A new fluorescent receptor HL was synthesized by an easy condensation reaction of ortho-vanillin and 1-(3-aminopropyl)imidazole.The probe HL was found to be highly selective and sensitive towards Zn^(2+)/Cu^(2+)ions i...A new fluorescent receptor HL was synthesized by an easy condensation reaction of ortho-vanillin and 1-(3-aminopropyl)imidazole.The probe HL was found to be highly selective and sensitive towards Zn^(2+)/Cu^(2+)ions in the presence of a wide range of metal cations.The interaction of HL with Zn^(2+)ions showed a distinct fluorescence enhancement(turn-on)at 470 nm.Moreover,after the subsequent addition of Cu^(2+)ions into the same solution,a fluorescence‘turn-off’phenomenon was observed.The sensing ability of the chemodosimeter HL towards Zn^(2+)was confirmed by fluorescence,UV-Vis and 1H NMR titration analysis.The binding mode of HL towards Zn^(2+)and Cu^(2+)was authenticated by single crystal X-ray analysis,which divulged the formation of dinuclear complexes 1 and 2.Furthermore,we performed NOESY and COSY studies of complexes 1 and 2 to detect their shapes and interlocking units.Moreover,the cytotoxicity of HL and 1 towards HeLa cancer cells was studied,and both were found to be non-cytotoxic in nature.This prompted us to explore the intracellular fluorescence turn-on sensing activity of HL with Zn^(2+)ions.The intracellular sensing behavior of HL towards Zn^(2+)was confirmed towards in two cancer cell lines viz.,HeLa and DU-145 cell lines.The limit of detection(LOD)for Zn^(2+)and Cu^(2+)sensing was found to be 31.044 nM and 11.64 nM,respectively.展开更多
Photocatalysis powered by unlimited solar energy is an effective strategy to resolve energy and environ-mental issues.To achieve an efficient photocatalytic system,photocatalysts need to be highly crystalline and poro...Photocatalysis powered by unlimited solar energy is an effective strategy to resolve energy and environ-mental issues.To achieve an efficient photocatalytic system,photocatalysts need to be highly crystalline and porous with excellent photostability under extreme conditions.In this case,covalent organic frame-works(COFs)have shown immense potential for photocatalytic applications owing to their unique struc-ture as well as electronic and photophysical characteristics.COFs possess a crystalline porous network with light absorption capabilities and excellent stability.Furthermore,functionalized COFs can be devel-oped through organic unit variation to obtain broader absorption,narrow bandgap,effective charge sep-aration,and transportation.Furthermore,high photocatalytic efficiency can be achieved via the formation of heterostructures through anchoring or post-synthetic modification.Our review is focused on the recent advancements in COFs as photocatalysts for various photocatalytic applications.Initially,we emphasize the topological design,linkage chemistry,and functionalization of COFs,underscoring the principles and requirements for high photocatalytic efficiency.This provides deep insights into the capa-bilities of COFs in different photocatalytic applications,covering areas such as hydrogen and oxygen evol-ution,carbon dioxide reduction,organic transformation,and organic pollutant degradation.Finally,we summarize the pivotal points that need urgent attention and outline future avenues,offering fresh per-spectives and contributing to revolutionary innovations in this rapidly evolving field.展开更多
The 1,3-dipolar cycloaddition reaction of cis-[Co(N_(3))_(2)(en)_(2)]NO_(3)1 with different organonitriles(NCR)under focussed microwave irradiation produced bis-tetrazolate complexes[Co(N_(4)CR)_(2)(en)_(2)](NO_(3)).I...The 1,3-dipolar cycloaddition reaction of cis-[Co(N_(3))_(2)(en)_(2)]NO_(3)1 with different organonitriles(NCR)under focussed microwave irradiation produced bis-tetrazolate complexes[Co(N_(4)CR)_(2)(en)_(2)](NO_(3)).Interestingly,in the case of 3-cyano pyridine the reaction produced both cis-and trans-isomers(cis-2 and trans-2),whereas for 4-cyano pyridine the compound obtained was exclusively cis(cis-3)and for 4-bromobenzonitrile it was only the trans-(trans-4)compound which was isolated.This indicates a probable role of remote substitution of the phenyl ring in dictating the formation of the preferential isomer.When starting from the trans-isomer of the diazido complex(trans-[Co(N_(3))_(2)(en)_(2)]ClO_(4),1a),upon reacting with different nitriles a mixture of cis-and trans-isomers of[Co(N_(4)CR)_(2)(en)_(2)]ClO_(4)was produced in each case,with a greater preference towards cis-geometry[R=4-NC_(5)H_(4)(cis-5 and trans-5),4-BrC_(6)H_(4)(cis-6 and trans-6)and C_(6)H_(5)(cis-7 and trans-7)].The preferential formation of the cis-analogue of compound trans-4 when starting from the trans-precursor was quite curious.A theoretical investigation of compounds trans-4 and cis-6 reveals that the greater stability of the trans-complex 4 may arise from additional van der Waals interactions in the solid state because of the presence of an extra DMF molecule as solvent of crystallization.However,an interacting counter-anion and a probable halogen–halogen interaction may also contribute to the formation of preferential isomers for cycloaddition complexes,even in the solution state.展开更多
A highly active phosphine-free ruthenium-arene complex,[(η^(6)-C_(6)H_(6))RuCl_(2)(C_(6)H_(5)NH_(2))],exhibits excellent catalytic performance for a one-pot conversion of aldehydes to primary amides at low temperatur...A highly active phosphine-free ruthenium-arene complex,[(η^(6)-C_(6)H_(6))RuCl_(2)(C_(6)H_(5)NH_(2))],exhibits excellent catalytic performance for a one-pot conversion of aldehydes to primary amides at low temperature(60°C),in water and without any inert gas protection.The reported catalyst performed exceptionally well for a huge range of aldehydes,including aromatic,heteroaromatic,aliphatic and conjugated systems,with a high tolerance for other functional groups.The development of such highly active catalysts using simple reagents will offer new opportunities for the development of improved phosphine-free catalytic systems for this and other related catalytic reactions.展开更多
文摘A new fluorescent receptor HL was synthesized by an easy condensation reaction of ortho-vanillin and 1-(3-aminopropyl)imidazole.The probe HL was found to be highly selective and sensitive towards Zn^(2+)/Cu^(2+)ions in the presence of a wide range of metal cations.The interaction of HL with Zn^(2+)ions showed a distinct fluorescence enhancement(turn-on)at 470 nm.Moreover,after the subsequent addition of Cu^(2+)ions into the same solution,a fluorescence‘turn-off’phenomenon was observed.The sensing ability of the chemodosimeter HL towards Zn^(2+)was confirmed by fluorescence,UV-Vis and 1H NMR titration analysis.The binding mode of HL towards Zn^(2+)and Cu^(2+)was authenticated by single crystal X-ray analysis,which divulged the formation of dinuclear complexes 1 and 2.Furthermore,we performed NOESY and COSY studies of complexes 1 and 2 to detect their shapes and interlocking units.Moreover,the cytotoxicity of HL and 1 towards HeLa cancer cells was studied,and both were found to be non-cytotoxic in nature.This prompted us to explore the intracellular fluorescence turn-on sensing activity of HL with Zn^(2+)ions.The intracellular sensing behavior of HL towards Zn^(2+)was confirmed towards in two cancer cell lines viz.,HeLa and DU-145 cell lines.The limit of detection(LOD)for Zn^(2+)and Cu^(2+)sensing was found to be 31.044 nM and 11.64 nM,respectively.
基金S.M.M.sincerely thanks SERB-DST,New Delhi,India(Project CRG/2020/001769)BRNS,Mumbai,India(Project 58/14/17/2020-BRNS/37215)+1 种基金Ministry of Textiles{Project 2/1/2021-NTTM(Pt.)}India for financial assessment.
文摘Photocatalysis powered by unlimited solar energy is an effective strategy to resolve energy and environ-mental issues.To achieve an efficient photocatalytic system,photocatalysts need to be highly crystalline and porous with excellent photostability under extreme conditions.In this case,covalent organic frame-works(COFs)have shown immense potential for photocatalytic applications owing to their unique struc-ture as well as electronic and photophysical characteristics.COFs possess a crystalline porous network with light absorption capabilities and excellent stability.Furthermore,functionalized COFs can be devel-oped through organic unit variation to obtain broader absorption,narrow bandgap,effective charge sep-aration,and transportation.Furthermore,high photocatalytic efficiency can be achieved via the formation of heterostructures through anchoring or post-synthetic modification.Our review is focused on the recent advancements in COFs as photocatalysts for various photocatalytic applications.Initially,we emphasize the topological design,linkage chemistry,and functionalization of COFs,underscoring the principles and requirements for high photocatalytic efficiency.This provides deep insights into the capa-bilities of COFs in different photocatalytic applications,covering areas such as hydrogen and oxygen evol-ution,carbon dioxide reduction,organic transformation,and organic pollutant degradation.Finally,we summarize the pivotal points that need urgent attention and outline future avenues,offering fresh per-spectives and contributing to revolutionary innovations in this rapidly evolving field.
文摘The 1,3-dipolar cycloaddition reaction of cis-[Co(N_(3))_(2)(en)_(2)]NO_(3)1 with different organonitriles(NCR)under focussed microwave irradiation produced bis-tetrazolate complexes[Co(N_(4)CR)_(2)(en)_(2)](NO_(3)).Interestingly,in the case of 3-cyano pyridine the reaction produced both cis-and trans-isomers(cis-2 and trans-2),whereas for 4-cyano pyridine the compound obtained was exclusively cis(cis-3)and for 4-bromobenzonitrile it was only the trans-(trans-4)compound which was isolated.This indicates a probable role of remote substitution of the phenyl ring in dictating the formation of the preferential isomer.When starting from the trans-isomer of the diazido complex(trans-[Co(N_(3))_(2)(en)_(2)]ClO_(4),1a),upon reacting with different nitriles a mixture of cis-and trans-isomers of[Co(N_(4)CR)_(2)(en)_(2)]ClO_(4)was produced in each case,with a greater preference towards cis-geometry[R=4-NC_(5)H_(4)(cis-5 and trans-5),4-BrC_(6)H_(4)(cis-6 and trans-6)and C_(6)H_(5)(cis-7 and trans-7)].The preferential formation of the cis-analogue of compound trans-4 when starting from the trans-precursor was quite curious.A theoretical investigation of compounds trans-4 and cis-6 reveals that the greater stability of the trans-complex 4 may arise from additional van der Waals interactions in the solid state because of the presence of an extra DMF molecule as solvent of crystallization.However,an interacting counter-anion and a probable halogen–halogen interaction may also contribute to the formation of preferential isomers for cycloaddition complexes,even in the solution state.
文摘A highly active phosphine-free ruthenium-arene complex,[(η^(6)-C_(6)H_(6))RuCl_(2)(C_(6)H_(5)NH_(2))],exhibits excellent catalytic performance for a one-pot conversion of aldehydes to primary amides at low temperature(60°C),in water and without any inert gas protection.The reported catalyst performed exceptionally well for a huge range of aldehydes,including aromatic,heteroaromatic,aliphatic and conjugated systems,with a high tolerance for other functional groups.The development of such highly active catalysts using simple reagents will offer new opportunities for the development of improved phosphine-free catalytic systems for this and other related catalytic reactions.
