The design and synthesis of a novel π-conjugated fiuorescent framework by external ligand-assisted C-H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein.These n...The design and synthesis of a novel π-conjugated fiuorescent framework by external ligand-assisted C-H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein.These novel fiuorescent materials could present full-color-tunable emissions with large Stokes shifts. Furthermore, the protocol provides an opportunity to rapidly screen novel organic single-molecule whitelight materials with high fiuorescence quantum yields. The robust organic and low-cost white lightemitting diodes could rapidly be fabricated using the white-light-emitting material. Experimental data and theoretical calculations indicate that in the white-light dual emission the relatively short wavelength from high-lying singlet state emission and the relatively long wavelength from low-lying singlet state emission. The anti-Kasha dual-emission systems will provide a foundation for the development and application of organic single-molecule white light materials, effectively promoting the development and innovation of luminescent materials. In addition, this method demonstrated its potential application in the synthesis of new near-infrared(NIR) fiuorescence materials with large Stokes shifts based on the olefination of heterocycles.展开更多
Glioblastoma,the most aggressive form of brain tumor,poses significant challenges in terms of treatment success and patient survival.Current treatment modalities for glioblastoma include radiation therapy,surgical int...Glioblastoma,the most aggressive form of brain tumor,poses significant challenges in terms of treatment success and patient survival.Current treatment modalities for glioblastoma include radiation therapy,surgical intervention,and chemotherapy.Unfortunately,the median survival rate remains dishearteningly low at 12–15 months.One of the major obstacles in treating glioblastoma is the recurrence of tumors,making chemotherapy the primary approach for secondary glioma patients.However,the efficacy of drugs is hampered by the presence of the blood-brain barrier and multidrug resistance mechanisms.Consequently,considerable research efforts have been directed toward understanding the underlying signaling pathways involved in glioma and developing targeted drugs.To tackle glioma,numerous studies have examined kinase-downstream signaling pathways such as RAS-RAF-MEKERK-MPAK.By targeting specific signaling pathways,heterocyclic compounds have demonstrated efficacy in glioma therapeutics.Additionally,key kinases including phosphatidylinositol 3-kinase(PI3K),serine/threonine kinase,cytoplasmic tyrosine kinase(CTK),receptor tyrosine kinase(RTK)and lipid kinase(LK)have been considered for investigation.These pathways play crucial roles in drug effectiveness in glioma treatment.Heterocyclic compounds,encompassing pyrimidine,thiazole,quinazoline,imidazole,indole,acridone,triazine,and other derivatives,have shown promising results in targeting these pathways.As part of this review,we propose exploring novel structures with low toxicity and high potency for glioma treatment.The development of these compounds should strive to overcome multidrug resistance mechanisms and efficiently penetrate the blood-brain barrier.By optimizing the chemical properties and designing compounds with enhanced drug-like characteristics,we can maximize their therapeutic value and minimize adverse effects.Considering the complex nature of glioblastoma,these novel structures should be rigorously tested and evaluated for their efficacy and safety profiles.展开更多
Heterogeneous porous carbon(PC)materials have gained unique importance in the catalysis community due to their captivating properties,including high specific surface area,tunable porosity,and function-ality.PC can pla...Heterogeneous porous carbon(PC)materials have gained unique importance in the catalysis community due to their captivating properties,including high specific surface area,tunable porosity,and function-ality.PC can play a prominent role in the sustainable synthesis of functional heterocycles,as they are a low-cost alternative while being an efficient and user-friendly material.This review examines the prepa-ration and applicability of these carbonaceous materials used as catalysts or support for biologically active heterocycles synthesis,including hydrogenation,oxidation,oxidative dehydrogenation,cross-coupling,and other organic reactions.Moreover,the challenges,potential future development directions,and opportuni-ties in the synthesis of potent bioactive heterocycles over PC materials have been addressed.This review will inspire further research to explore novel PC materials and their implications in heterocyclization.展开更多
An inexpensive phosphine catalyst was used effectively for a transition-metal-free acyl-transfer of N-containing heteroaryl ketones for the rapid synthesis of N-fused heterocycles.The key pre-aromatic spirocyclic inte...An inexpensive phosphine catalyst was used effectively for a transition-metal-free acyl-transfer of N-containing heteroaryl ketones for the rapid synthesis of N-fused heterocycles.The key pre-aromatic spirocyclic intermediate initialized by the single electron transfer(SET)process of Togni's reagentⅡpromoted by the tertiary phosphine resulted in an intriguing and alternative tactic for the cleavage of C–C bonds.By using inexpensive tertiary phosphine as the catalyst,this skeleton-reorganizing approach of N-containing heteroaryl ketones allows a streamlined assembly of complex N-fused heterocycles with broad functional group tolerance.展开更多
Interaction between bovine serum albumin(BSA) and phosphorus heterocycles(PHs) was studied using multispectroscopic techniques. The results indicated the high binding affinity of PHs to BSA as it quenches the intrinsi...Interaction between bovine serum albumin(BSA) and phosphorus heterocycles(PHs) was studied using multispectroscopic techniques. The results indicated the high binding affinity of PHs to BSA as it quenches the intrinsic fluorescence of BSA. The experimental data suggested the fluorescence quenching mechanism between PHs and BSA as a dynamic quenching. From the UV–vis studies, the apparent association constant(K_(app)) was found to be 9.25×10~2, 1.27×10~4and 9.01×10~2L/mol for the interaction of BSA with PH-1, PH-2 and PH-3,respectively. According to the F?rster's non-radiation energy transfer(FRET) theory, the binding distances between BSA and PHs were calculated. The binding distances(r) of PH-1, PH-2 and PH-3 were found to be2.86, 3.03, and 5.12 nm, respectively, indicating energy transfer occurs between BSA and PHs. The binding constants of the PHs obtained from the fluorescence quenching data were found to be decreased with increase of temperature. The negative values of the thermodynamic parameters ΔH, ΔS and ΔG at different temperatures revealed that the binding process is spontaneous; hydrogen bonds and van der Waals interaction were the main force to stabilize the complex. The microenvironment of the protein-binding site was studied by synchronous fluorescence and circular dichroism(CD) techniques and data indicated that the conformation of BSA changed in the presence of PHs. Finally, we studied the BSA-PHs docking using Auto Dock and results suggest that PHs is located in the cleft between the domains of BSA.展开更多
P450 fatty acid decarboxylase Ole T from Staphylococcus aureus(Ole TSA)is a novel cytochrome P450 enzyme that catalyzes the oxidative decarboxylation of fatty acids to yield primarily terminal alkenes and CO_(2) or mi...P450 fatty acid decarboxylase Ole T from Staphylococcus aureus(Ole TSA)is a novel cytochrome P450 enzyme that catalyzes the oxidative decarboxylation of fatty acids to yield primarily terminal alkenes and CO_(2) or minor a-andβ-hydroxylated fatty acids as side-products.In this work,the interactions between a series of cycloalkyl phosphorus heterocycles(CPHs)and Ole TSAwere investigated in detail by fluorescence titration experiment,ultraviolet-visible(UV-vis)and31 P NMR spectroscopies.Fluorescence titration experiment results clearly showed that a dynamic quenching occurred when CPH-6,a representative CPHs,interacted with Ole TSAwith a binding constant value of 15.2×104 M-1 at 293 K.The thermodynamic parameters(ΔH,ΔS andΔG)showed that the hydrogen bond and van der Waals force played major roles in the interaction between Ole TSAand CPHs.The UV-vis and31 P NMR studies indicated the penetration of CPH-6 into the interior environment of Ole TSA,which greatly affects the enzymatic activity of Ole TSA.Therefore,our study revealed an effective way to use phosphorus heterocyclic compounds to modulate the activity of cytochrome P450 enzymes.展开更多
Benzimidazoles, benzoxazoles, and benzothiazoles derivatives were synthesized from condensation of aldehydes and 1,2-phenylenediamine or ortho-aminophenol or ortho-aminothiophenol in the presence of catalytic amount o...Benzimidazoles, benzoxazoles, and benzothiazoles derivatives were synthesized from condensation of aldehydes and 1,2-phenylenediamine or ortho-aminophenol or ortho-aminothiophenol in the presence of catalytic amount of Fe（Ⅲ）-Schiff base/SBA-15 in water medium. Short reaction times, good to excellent yields, easy availability, reusability, and use of an eco-friendly catalyst are some of the significant attributes of the present method.展开更多
（~）-Calanolide A was the first natural product identified as an active agent against HIV-1 and Mycobacterium tuberculosis （Mtb）. In devising a scaffold-hopping strategy of structure modification of （＋）-calanoli...（~）-Calanolide A was the first natural product identified as an active agent against HIV-1 and Mycobacterium tuberculosis （Mtb）. In devising a scaffold-hopping strategy of structure modification of （＋）-calanolide A, we focused on the synthesis of calanolides by replacing ring D with various five or six membered nitrogen-containing heterocycles, hoping to get further understanding of the structure- activity relationship.展开更多
Nucleophilic chiral phosphine catalysis has been prosperous in asymmetric synthesis over the past two decades. Various tunable chiral phosphines display excellent activity and selectivity in asymmetric transformations...Nucleophilic chiral phosphine catalysis has been prosperous in asymmetric synthesis over the past two decades. Various tunable chiral phosphines display excellent activity and selectivity in asymmetric transformations including acycloaddition reactions and cycloaddition reactions. Enantiomerically enriched cyclic compounds are ubiquitous in natural products and drug molecules. These phosphinecatalyzed reactions provide effective and extensive strategies for the synthesis of a series of complex cyclic compounds as well as the synthesis of chiral compounds which could be easily transformed to carbocycles and heterocycles. This minireview summarizes recent developments in this area and highlights meaningful breakthroughs.展开更多
Polynitrogen heterocycles are readily available and have recently arisen as versatile synthons for the formation of various C-C and C-X bonds,and medicinally active nitrogen-containing heterocycles.Several cascade rea...Polynitrogen heterocycles are readily available and have recently arisen as versatile synthons for the formation of various C-C and C-X bonds,and medicinally active nitrogen-containing heterocycles.Several cascade reactions,including annulation,radical cascade,and borylation reactions,have been reported in which polynitrogen heterocycles are applied as arylation reagents.The success of these exceptional reactions illustrates the great synthetic potential of polynitrogen heterocycles,which provides a direct and useful approach to arylation reactions and the synthesis of nitrogen-containing heterocycles.The use of photocatalysts to effectively transfer energy from visible light to non-absorbing compounds has gained increasing attention as this method allows for the mild and efficient generation of radicals in a controlled manner.This approach has thus led to new methods that involve unique bond formation reactions.In addition,the use of free radical intermediates stabilized by transition metal catalysts is a powerful way to construct new chemical bonds.The aim of this review is to highlight the rapidly expanding area of radical-initiated denitrogenative cascade reactions of polynitrogen heterocycles and elaborate on their mechanisms from a new perspective by using photocatalysis and metal-based catalysis.展开更多
Research on pollution characteristics and toxicities of emerging polycyclic aromatic sulfur heterocycles(PASHs) in PM_(2.5) has not been reported due to the lack of analytical method with the needed performance.In the...Research on pollution characteristics and toxicities of emerging polycyclic aromatic sulfur heterocycles(PASHs) in PM_(2.5) has not been reported due to the lack of analytical method with the needed performance.In the present study,a novel method for the determination of 14 PASHs in PM_(2.5) was developed using atmospheric pressure gas chro matography-tandem mass spectrometry(APGC-MS/MS).Atmospheric pressure chemical ionization was operated with multiple reaction monitoring in positive ionization mode.High sensitivity(method detection limit <1.673 pg/m^(3)),acceptable re coveries(67.6%-120.8%) and precisions(RSD of 2.2%-15.4%) were obtained.The method was successfully applied for analyzing PASHs in 10 PM_(2.5) samples collected from Taiyuan,a typical industrial city in China,in 2016,The total concentrations were from 929 pg/m^(3) to 14,593 pg/m^(3).The determined levels indicated that further investigations on environmental fate and toxicities of PM_(2.5)-bound PASHs may be needed.展开更多
New functionalized fused heterocycles, such as, 1,3,6,9,11-pentasubstituted-pyrido[3,2-f:6,5-f']bis([1,2,4]triazolo[4,3-a]-pyrimidin-5(1H)-ones (6) and 1,3-disubstituted-7-[(E)-2-(thiophen-2-yl)ethenyl]-1,4,9,9a-t...New functionalized fused heterocycles, such as, 1,3,6,9,11-pentasubstituted-pyrido[3,2-f:6,5-f']bis([1,2,4]triazolo[4,3-a]-pyrimidin-5(1H)-ones (6) and 1,3-disubstituted-7-[(E)-2-(thiophen-2-yl)ethenyl]-1,4,9,9a-tetrahydro-6H-[1,2,4]triazino[4,3-b][1,2,4,5]-tetrazin-6-ones (16) were synthesized via reaction of the hydrazonoyl chlorides (1) with 1,3,6-triphenyl-9-thioxo-9,10-dihydro-pyrimido [4,5-b]pyrido[4,5-d][1,2,4]triazolo[4,3-a]pyrimidin-5,7(1H,8H)-di-one (5) and 4-amino-6-[(2-thiophen-2-yl)ethenyl]-3-thioxo-3,4-dihydro-[1,2,4]triazin-5(2H)-one (11), respectively. The mechanism and the regioselectivity of the studied reactions have been discussed. The biological activity of the products has been evaluated against some fungi and bacteria species. The tested compounds exhibited moderate activity against the bacteria species.展开更多
Cyanine dyes of zero/bis-zero methine incorporating imid-azo(1,2-a)Pyridine (quinoline) or pyrazino(1,2-a)pyridine (quinoline) with stable C-N bond were synthesized using keto-oxime methylene C-link heterocyclic quate...Cyanine dyes of zero/bis-zero methine incorporating imid-azo(1,2-a)Pyridine (quinoline) or pyrazino(1,2-a)pyridine (quinoline) with stable C-N bond were synthesized using keto-oxime methylene C-link heterocyclic quaternary salts [1-phenyl-3-methyl-pyrazolino-4-keto-oxime-α-methylene-bis-pyridin-(quinoin)-1(4)-di-ium-iodide(ethiodide) salts and 1-phenyl-3-methyl-pyrazolino- 4-ketooxime-α-methylene-N-2-methyl-bis pyridin (quinoin)-1(4)-di-ium-iodide(ethiodide) salts]. Such heterocyclic precursors and related dyes were identified by elemental and spectral analyses. The absorption spectra properties of such dyes were investigated in 95% Ethanol to attempt and throw some light on the influence of such new heterocyclic nuclei and to compare or evaluate spectral behaviors. The absorption spectra of dyes in different pure solvents were examined in the visible region showing solvatochromism and the colour changes of dyes with solvents having different polarities. This permits a selection of the optimal solvent (fractional solvent) when such dyes are applied as photosensitizers. The spectral behavior of some selected newly synthesized cyanine dyes is observed in mixed solvents of different polarities and progressively increasing quantities of one solvent over the other were studied and showed an increase in the absorbance of CT band with increasing proportion of that solvent. Evidence for hydrogen bond formation between the solute molecules and solvent molecules allows measurement of certain energies such as hydrogen bonding, orientation, and free energies.展开更多
Ma＇s CuI/proline procedure for the catalytic cross coupling between nitrogen heterocycles and aryl halides was markedly improved. The key finding was that K3PO4 was a much better base than K2CO3 for the reaction. Wit...Ma＇s CuI/proline procedure for the catalytic cross coupling between nitrogen heterocycles and aryl halides was markedly improved. The key finding was that K3PO4 was a much better base than K2CO3 for the reaction. With this new reaction condition the cross coupling with aryl iodides could be accomplished in 1,4-dioxane instead of DMSO. This reactin also could be carried out in DMF. Furthermore, the coupling yields under the new conditions are usually higher than in Ma＇s original methods.展开更多
The ligand exchange reaction with heterocycles containing nitrogen, oxygen or sulfur atoms was carried out. For the reaction with heterocycles, the order of the reactivity was S-heterocycles > N-heterocycles > O...The ligand exchange reaction with heterocycles containing nitrogen, oxygen or sulfur atoms was carried out. For the reaction with heterocycles, the order of the reactivity was S-heterocycles > N-heterocycles > O-heterocycles. Furthermore, when the results for the heterocycles were compared to those for the corresponding hydrocarbons, the hydrocarbons had a higher reactivity. These results mean that the reactivity would be mainly governed by the electron density of these arenes.展开更多
An intramolecular selenocyclizations of olefins mediated by a commercially available hypervalent iodine(Ⅲ) reagent,PhIO,was developed.This method provided access to a wide range of selenenylated heterocycles under am...An intramolecular selenocyclizations of olefins mediated by a commercially available hypervalent iodine(Ⅲ) reagent,PhIO,was developed.This method provided access to a wide range of selenenylated heterocycles under ambient conditions.The striking advantages of this protocol over all previous methods include mild reaction conditions,easy operation,good yields,high levels of functional group compatibility,large-scale application and suitability for the late-stage functionalization of complex molecules of biological importance.展开更多
Novel stable high spin molecules possessing three different arranged fashions are designed with - · N-N< as a spin-containing(SC) fragment, phenylene as an end group and various aromatic molecules, such as ben...Novel stable high spin molecules possessing three different arranged fashions are designed with - · N-N< as a spin-containing(SC) fragment, phenylene as an end group and various aromatic molecules, such as benzene(1), 2,6-pyridine(2), 3,5-pyridine(3), pyridazine(4), 4,6-pyrimidine(5), 2,6-pyrimidine(6), pyrazine(7) and triazine(8), as a ferromagnetic coupling(FC) unit. The effects of the different coupling units on the spin multiplicities of the ground states and their stabilities were investigated by means of AM1-CI approach. It has been found that the spin densities on the two atoms of the SC fragment are different from delocalization results in the specific stability of - · N-N<. In these molecules, the stabilities of the triplet states decrease when the distance between the atoms of central SC(-N-) increases. It is shown that the heterocycles as the coupling units have influence on the stabilities of the high-spin ground states. That the heteroatom lying in m -phenyl can improve ferromagnetic coupling, while the heteroatom lying in o -phenyl or p -phenyl is not in favor of the ferromagnetic coupling.展开更多
The treatment of 5 amino 1 (4 chlorophenyl) 1,2,3 triazol 4 carbohydrazide with equimolecular aryl isothiocyanate gave new derivatives 1 a—l . Twelve title compounds were obtained in 42% to 87% yields whe...The treatment of 5 amino 1 (4 chlorophenyl) 1,2,3 triazol 4 carbohydrazide with equimolecular aryl isothiocyanate gave new derivatives 1 a—l . Twelve title compounds were obtained in 42% to 87% yields when compounds 1 a—l were respectively treated with sodium hydroxide aqueous solution(2 mol/L). The products of Dimroth rearrangement were not observed in the experiment. The structures of all the compounds were confirmed by means of IR, 1H NMR, MS and elementary analysis.展开更多
We have explored the chemistry of N-oxide heterocycles and imidazoles replacing ring D of the natural product（＋）-calanolide A, and have synthesized 12 new analogues, two of which were active against both R Mtb and ...We have explored the chemistry of N-oxide heterocycles and imidazoles replacing ring D of the natural product（＋）-calanolide A, and have synthesized 12 new analogues, two of which were active against both R Mtb and NR Mtb with MIC values of 12.5 mg/m L, which would lead to further optimization for more potent anti-TB candidates.展开更多
基金the Fundamental Research Funds for the Central Universities (Nos. 2024CDJXY0022023CDJYGRH-YB17+4 种基金2022CDJXY-025)the Venture & Innovation Support Program for Chongqing Overseas Returnees (No. cx2022061)the Natural Science Foundation of Chongqing (No. CSTB2022NSCQ-MSX1123)the Chongqing Talents: Exceptional Young Talents Project (No. cstc2021ycjh-bgzxm0067)the Hongshen Young Scholars Program from Chongqing University (No. 0247001104426) for financial support。
文摘The design and synthesis of a novel π-conjugated fiuorescent framework by external ligand-assisted C-H olefination of heterocycles with excellent regioselectivity and broad substrate scope are reported herein.These novel fiuorescent materials could present full-color-tunable emissions with large Stokes shifts. Furthermore, the protocol provides an opportunity to rapidly screen novel organic single-molecule whitelight materials with high fiuorescence quantum yields. The robust organic and low-cost white lightemitting diodes could rapidly be fabricated using the white-light-emitting material. Experimental data and theoretical calculations indicate that in the white-light dual emission the relatively short wavelength from high-lying singlet state emission and the relatively long wavelength from low-lying singlet state emission. The anti-Kasha dual-emission systems will provide a foundation for the development and application of organic single-molecule white light materials, effectively promoting the development and innovation of luminescent materials. In addition, this method demonstrated its potential application in the synthesis of new near-infrared(NIR) fiuorescence materials with large Stokes shifts based on the olefination of heterocycles.
基金The authors are thankful to Dr.Mayur Yergeri and Science and Engineering Research Board(SERB),Government of India,New Delhi,(CRG/2019/001452).
文摘Glioblastoma,the most aggressive form of brain tumor,poses significant challenges in terms of treatment success and patient survival.Current treatment modalities for glioblastoma include radiation therapy,surgical intervention,and chemotherapy.Unfortunately,the median survival rate remains dishearteningly low at 12–15 months.One of the major obstacles in treating glioblastoma is the recurrence of tumors,making chemotherapy the primary approach for secondary glioma patients.However,the efficacy of drugs is hampered by the presence of the blood-brain barrier and multidrug resistance mechanisms.Consequently,considerable research efforts have been directed toward understanding the underlying signaling pathways involved in glioma and developing targeted drugs.To tackle glioma,numerous studies have examined kinase-downstream signaling pathways such as RAS-RAF-MEKERK-MPAK.By targeting specific signaling pathways,heterocyclic compounds have demonstrated efficacy in glioma therapeutics.Additionally,key kinases including phosphatidylinositol 3-kinase(PI3K),serine/threonine kinase,cytoplasmic tyrosine kinase(CTK),receptor tyrosine kinase(RTK)and lipid kinase(LK)have been considered for investigation.These pathways play crucial roles in drug effectiveness in glioma treatment.Heterocyclic compounds,encompassing pyrimidine,thiazole,quinazoline,imidazole,indole,acridone,triazine,and other derivatives,have shown promising results in targeting these pathways.As part of this review,we propose exploring novel structures with low toxicity and high potency for glioma treatment.The development of these compounds should strive to overcome multidrug resistance mechanisms and efficiently penetrate the blood-brain barrier.By optimizing the chemical properties and designing compounds with enhanced drug-like characteristics,we can maximize their therapeutic value and minimize adverse effects.Considering the complex nature of glioblastoma,these novel structures should be rigorously tested and evaluated for their efficacy and safety profiles.
文摘Heterogeneous porous carbon(PC)materials have gained unique importance in the catalysis community due to their captivating properties,including high specific surface area,tunable porosity,and function-ality.PC can play a prominent role in the sustainable synthesis of functional heterocycles,as they are a low-cost alternative while being an efficient and user-friendly material.This review examines the prepa-ration and applicability of these carbonaceous materials used as catalysts or support for biologically active heterocycles synthesis,including hydrogenation,oxidation,oxidative dehydrogenation,cross-coupling,and other organic reactions.Moreover,the challenges,potential future development directions,and opportuni-ties in the synthesis of potent bioactive heterocycles over PC materials have been addressed.This review will inspire further research to explore novel PC materials and their implications in heterocyclization.
基金the financial support from the National Natural Science Foundation of China(Nos.21971205 and 22271231)the Natural Science Basic Research Plan in Shaanxi Province of China(No.2023-JC-YB-126)+1 种基金Natural Science Basic Research Plan for Distinguished Young Scholars in Shaanxi Province of China(No.2022JC-08)Key Research and Invention Program in Shaanxi Province of China(No.2021SF-299)。
文摘An inexpensive phosphine catalyst was used effectively for a transition-metal-free acyl-transfer of N-containing heteroaryl ketones for the rapid synthesis of N-fused heterocycles.The key pre-aromatic spirocyclic intermediate initialized by the single electron transfer(SET)process of Togni's reagentⅡpromoted by the tertiary phosphine resulted in an intriguing and alternative tactic for the cleavage of C–C bonds.By using inexpensive tertiary phosphine as the catalyst,this skeleton-reorganizing approach of N-containing heteroaryl ketones allows a streamlined assembly of complex N-fused heterocycles with broad functional group tolerance.
文摘Interaction between bovine serum albumin(BSA) and phosphorus heterocycles(PHs) was studied using multispectroscopic techniques. The results indicated the high binding affinity of PHs to BSA as it quenches the intrinsic fluorescence of BSA. The experimental data suggested the fluorescence quenching mechanism between PHs and BSA as a dynamic quenching. From the UV–vis studies, the apparent association constant(K_(app)) was found to be 9.25×10~2, 1.27×10~4and 9.01×10~2L/mol for the interaction of BSA with PH-1, PH-2 and PH-3,respectively. According to the F?rster's non-radiation energy transfer(FRET) theory, the binding distances between BSA and PHs were calculated. The binding distances(r) of PH-1, PH-2 and PH-3 were found to be2.86, 3.03, and 5.12 nm, respectively, indicating energy transfer occurs between BSA and PHs. The binding constants of the PHs obtained from the fluorescence quenching data were found to be decreased with increase of temperature. The negative values of the thermodynamic parameters ΔH, ΔS and ΔG at different temperatures revealed that the binding process is spontaneous; hydrogen bonds and van der Waals interaction were the main force to stabilize the complex. The microenvironment of the protein-binding site was studied by synchronous fluorescence and circular dichroism(CD) techniques and data indicated that the conformation of BSA changed in the presence of PHs. Finally, we studied the BSA-PHs docking using Auto Dock and results suggest that PHs is located in the cleft between the domains of BSA.
基金supported by the China Scholarship Council and Fujian University-Industry Research Cooperation Project(Project No.:2018N5013)。
文摘P450 fatty acid decarboxylase Ole T from Staphylococcus aureus(Ole TSA)is a novel cytochrome P450 enzyme that catalyzes the oxidative decarboxylation of fatty acids to yield primarily terminal alkenes and CO_(2) or minor a-andβ-hydroxylated fatty acids as side-products.In this work,the interactions between a series of cycloalkyl phosphorus heterocycles(CPHs)and Ole TSAwere investigated in detail by fluorescence titration experiment,ultraviolet-visible(UV-vis)and31 P NMR spectroscopies.Fluorescence titration experiment results clearly showed that a dynamic quenching occurred when CPH-6,a representative CPHs,interacted with Ole TSAwith a binding constant value of 15.2×104 M-1 at 293 K.The thermodynamic parameters(ΔH,ΔS andΔG)showed that the hydrogen bond and van der Waals force played major roles in the interaction between Ole TSAand CPHs.The UV-vis and31 P NMR studies indicated the penetration of CPH-6 into the interior environment of Ole TSA,which greatly affects the enzymatic activity of Ole TSA.Therefore,our study revealed an effective way to use phosphorus heterocyclic compounds to modulate the activity of cytochrome P450 enzymes.
基金Payame Noor University for its financial support of this study
文摘Benzimidazoles, benzoxazoles, and benzothiazoles derivatives were synthesized from condensation of aldehydes and 1,2-phenylenediamine or ortho-aminophenol or ortho-aminothiophenol in the presence of catalytic amount of Fe（Ⅲ）-Schiff base/SBA-15 in water medium. Short reaction times, good to excellent yields, easy availability, reusability, and use of an eco-friendly catalyst are some of the significant attributes of the present method.
基金supported financially by the joint grant of the National Natural Science Foundation of China(NSFC)National Institute of Health(NIH)of USA(No.81161120402)the National 863 Program of China(No.2012AA020303)
文摘（~）-Calanolide A was the first natural product identified as an active agent against HIV-1 and Mycobacterium tuberculosis （Mtb）. In devising a scaffold-hopping strategy of structure modification of （＋）-calanolide A, we focused on the synthesis of calanolides by replacing ring D with various five or six membered nitrogen-containing heterocycles, hoping to get further understanding of the structure- activity relationship.
基金financial support from the National Basic Research Program of China(973 Project,No.2015CB856603)the National Natural Science Foundation of China(Nos.20472096,21372241,21361140350,20672127,21421091,21372250,21121062,21302203,20732008 and 21572052)
文摘Nucleophilic chiral phosphine catalysis has been prosperous in asymmetric synthesis over the past two decades. Various tunable chiral phosphines display excellent activity and selectivity in asymmetric transformations including acycloaddition reactions and cycloaddition reactions. Enantiomerically enriched cyclic compounds are ubiquitous in natural products and drug molecules. These phosphinecatalyzed reactions provide effective and extensive strategies for the synthesis of a series of complex cyclic compounds as well as the synthesis of chiral compounds which could be easily transformed to carbocycles and heterocycles. This minireview summarizes recent developments in this area and highlights meaningful breakthroughs.
文摘Polynitrogen heterocycles are readily available and have recently arisen as versatile synthons for the formation of various C-C and C-X bonds,and medicinally active nitrogen-containing heterocycles.Several cascade reactions,including annulation,radical cascade,and borylation reactions,have been reported in which polynitrogen heterocycles are applied as arylation reagents.The success of these exceptional reactions illustrates the great synthetic potential of polynitrogen heterocycles,which provides a direct and useful approach to arylation reactions and the synthesis of nitrogen-containing heterocycles.The use of photocatalysts to effectively transfer energy from visible light to non-absorbing compounds has gained increasing attention as this method allows for the mild and efficient generation of radicals in a controlled manner.This approach has thus led to new methods that involve unique bond formation reactions.In addition,the use of free radical intermediates stabilized by transition metal catalysts is a powerful way to construct new chemical bonds.The aim of this review is to highlight the rapidly expanding area of radical-initiated denitrogenative cascade reactions of polynitrogen heterocycles and elaborate on their mechanisms from a new perspective by using photocatalysis and metal-based catalysis.
基金financial support from the National Natural Science Foundation of China (Nos.91843301 and 91543202)National Key Research and Development Program Cooperation on Scientific and Technological Innovation in Hong Kong,Macao and Taiwan (No. 2017YFE0191000)。
文摘Research on pollution characteristics and toxicities of emerging polycyclic aromatic sulfur heterocycles(PASHs) in PM_(2.5) has not been reported due to the lack of analytical method with the needed performance.In the present study,a novel method for the determination of 14 PASHs in PM_(2.5) was developed using atmospheric pressure gas chro matography-tandem mass spectrometry(APGC-MS/MS).Atmospheric pressure chemical ionization was operated with multiple reaction monitoring in positive ionization mode.High sensitivity(method detection limit <1.673 pg/m^(3)),acceptable re coveries(67.6%-120.8%) and precisions(RSD of 2.2%-15.4%) were obtained.The method was successfully applied for analyzing PASHs in 10 PM_(2.5) samples collected from Taiyuan,a typical industrial city in China,in 2016,The total concentrations were from 929 pg/m^(3) to 14,593 pg/m^(3).The determined levels indicated that further investigations on environmental fate and toxicities of PM_(2.5)-bound PASHs may be needed.
文摘New functionalized fused heterocycles, such as, 1,3,6,9,11-pentasubstituted-pyrido[3,2-f:6,5-f']bis([1,2,4]triazolo[4,3-a]-pyrimidin-5(1H)-ones (6) and 1,3-disubstituted-7-[(E)-2-(thiophen-2-yl)ethenyl]-1,4,9,9a-tetrahydro-6H-[1,2,4]triazino[4,3-b][1,2,4,5]-tetrazin-6-ones (16) were synthesized via reaction of the hydrazonoyl chlorides (1) with 1,3,6-triphenyl-9-thioxo-9,10-dihydro-pyrimido [4,5-b]pyrido[4,5-d][1,2,4]triazolo[4,3-a]pyrimidin-5,7(1H,8H)-di-one (5) and 4-amino-6-[(2-thiophen-2-yl)ethenyl]-3-thioxo-3,4-dihydro-[1,2,4]triazin-5(2H)-one (11), respectively. The mechanism and the regioselectivity of the studied reactions have been discussed. The biological activity of the products has been evaluated against some fungi and bacteria species. The tested compounds exhibited moderate activity against the bacteria species.
文摘Cyanine dyes of zero/bis-zero methine incorporating imid-azo(1,2-a)Pyridine (quinoline) or pyrazino(1,2-a)pyridine (quinoline) with stable C-N bond were synthesized using keto-oxime methylene C-link heterocyclic quaternary salts [1-phenyl-3-methyl-pyrazolino-4-keto-oxime-α-methylene-bis-pyridin-(quinoin)-1(4)-di-ium-iodide(ethiodide) salts and 1-phenyl-3-methyl-pyrazolino- 4-ketooxime-α-methylene-N-2-methyl-bis pyridin (quinoin)-1(4)-di-ium-iodide(ethiodide) salts]. Such heterocyclic precursors and related dyes were identified by elemental and spectral analyses. The absorption spectra properties of such dyes were investigated in 95% Ethanol to attempt and throw some light on the influence of such new heterocyclic nuclei and to compare or evaluate spectral behaviors. The absorption spectra of dyes in different pure solvents were examined in the visible region showing solvatochromism and the colour changes of dyes with solvents having different polarities. This permits a selection of the optimal solvent (fractional solvent) when such dyes are applied as photosensitizers. The spectral behavior of some selected newly synthesized cyanine dyes is observed in mixed solvents of different polarities and progressively increasing quantities of one solvent over the other were studied and showed an increase in the absorbance of CT band with increasing proportion of that solvent. Evidence for hydrogen bond formation between the solute molecules and solvent molecules allows measurement of certain energies such as hydrogen bonding, orientation, and free energies.
文摘Ma＇s CuI/proline procedure for the catalytic cross coupling between nitrogen heterocycles and aryl halides was markedly improved. The key finding was that K3PO4 was a much better base than K2CO3 for the reaction. With this new reaction condition the cross coupling with aryl iodides could be accomplished in 1,4-dioxane instead of DMSO. This reactin also could be carried out in DMF. Furthermore, the coupling yields under the new conditions are usually higher than in Ma＇s original methods.
文摘The ligand exchange reaction with heterocycles containing nitrogen, oxygen or sulfur atoms was carried out. For the reaction with heterocycles, the order of the reactivity was S-heterocycles > N-heterocycles > O-heterocycles. Furthermore, when the results for the heterocycles were compared to those for the corresponding hydrocarbons, the hydrocarbons had a higher reactivity. These results mean that the reactivity would be mainly governed by the electron density of these arenes.
基金supported by the Natural Science Foundation of Jiangsu Province (No.BK20170439)Science and Technology Plan Projects of Nantong (Nos.JC2019102 and JC2020072)。
文摘An intramolecular selenocyclizations of olefins mediated by a commercially available hypervalent iodine(Ⅲ) reagent,PhIO,was developed.This method provided access to a wide range of selenenylated heterocycles under ambient conditions.The striking advantages of this protocol over all previous methods include mild reaction conditions,easy operation,good yields,high levels of functional group compatibility,large-scale application and suitability for the late-stage functionalization of complex molecules of biological importance.
基金Supported by the National Natural Science Foundation of China( No.2 980 4 0 0 2,2 0 2 74 0 0 6 ) ,FokYingTungEducationFoundation( No.710 13) and Foundation of Northeast Normal University( No.1114 34)
文摘Novel stable high spin molecules possessing three different arranged fashions are designed with - · N-N< as a spin-containing(SC) fragment, phenylene as an end group and various aromatic molecules, such as benzene(1), 2,6-pyridine(2), 3,5-pyridine(3), pyridazine(4), 4,6-pyrimidine(5), 2,6-pyrimidine(6), pyrazine(7) and triazine(8), as a ferromagnetic coupling(FC) unit. The effects of the different coupling units on the spin multiplicities of the ground states and their stabilities were investigated by means of AM1-CI approach. It has been found that the spin densities on the two atoms of the SC fragment are different from delocalization results in the specific stability of - · N-N<. In these molecules, the stabilities of the triplet states decrease when the distance between the atoms of central SC(-N-) increases. It is shown that the heterocycles as the coupling units have influence on the stabilities of the high-spin ground states. That the heteroatom lying in m -phenyl can improve ferromagnetic coupling, while the heteroatom lying in o -phenyl or p -phenyl is not in favor of the ferromagnetic coupling.
文摘The treatment of 5 amino 1 (4 chlorophenyl) 1,2,3 triazol 4 carbohydrazide with equimolecular aryl isothiocyanate gave new derivatives 1 a—l . Twelve title compounds were obtained in 42% to 87% yields when compounds 1 a—l were respectively treated with sodium hydroxide aqueous solution(2 mol/L). The products of Dimroth rearrangement were not observed in the experiment. The structures of all the compounds were confirmed by means of IR, 1H NMR, MS and elementary analysis.
基金supported by Bill and Melinda Gates Foundation Grant (No. OPP1024029)supported financially by the National Natural Science Foundation of China (No. 91213303)
文摘We have explored the chemistry of N-oxide heterocycles and imidazoles replacing ring D of the natural product（＋）-calanolide A, and have synthesized 12 new analogues, two of which were active against both R Mtb and NR Mtb with MIC values of 12.5 mg/m L, which would lead to further optimization for more potent anti-TB candidates.
基金financial supported by National Natural Science Foundation of China(No.21372079)National High Technology Research Development Program of China(863 Program,No. 2011AA10A207)+3 种基金Shanghai Pujiang Program(No.14PJD012)Key Projects in the National Science & Technology Pillar Program(No. 2011BAE06B05)the Fundamental Research Funds for the Central Universitiespartly supported by Australia DC Foundation
文摘An efficient synthetic pathway to 2-oxo-1,2-dihydropyridine-fused 1,3-diaza heterocycles from heterocyclic ketene aminals,phathalic anhydride and ethyl cyanacetate was established.This protocol involved aza-ene reaction/imine-enamine tautomerization/enamine-ester exchange/ring-opening reaction sequence.
