sup>−</sup> groups had entered the graphite layers. The SEM images showed that the graphite layers were completely opened, and the pore structure was clearly observed. The sulfur-free EG prepared by the method does not cause environmental pollution and has broad application prospects.</p><h3>Graphical abstract</h3><p>Natural flake graphite is composed of carbon atoms and has a layered structure. Oxidant oxidizes the edges of the graphite layer, causing the interplanar spacing to increase, and the intercalation agent molecules could enter the layers. The expandable graphite was synthesized, and microwave irradiation technology was adopted to prepare expanded graphite.</p><figure><div><div><div><picture><source><img></source></picture></div></div></div></figure></div>","PeriodicalId":50242,"journal":{"name":"Journal of Chemical Sciences","volume":"135 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2023-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5038641","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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