Pyrrole is a heterocycle with four carbon atoms and a nitrogen atom,which is extensively used in the pesticide and pharmaceutical industries.In addition,it has a series of analogs such as pyrrolidine,pyrroline,and pyr...Pyrrole is a heterocycle with four carbon atoms and a nitrogen atom,which is extensively used in the pesticide and pharmaceutical industries.In addition,it has a series of analogs such as pyrrolidine,pyrroline,and pyrrolidone.Pesticides containing pyrrole and its analogs have been formally marketed as fungicides,including fenpiclonil,fludioxonil,the insecticide chlorfenapyr,and the herbicide fluorochloridone.In this paper,we analyze the structure-activity relationships(SARs)of pesticides containing these structures.We summarize the characteristics possessed by the most highly active pyrrole and its analogs and provide an overview of research on pyrrole compounds with insecticidal,antimicrobial,herbicidal,and antiviral properties in the past 20 years.It is hoped to provide ideas for the development and design of this type compounds in pesticides and to assist researchers in this area.展开更多
A palladium-catalyzed three-component annulation of anilines,alkyne esters,and alkynes has been developed for the synthesis of polysubstituted pyrroles.The protocol demonstrates broad substrate scope and good function...A palladium-catalyzed three-component annulation of anilines,alkyne esters,and alkynes has been developed for the synthesis of polysubstituted pyrroles.The protocol demonstrates broad substrate scope and good functional group compatibility.The application experiments including gram-scale synthesis and derivatization of the product are performed to illustrate the synthetic potential.This method offers mild conditions and efficient access to polysubstituted pyrroles.展开更多
Pyrrolo[3,2-b]pyrrole is a good building block for radical photoini-tiators.In this study,free-radical photoinitiator 1,4-bis(4-bro-mophenyl)-2,5-bis(4-(trifluo-romethyl)phenyl)-1,4-dihydropy-rrolo[3,2-b]pyrrole(PyBF)...Pyrrolo[3,2-b]pyrrole is a good building block for radical photoini-tiators.In this study,free-radical photoinitiator 1,4-bis(4-bro-mophenyl)-2,5-bis(4-(trifluo-romethyl)phenyl)-1,4-dihydropy-rrolo[3,2-b]pyrrole(PyBF),con-taining a symmetric trifluo-romethyl(-CF3)end group,is syn-thesized via a one-step aldehyde-ketone condensation re-action for light-emitting diode(LED)photopolymerization.The-CF3 groups are incorporated into the 2,5-phenyl on the pyrrolo[3,2-b]pyrrole core.PyBF rapidly initiates the photopolymerization of acrylate pre-polymers and monomers under LED illumination at 365 and 405 nm.A possible photolysis mechanism is provided.In the presence of amines,PyBF increases the gel fraction rate of polyethylene glycol diacrylate(PEGDA)from 63.4%to 80.0%,indicating good potential as a two-component photoinitiator.PyBF exhibits a thermal decomposition temperature in an ex-cess of 300℃,comparable to that of a commercial photoinitiator(diphenyl(2,4,6-trimethyl-benzoyl)phosphine oxide,TPO),indicating its thermal stability.PyBF shows low migration in light-curing materials.Scanning electron microscopy images indicate that the materials of the PyBF/TPO/PEGDA mixture cured using the PyBF/TPO two-component photoinitia-tor system exhibit a smooth surface,in contrast to those cured with PyBF/PEGDA and TPO/PEGDA systems.The cured materials also display low curing shrinkage.Therefore,the pyrrolo[3,2-b]pyrrole radical photoinitiator exhibits high photoactivity in visible-light pho-topolymerization reactions.展开更多
Hepatic sinusoidal obstruction syndrome (HSOS) can be caused by the intake of pyrrolizidine alkaloids (PAs). To date, PAs-induced HSOS has not been extensively studied. In view of the difference in etiology of HSOS be...Hepatic sinusoidal obstruction syndrome (HSOS) can be caused by the intake of pyrrolizidine alkaloids (PAs). To date, PAs-induced HSOS has not been extensively studied. In view of the difference in etiology of HSOS between the West and China, clinical profiles, imaging findings, treatment, and outcomes of HSOS associated with hematopoietic stem cell transplantation or oxaliplatin might be hardly extrapolated to PAs-induced HSOS. Reactive metabolites derived from PAs form pyrrole-protein adducts that result in toxic destruction of hepatic sinusoidal endothelial cells. PAs-induced HSOS typically manifests as painful hepatomegaly, ascites, and jaundice. Laboratory tests revealed abnormal liver function tests were observed in most of the patients with PAs-induced HSOS. In addition, contrast computed tomography and magnetic resonance imaging scan show that patients with PAs-induced HSOS have distinct imaging features, which reveal that radiological imaging provides an effective noninvasive method for the diagnosis of PAs-induced HSOS. Liver biopsy and histological examination showed that PAs-induced HSOS displayed distinct features in acute and chronic stages. Therapeutic strategies for PAs-induced HSOS include rigorous fluid management, anticoagulant therapy, glucocorticoids, transjugular intrahepatic portosystemic shunt, liver transplantation, etc. The aim of this review is to describe the pathogenesis, clinical profiles, diagnostic criteria, treatment, and outcomes of PAs-induced HSOS.展开更多
Calix[4]pyrroles, as a class of new molecular receptor in the area of supramolecular chemistry, have displayed interesting anion and neutral substrate binding properties. In this paper, several new calix[4]pyrrole mac...Calix[4]pyrroles, as a class of new molecular receptor in the area of supramolecular chemistry, have displayed interesting anion and neutral substrate binding properties. In this paper, several new calix[4]pyrrole macrocycles were synthesised and characterized.展开更多
The polymerization thermokinetics of pyrrole in the presence of iron trichloride art studied by using a Calvet microcalorimoter. The apparent activation energy, the pre-exponential constant and reaction order of this ...The polymerization thermokinetics of pyrrole in the presence of iron trichloride art studied by using a Calvet microcalorimoter. The apparent activation energy, the pre-exponential constant and reaction order of this reaction in the temperature range of 25.2—37℃ are 34.5 KJ·mol^(-1), 10^(2.74)S^(-1) and 1 respectively. The activation free-energies of this reaction at 25.2°, 30°and 37℃ are 91.8, 92.9 and 94.2 KJ·mol^(-1) respectively.展开更多
We herein disclose a series of novel pyrrole derivatives as well as fused pyrrolopyridines 6a,b and 7a,b, pyrrolopyrazoles 8a, b, pyrrolo[2,3-d]pyrimidine derivatives 10a-d, 12a,b, 14a,b, 18a,b, 20a,b, 21a,b, 22a,b, 2...We herein disclose a series of novel pyrrole derivatives as well as fused pyrrolopyridines 6a,b and 7a,b, pyrrolopyrazoles 8a, b, pyrrolo[2,3-d]pyrimidine derivatives 10a-d, 12a,b, 14a,b, 18a,b, 20a,b, 21a,b, 22a,b, 23a,b, 24a,b, 31a,b, 36a,b, 40a,b, pyrrolo[1,2,6]thiadiazine derivatives 19a,b, pyrrolotriazolopyrimidines 25a,b, 26a,b, 27a,b and 28a,b, pyrrolo[2,3-d][1,2,3]triazine derivatives 32a,b and pyrrolo[2,3-d][1,3]oxazine derivatives 39a,b as novel compounds. All compounds were evaluated for their anti-inflammatory, analgesic (compared to the reference drug Indomethacin) and antimicrobial activities (compared to the reference drug Ampicillin and Fluconazole). Compounds 4d, 5b-d, 6a,b, 9c,d, 10d, 12ab, 13b, 19a,b, 21b, 23b, 31a,b, 38b and 40a were found to be the most active anti-inflammatory drugs exhibiting potency ranging from 1 - 1.01 compared to the reference drug indomethacin. In addition to docking study of these highly active twenty compounds against the active site of cyclooxygenase-2 enzyme (COX-2), among the tested compounds, compounds 5d, 9d, 11b, 12a, 13b and 32a showed multiple activities;anti-inflammatory, analgesic and anti-bacterial activities.展开更多
Pyrroles are important structural units of natural products,drug molecules,biomolecules and functional material molecules.Efficient synthesis ofα-functionalized pyrroles with different substituents from easily access...Pyrroles are important structural units of natural products,drug molecules,biomolecules and functional material molecules.Efficient synthesis ofα-functionalized pyrroles with different substituents from easily accessible starting materials is still challenging.Herein,a facile and regioselective coarctate reaction of enynals involving a free carbene intermediate has been developed,which allows the divergent and practical de novo synthesis of variousα-furanyl pyrroles andα-cyclopropenyl pyrroles derivatives with good to excellent yields and high efficiency under mild conditions.This approach features readily accessible starting materials,high functional group compatibility,step economy and scalability,which would complement previous methods and support expansion of the toolbox for the synthesis of valuable,but previously inaccessible,highly substituted and electron-richα-functionalized pyrroles.展开更多
Highly enantioselective Rh-catalyzed partial hydrogenation of unprotected simple 2-alkyl-5-aryl-disubstituted pyrroles has been successfully developed,generating a series of chiral 1-pyrroline derivatives generally wi...Highly enantioselective Rh-catalyzed partial hydrogenation of unprotected simple 2-alkyl-5-aryl-disubstituted pyrroles has been successfully developed,generating a series of chiral 1-pyrroline derivatives generally with excellent results(95%-99%yields,91%-96%ee).Moreover,2,5-aryl-1H-pyrroles were hydrogenated well in high yields and good enantioselectivities.This efficient protocol features easily accessible substrates,wide substrate scope,well functional group compatibility,commercially available rhodium precursor and chiral ligand.It provides a versatile route to access chiral 1-pyrroline derivatives that are of great importance in organic synthesis and pharmaceutical chemistry.展开更多
Michael addition of indole and pyrrole to a variety of α, β-unsaturated ketones was efficiently promoted by a catalytic amount of GaCl3 in aqueous media to afford the corresponding products in good to excellent yields.
With home-made multi-walled carbon nanotubes （MWCNTs, simplified as CNTs in later text） as support, CNT-supported Co-Mo-S catalysts, denoted as x%（mass percentage）MoiCoj/CNTs, were prepared. Their catalytic perfor...With home-made multi-walled carbon nanotubes （MWCNTs, simplified as CNTs in later text） as support, CNT-supported Co-Mo-S catalysts, denoted as x%（mass percentage）MoiCoj/CNTs, were prepared. Their catalytic performance for thiophene hydrodesulfurization （HDS） and pyrrole hydrodenitrification （HDN） reactions was studied, and compared with the reference system sup- ported by AC. Over the 7.24%Mo3Co1/CNTs catalyst at reaction condition of 1.5 MPa, 613 K, C4H4S/H2=3.7/96.3（molar ratio） and GHSV≈8000 mlswP/（g-cat.h）, the specific HDS activity of thiophene reached 3.29 mmolc4H4S/（s.molMo）, which was 1.32 times as high as that （2.49 mmolc4H4S/（s.molMo）） of the AC-based counterpart, and was 2.47 times as high as that （1.33 mmolc4H4S/（s-molMo）） of the catalysts supported by AC with the respective optimal MoaCol-loading amount, 16.90%Mo3Co1/AC. Analogous reaction-chemical behaviours were also observed in the case of pyrrole HDN. It was experimentally found that using the CNTs in place of AC as support of the catalyst caused little change in the apparent activation energy for the thiophene HDS or pyrrole HDN reaction, but led to a significant increase in the concentration of catalytically active Mo-species （Mo^4＋） at the surface of the functioning catalyst. On the other hand, H2-TPD measurements revealed that the CNT-supported catalyst could reversibly adsorb a greater amount of hydrogen under atmospheric pressure at temperatures ranging from room temperature to about 673 K. This unique feature would help to generate microenvironments with higher stationarystate concentration of active hydrogen-adspecies at the surface of the functioning catalyst. Both factors mentioned above were favorable to increasing the rate of thiophene HDS and pyrrole HDN reactions.展开更多
A convenient and effective Paal-Knorr condensations of 2,5-hexanedione with most amines have been carried out at room temperature under solvent-free condition.Macroporous strongly acidic styrol resin(D001) as a novel,...A convenient and effective Paal-Knorr condensations of 2,5-hexanedione with most amines have been carried out at room temperature under solvent-free condition.Macroporous strongly acidic styrol resin(D001) as a novel,efficient,cost-effective,and reusable solid acid catalyst for the synthesis of pyrroles under the same conditions.The pyrroles were obtained in high yields in short reaction times.展开更多
Pyridinic N is widely regarded as the active center while pyrrolic N has low‐activity in metal‐free N‐doped carbon for electrocatalytic CO_(2) reduction reaction(CO_(2)RR)to CO,but this viewpoint remains open to qu...Pyridinic N is widely regarded as the active center while pyrrolic N has low‐activity in metal‐free N‐doped carbon for electrocatalytic CO_(2) reduction reaction(CO_(2)RR)to CO,but this viewpoint remains open to question.In this study,through density functional theoretical calculations,we first illustrate that the intrinsic activity of pyrrolic N is high enough for effectively catalyzing CO_(2)RR,however,due to the interplay with the neighboring pyridinic N sites,the activity of pyrrolic N is dramatically suppressed.Then,experimentally,metal‐free N‐doped carbon spheres(NCS)electrocatalysts without significant pyridinic N content are prepared for CO_(2)RR.The pyrrolic N in NCS shows a direct‐positive correlation with the performance for CO_(2)RR,representing the active center with high activity.The optimum NCS could produce syngas with a wide range of CO/H_(2) ratio(0.09 to 12)in CO_(2)RR depending on the applied potential,meanwhile,the best selectivity of 71%for CO can be obtained.Intentionally adding a small amount of pyridinic N to the optimum NCS dramatically decreases the activity for CO_(2)RR,further verifying the suppressed activity of pyrrolic N sites by the neighboring pyridinic N sites.This work reveals the interaction between a variety of N species in N‐doped carbon,and the potential of pyrrolic N as the new type of active site for electrocatalysts,which can improve our understanding of the electrocatalysis mechanism and be helpful for the rational design of high‐efficient electrocatalysts.展开更多
A phytochemical investigation of the EtOH extract of the flowers of Lagerstroemia indica L.led to the isolation and char-acterization of a new pyrrole alkaloid,named lagerindicine(1),along with four known compounds(2-...A phytochemical investigation of the EtOH extract of the flowers of Lagerstroemia indica L.led to the isolation and char-acterization of a new pyrrole alkaloid,named lagerindicine(1),along with four known compounds(2-5).Their structures were elucidated by the detailed spectroscopic analysis and comparison with literature data,whereas the structure,in par-ticularly,the absolute configuration(AC)of 1,was firmly determined by total synthesis.All the isolates were evaluated for their cytotoxic effects against human colon cancer cell(HCT-116),and compound 3 exhibited weak cytotoxicity with IC50 value of 28.4μM.展开更多
The electrochemical performance of lithium-sulfur(Li-S)batteries is strongly hampered by the shuttle effect and slow redox kinetics of lithium polysulfides(Li PSs).Surface modified interlayer of a separator of Li-S ba...The electrochemical performance of lithium-sulfur(Li-S)batteries is strongly hampered by the shuttle effect and slow redox kinetics of lithium polysulfides(Li PSs).Surface modified interlayer of a separator of Li-S batteries is demonstrated to be an effective strategy to overcome this problem.Herein,cobalt nanoparticles confined in nitrogen co-doped porous carbon framework(Co-CN)were developed from pyrolysis of ZIF-67 and used as interlayer of PP separator for Li-S batteries,and were functionalized by four pyrrole derivatives,1-phenylpyrrole,1-methyl pyrrole,1-(p-toluenesulfonyl)pyrrole,and 1-pyrrole,respectively,which were screened in terms of the electron-withdrawing/donating ability of the substituent groups on the pyrrolic nitrogen.The impact of the molecular structure of pyrrole derivatives on the interaction with Li PSs and the electrochemical performance of Li-S batteries were explored by nuclear magnetic resonance and theoretical calculation.It is uncovered that 1-phenylpyrrole shows the highest enhancement of redox kinetics of Li PSs,attributing to the optimal interaction with Co nanoparticles and Li PSs.Therefore,1-phenylpyrrole modified Co-CN interlayer enables the best electrochemical performance for the Li-S batteries,delivering a specific capacity of 562 m Ah g^(-1)at 5 C and a capacity of 538,526,and 449 m Ah g^(-1)after 500 cycles at 1,2,and 3 C,respectively.At a high sulfur loading of 5.5 mg cm^(-2),it achieves a capacity of 440 m Ah g^(-1)after 500 cycles at 1 C.This work reveals the interaction mechanism among Li PSs,Co nanoparticles and the molecular modifiers in improving the electrochemical performance of Li-S batteries.展开更多
To achieve the red-shifted absorptions and appropriate energy levels of A-D-A type non-fullerene acceptors(NFAs), in this work, we design and synthesize two new NFAs, named TPDCIC and TPDCNC, whose electron-donating(D...To achieve the red-shifted absorptions and appropriate energy levels of A-D-A type non-fullerene acceptors(NFAs), in this work, we design and synthesize two new NFAs, named TPDCIC and TPDCNC, whose electron-donating(D) unit is constructed by a thieno[3,4-c]pyrrole-4,6-dione(TPD) core attached to two cyclopentadithiophene(CPDT) moieties at both sides, and the electronaccepting(A) end-groups are 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile(IC) and 2-(3-oxo-2,3-dihydro-1 H-cyclopenta[b]naphthalen-1-ylidene)malononitrile(NC), respectively. Benefiting from TPD core, which easily forms quinoid structure and O···H or O···S intramolecular noncovalent interactions, TPDCIC and TPDCNC show more delocalization of π-electrons and perfect planar molecular geometries, giving the absorption ranges extended to 822 and 852 nm, respectively. Furthermore, the highest occupied molecular orbital(HOMO) levels of TPDCIC and TPDCNC remain relatively low-lying due to the electronegativity of the carbonyl groups on TPD core. Considering that the absorptions and energy levels of the two NFAs match well with those of a widely used polymer donor, PBDB-T, we fabricate two kinds of organic solar cells(OSCs) based on the PBDB-T:TPDCIC and PBDB-T:TPDCNC blended films, respectively. Through a series of optimizations, the TPDCIC-based devices yield an impressing power conversion efficiency(PCE)of 10.12% with a large short-circuit current density(JSC) of 18.16 mA·cm-2, and the TPDCNC-based ones exhibit a comparable PCE of9.80% with a JSC of 17.40 mA·cm-2. Our work is the first report of the TPD-core-based A-D-A type NFAs, providing a good reference for the molecular design of high-performance NFAs.展开更多
Supramolecular interaction of calix[4]pyrroles with several inorganic anions is reported by addition of calix[4]pyrroles to background electrolyte (BGE) in CZE. The retention time (t(R)) of all anions increased with i...Supramolecular interaction of calix[4]pyrroles with several inorganic anions is reported by addition of calix[4]pyrroles to background electrolyte (BGE) in CZE. The retention time (t(R)) of all anions increased with increasing concentration of calix[4]pyrroles. The effect on F- is most evident.展开更多
An efficient 1-methylimidazole-catalyzed synthesis of dialkyl 2-[（4-methylphenyl）sulfonyl]-1H-pyrrole-3,4-dicarboxylates is described.The reactive 1：1 zwitterionic intermediate formed by the addition of 1-methylimi...An efficient 1-methylimidazole-catalyzed synthesis of dialkyl 2-[（4-methylphenyl）sulfonyl]-1H-pyrrole-3,4-dicarboxylates is described.The reactive 1：1 zwitterionic intermediate formed by the addition of 1-methylimidazole to dialkyl acetylenedicarboxylates is trapped by tosylmethyl isocyanide（TOSMIC） to afford the title compounds in excellent yields.展开更多
An undescribed pyrrole acid,1-(4′-methoxy-4′-oxobutyl)-1 H-pyrrole-2,5-dicarboxylic acid(1)and one known pyr-role acid(2)were isolated from the fruits of Phyllanthus emblica.The structures of these compounds were el...An undescribed pyrrole acid,1-(4′-methoxy-4′-oxobutyl)-1 H-pyrrole-2,5-dicarboxylic acid(1)and one known pyr-role acid(2)were isolated from the fruits of Phyllanthus emblica.The structures of these compounds were elucidated via the comprehensive analyses of IR,HRESIMS,1D and 2D spectroscopic data.A series of biological assays revealed that compounds 1 and 2 could inhibit LPS-induced over-production of nitric oxide(NO),interleukin-6(IL-6),monocyte chemotactic protein 1(MCP-1)and tumor necrosis factor-α(TNF-α)by reducing the phosphorylation of extracellular regulated protein kinases(ERK)and c-Jun N-terminal kinases(JNK)in RAW 264.7 cells.Additionally,compounds 1 and 2 were found to reduce lipid deposition and increase the mRNA expression of ATP-binding cassette transporter A1 in oxidized low-density lipoprotein-treated RAW264.7 macrophages.展开更多
One simple and versatile method is established far the synthesis of DNA recognition molecules-polyamides containing alternating N-methylpyrrole and N-methylimidazole without necessitating NH2- group protection.
基金financial support from the National Natural Science Foundation of China(No.32072445)the Science and Technology Plan Project of Guizhou Province(Qiankehezhicheng[2024]the general 083)+5 种基金the Program of Introducing Talents to Chinese Universities(No.D20023)the Central Government Guides Local Science and Technology Development Fund Projects(Qiankehezhongyindi(2023)001)Key Agricultural Technology R&D Projects of the Xinjiang Production and Construction Corps(NYHXGG,2023AA602)the Frontiers Science Centre for Asymmetric Synthesis and Medicinal Molecules,Department of Education,Guizhou Province[Qianjiaohe KY(2020)004]the specific research fund of The Innovation Platform for Academicians of Hainan Province(No.SQ2020PTZ0009)。
文摘Pyrrole is a heterocycle with four carbon atoms and a nitrogen atom,which is extensively used in the pesticide and pharmaceutical industries.In addition,it has a series of analogs such as pyrrolidine,pyrroline,and pyrrolidone.Pesticides containing pyrrole and its analogs have been formally marketed as fungicides,including fenpiclonil,fludioxonil,the insecticide chlorfenapyr,and the herbicide fluorochloridone.In this paper,we analyze the structure-activity relationships(SARs)of pesticides containing these structures.We summarize the characteristics possessed by the most highly active pyrrole and its analogs and provide an overview of research on pyrrole compounds with insecticidal,antimicrobial,herbicidal,and antiviral properties in the past 20 years.It is hoped to provide ideas for the development and design of this type compounds in pesticides and to assist researchers in this area.
文摘A palladium-catalyzed three-component annulation of anilines,alkyne esters,and alkynes has been developed for the synthesis of polysubstituted pyrroles.The protocol demonstrates broad substrate scope and good functional group compatibility.The application experiments including gram-scale synthesis and derivatization of the product are performed to illustrate the synthetic potential.This method offers mild conditions and efficient access to polysubstituted pyrroles.
基金the financial support of the Tianjin Technical Expert Project(22YDTPJC00620)。
文摘Pyrrolo[3,2-b]pyrrole is a good building block for radical photoini-tiators.In this study,free-radical photoinitiator 1,4-bis(4-bro-mophenyl)-2,5-bis(4-(trifluo-romethyl)phenyl)-1,4-dihydropy-rrolo[3,2-b]pyrrole(PyBF),con-taining a symmetric trifluo-romethyl(-CF3)end group,is syn-thesized via a one-step aldehyde-ketone condensation re-action for light-emitting diode(LED)photopolymerization.The-CF3 groups are incorporated into the 2,5-phenyl on the pyrrolo[3,2-b]pyrrole core.PyBF rapidly initiates the photopolymerization of acrylate pre-polymers and monomers under LED illumination at 365 and 405 nm.A possible photolysis mechanism is provided.In the presence of amines,PyBF increases the gel fraction rate of polyethylene glycol diacrylate(PEGDA)from 63.4%to 80.0%,indicating good potential as a two-component photoinitiator.PyBF exhibits a thermal decomposition temperature in an ex-cess of 300℃,comparable to that of a commercial photoinitiator(diphenyl(2,4,6-trimethyl-benzoyl)phosphine oxide,TPO),indicating its thermal stability.PyBF shows low migration in light-curing materials.Scanning electron microscopy images indicate that the materials of the PyBF/TPO/PEGDA mixture cured using the PyBF/TPO two-component photoinitia-tor system exhibit a smooth surface,in contrast to those cured with PyBF/PEGDA and TPO/PEGDA systems.The cured materials also display low curing shrinkage.Therefore,the pyrrolo[3,2-b]pyrrole radical photoinitiator exhibits high photoactivity in visible-light pho-topolymerization reactions.
基金Supported by National Natural Science Foundation of China,No.81570555 and No.81770582
文摘Hepatic sinusoidal obstruction syndrome (HSOS) can be caused by the intake of pyrrolizidine alkaloids (PAs). To date, PAs-induced HSOS has not been extensively studied. In view of the difference in etiology of HSOS between the West and China, clinical profiles, imaging findings, treatment, and outcomes of HSOS associated with hematopoietic stem cell transplantation or oxaliplatin might be hardly extrapolated to PAs-induced HSOS. Reactive metabolites derived from PAs form pyrrole-protein adducts that result in toxic destruction of hepatic sinusoidal endothelial cells. PAs-induced HSOS typically manifests as painful hepatomegaly, ascites, and jaundice. Laboratory tests revealed abnormal liver function tests were observed in most of the patients with PAs-induced HSOS. In addition, contrast computed tomography and magnetic resonance imaging scan show that patients with PAs-induced HSOS have distinct imaging features, which reveal that radiological imaging provides an effective noninvasive method for the diagnosis of PAs-induced HSOS. Liver biopsy and histological examination showed that PAs-induced HSOS displayed distinct features in acute and chronic stages. Therapeutic strategies for PAs-induced HSOS include rigorous fluid management, anticoagulant therapy, glucocorticoids, transjugular intrahepatic portosystemic shunt, liver transplantation, etc. The aim of this review is to describe the pathogenesis, clinical profiles, diagnostic criteria, treatment, and outcomes of PAs-induced HSOS.
文摘Calix[4]pyrroles, as a class of new molecular receptor in the area of supramolecular chemistry, have displayed interesting anion and neutral substrate binding properties. In this paper, several new calix[4]pyrrole macrocycles were synthesised and characterized.
文摘The polymerization thermokinetics of pyrrole in the presence of iron trichloride art studied by using a Calvet microcalorimoter. The apparent activation energy, the pre-exponential constant and reaction order of this reaction in the temperature range of 25.2—37℃ are 34.5 KJ·mol^(-1), 10^(2.74)S^(-1) and 1 respectively. The activation free-energies of this reaction at 25.2°, 30°and 37℃ are 91.8, 92.9 and 94.2 KJ·mol^(-1) respectively.
文摘We herein disclose a series of novel pyrrole derivatives as well as fused pyrrolopyridines 6a,b and 7a,b, pyrrolopyrazoles 8a, b, pyrrolo[2,3-d]pyrimidine derivatives 10a-d, 12a,b, 14a,b, 18a,b, 20a,b, 21a,b, 22a,b, 23a,b, 24a,b, 31a,b, 36a,b, 40a,b, pyrrolo[1,2,6]thiadiazine derivatives 19a,b, pyrrolotriazolopyrimidines 25a,b, 26a,b, 27a,b and 28a,b, pyrrolo[2,3-d][1,2,3]triazine derivatives 32a,b and pyrrolo[2,3-d][1,3]oxazine derivatives 39a,b as novel compounds. All compounds were evaluated for their anti-inflammatory, analgesic (compared to the reference drug Indomethacin) and antimicrobial activities (compared to the reference drug Ampicillin and Fluconazole). Compounds 4d, 5b-d, 6a,b, 9c,d, 10d, 12ab, 13b, 19a,b, 21b, 23b, 31a,b, 38b and 40a were found to be the most active anti-inflammatory drugs exhibiting potency ranging from 1 - 1.01 compared to the reference drug indomethacin. In addition to docking study of these highly active twenty compounds against the active site of cyclooxygenase-2 enzyme (COX-2), among the tested compounds, compounds 5d, 9d, 11b, 12a, 13b and 32a showed multiple activities;anti-inflammatory, analgesic and anti-bacterial activities.
基金the National Natural Science Foundation of China(Nos.22071062 and 22271096)the Fundamental Research Funds for the Central Universities,SCUT(No.2022ZYGXZR107)funded by the National Postdoctoral Research Program(No.GZC20230839)。
文摘Pyrroles are important structural units of natural products,drug molecules,biomolecules and functional material molecules.Efficient synthesis ofα-functionalized pyrroles with different substituents from easily accessible starting materials is still challenging.Herein,a facile and regioselective coarctate reaction of enynals involving a free carbene intermediate has been developed,which allows the divergent and practical de novo synthesis of variousα-furanyl pyrroles andα-cyclopropenyl pyrroles derivatives with good to excellent yields and high efficiency under mild conditions.This approach features readily accessible starting materials,high functional group compatibility,step economy and scalability,which would complement previous methods and support expansion of the toolbox for the synthesis of valuable,but previously inaccessible,highly substituted and electron-richα-functionalized pyrroles.
基金support from the National Natural Science Foundation of China(No.22071187)the Natural Science Foundation of Jiangsu Province(No.BK20190213)the Natural Science Foundation of Hubei Province(Nos.2020CFA036,2021CFA069).
文摘Highly enantioselective Rh-catalyzed partial hydrogenation of unprotected simple 2-alkyl-5-aryl-disubstituted pyrroles has been successfully developed,generating a series of chiral 1-pyrroline derivatives generally with excellent results(95%-99%yields,91%-96%ee).Moreover,2,5-aryl-1H-pyrroles were hydrogenated well in high yields and good enantioselectivities.This efficient protocol features easily accessible substrates,wide substrate scope,well functional group compatibility,commercially available rhodium precursor and chiral ligand.It provides a versatile route to access chiral 1-pyrroline derivatives that are of great importance in organic synthesis and pharmaceutical chemistry.
基金support by the Natural Science Foundation of Zhejiang Province(No.Y4051137,Y405015 and Y4080177)
文摘Michael addition of indole and pyrrole to a variety of α, β-unsaturated ketones was efficiently promoted by a catalytic amount of GaCl3 in aqueous media to afford the corresponding products in good to excellent yields.
基金Supported by National Natural Science Foundation of China (No. 20473063 and No. 20590364).
文摘With home-made multi-walled carbon nanotubes （MWCNTs, simplified as CNTs in later text） as support, CNT-supported Co-Mo-S catalysts, denoted as x%（mass percentage）MoiCoj/CNTs, were prepared. Their catalytic performance for thiophene hydrodesulfurization （HDS） and pyrrole hydrodenitrification （HDN） reactions was studied, and compared with the reference system sup- ported by AC. Over the 7.24%Mo3Co1/CNTs catalyst at reaction condition of 1.5 MPa, 613 K, C4H4S/H2=3.7/96.3（molar ratio） and GHSV≈8000 mlswP/（g-cat.h）, the specific HDS activity of thiophene reached 3.29 mmolc4H4S/（s.molMo）, which was 1.32 times as high as that （2.49 mmolc4H4S/（s.molMo）） of the AC-based counterpart, and was 2.47 times as high as that （1.33 mmolc4H4S/（s-molMo）） of the catalysts supported by AC with the respective optimal MoaCol-loading amount, 16.90%Mo3Co1/AC. Analogous reaction-chemical behaviours were also observed in the case of pyrrole HDN. It was experimentally found that using the CNTs in place of AC as support of the catalyst caused little change in the apparent activation energy for the thiophene HDS or pyrrole HDN reaction, but led to a significant increase in the concentration of catalytically active Mo-species （Mo^4＋） at the surface of the functioning catalyst. On the other hand, H2-TPD measurements revealed that the CNT-supported catalyst could reversibly adsorb a greater amount of hydrogen under atmospheric pressure at temperatures ranging from room temperature to about 673 K. This unique feature would help to generate microenvironments with higher stationarystate concentration of active hydrogen-adspecies at the surface of the functioning catalyst. Both factors mentioned above were favorable to increasing the rate of thiophene HDS and pyrrole HDN reactions.
文摘A convenient and effective Paal-Knorr condensations of 2,5-hexanedione with most amines have been carried out at room temperature under solvent-free condition.Macroporous strongly acidic styrol resin(D001) as a novel,efficient,cost-effective,and reusable solid acid catalyst for the synthesis of pyrroles under the same conditions.The pyrroles were obtained in high yields in short reaction times.
文摘Pyridinic N is widely regarded as the active center while pyrrolic N has low‐activity in metal‐free N‐doped carbon for electrocatalytic CO_(2) reduction reaction(CO_(2)RR)to CO,but this viewpoint remains open to question.In this study,through density functional theoretical calculations,we first illustrate that the intrinsic activity of pyrrolic N is high enough for effectively catalyzing CO_(2)RR,however,due to the interplay with the neighboring pyridinic N sites,the activity of pyrrolic N is dramatically suppressed.Then,experimentally,metal‐free N‐doped carbon spheres(NCS)electrocatalysts without significant pyridinic N content are prepared for CO_(2)RR.The pyrrolic N in NCS shows a direct‐positive correlation with the performance for CO_(2)RR,representing the active center with high activity.The optimum NCS could produce syngas with a wide range of CO/H_(2) ratio(0.09 to 12)in CO_(2)RR depending on the applied potential,meanwhile,the best selectivity of 71%for CO can be obtained.Intentionally adding a small amount of pyridinic N to the optimum NCS dramatically decreases the activity for CO_(2)RR,further verifying the suppressed activity of pyrrolic N sites by the neighboring pyridinic N sites.This work reveals the interaction between a variety of N species in N‐doped carbon,and the potential of pyrrolic N as the new type of active site for electrocatalysts,which can improve our understanding of the electrocatalysis mechanism and be helpful for the rational design of high‐efficient electrocatalysts.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.81991521,41676073)the National Key Research and Development Program of China(No.2018YFC0310903)+2 种基金the Drug Innovation Major Project(No.2018ZX09711-001-001-009)the SKLDR/SIMM Project(No.SIMM1903ZZ-04)Changsha Engineering Technology Research Center of Woody flower(kq1907081).
文摘A phytochemical investigation of the EtOH extract of the flowers of Lagerstroemia indica L.led to the isolation and char-acterization of a new pyrrole alkaloid,named lagerindicine(1),along with four known compounds(2-5).Their structures were elucidated by the detailed spectroscopic analysis and comparison with literature data,whereas the structure,in par-ticularly,the absolute configuration(AC)of 1,was firmly determined by total synthesis.All the isolates were evaluated for their cytotoxic effects against human colon cancer cell(HCT-116),and compound 3 exhibited weak cytotoxicity with IC50 value of 28.4μM.
基金supported by the National Key Research and Development Program of China(Grant No.2017YFA0206703)the National Natural Science Foundation of China(Grant No.U2032151)。
文摘The electrochemical performance of lithium-sulfur(Li-S)batteries is strongly hampered by the shuttle effect and slow redox kinetics of lithium polysulfides(Li PSs).Surface modified interlayer of a separator of Li-S batteries is demonstrated to be an effective strategy to overcome this problem.Herein,cobalt nanoparticles confined in nitrogen co-doped porous carbon framework(Co-CN)were developed from pyrolysis of ZIF-67 and used as interlayer of PP separator for Li-S batteries,and were functionalized by four pyrrole derivatives,1-phenylpyrrole,1-methyl pyrrole,1-(p-toluenesulfonyl)pyrrole,and 1-pyrrole,respectively,which were screened in terms of the electron-withdrawing/donating ability of the substituent groups on the pyrrolic nitrogen.The impact of the molecular structure of pyrrole derivatives on the interaction with Li PSs and the electrochemical performance of Li-S batteries were explored by nuclear magnetic resonance and theoretical calculation.It is uncovered that 1-phenylpyrrole shows the highest enhancement of redox kinetics of Li PSs,attributing to the optimal interaction with Co nanoparticles and Li PSs.Therefore,1-phenylpyrrole modified Co-CN interlayer enables the best electrochemical performance for the Li-S batteries,delivering a specific capacity of 562 m Ah g^(-1)at 5 C and a capacity of 538,526,and 449 m Ah g^(-1)after 500 cycles at 1,2,and 3 C,respectively.At a high sulfur loading of 5.5 mg cm^(-2),it achieves a capacity of 440 m Ah g^(-1)after 500 cycles at 1 C.This work reveals the interaction mechanism among Li PSs,Co nanoparticles and the molecular modifiers in improving the electrochemical performance of Li-S batteries.
基金financially supported by the National Natural Science Foundation of China (Nos. 21875216, 21734008)Zhejiang Province Science and Technology Plan (No. 2018C01047)the financial support from Research Grant Council of Hong Kong (General Research Fund No. 14314216, CUHK Direct Grant No. 4053227)
文摘To achieve the red-shifted absorptions and appropriate energy levels of A-D-A type non-fullerene acceptors(NFAs), in this work, we design and synthesize two new NFAs, named TPDCIC and TPDCNC, whose electron-donating(D) unit is constructed by a thieno[3,4-c]pyrrole-4,6-dione(TPD) core attached to two cyclopentadithiophene(CPDT) moieties at both sides, and the electronaccepting(A) end-groups are 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile(IC) and 2-(3-oxo-2,3-dihydro-1 H-cyclopenta[b]naphthalen-1-ylidene)malononitrile(NC), respectively. Benefiting from TPD core, which easily forms quinoid structure and O···H or O···S intramolecular noncovalent interactions, TPDCIC and TPDCNC show more delocalization of π-electrons and perfect planar molecular geometries, giving the absorption ranges extended to 822 and 852 nm, respectively. Furthermore, the highest occupied molecular orbital(HOMO) levels of TPDCIC and TPDCNC remain relatively low-lying due to the electronegativity of the carbonyl groups on TPD core. Considering that the absorptions and energy levels of the two NFAs match well with those of a widely used polymer donor, PBDB-T, we fabricate two kinds of organic solar cells(OSCs) based on the PBDB-T:TPDCIC and PBDB-T:TPDCNC blended films, respectively. Through a series of optimizations, the TPDCIC-based devices yield an impressing power conversion efficiency(PCE)of 10.12% with a large short-circuit current density(JSC) of 18.16 mA·cm-2, and the TPDCNC-based ones exhibit a comparable PCE of9.80% with a JSC of 17.40 mA·cm-2. Our work is the first report of the TPD-core-based A-D-A type NFAs, providing a good reference for the molecular design of high-performance NFAs.
基金the Nature Science Foundation of Gansu Provice (NO. A52).
文摘Supramolecular interaction of calix[4]pyrroles with several inorganic anions is reported by addition of calix[4]pyrroles to background electrolyte (BGE) in CZE. The retention time (t(R)) of all anions increased with increasing concentration of calix[4]pyrroles. The effect on F- is most evident.
基金supported by the Research Council of the University of Tehran as research project(No6102036/ 1/03)
文摘An efficient 1-methylimidazole-catalyzed synthesis of dialkyl 2-[（4-methylphenyl）sulfonyl]-1H-pyrrole-3,4-dicarboxylates is described.The reactive 1：1 zwitterionic intermediate formed by the addition of 1-methylimidazole to dialkyl acetylenedicarboxylates is trapped by tosylmethyl isocyanide（TOSMIC） to afford the title compounds in excellent yields.
基金Scientific and technological innovation project of China Academy of Chinese Medical Sciences(CI2021A04409,CI2021A04404,CI2021A04405)the fundamental research funds for the central public welfare research institutes(No.ZZ13-YQ-061,ZXKT22012,ZXKT22039).
文摘An undescribed pyrrole acid,1-(4′-methoxy-4′-oxobutyl)-1 H-pyrrole-2,5-dicarboxylic acid(1)and one known pyr-role acid(2)were isolated from the fruits of Phyllanthus emblica.The structures of these compounds were elucidated via the comprehensive analyses of IR,HRESIMS,1D and 2D spectroscopic data.A series of biological assays revealed that compounds 1 and 2 could inhibit LPS-induced over-production of nitric oxide(NO),interleukin-6(IL-6),monocyte chemotactic protein 1(MCP-1)and tumor necrosis factor-α(TNF-α)by reducing the phosphorylation of extracellular regulated protein kinases(ERK)and c-Jun N-terminal kinases(JNK)in RAW 264.7 cells.Additionally,compounds 1 and 2 were found to reduce lipid deposition and increase the mRNA expression of ATP-binding cassette transporter A1 in oxidized low-density lipoprotein-treated RAW264.7 macrophages.
基金Professor Pang Zhang for his encouragementthe National Natural Science Foundation of China !298
文摘One simple and versatile method is established far the synthesis of DNA recognition molecules-polyamides containing alternating N-methylpyrrole and N-methylimidazole without necessitating NH2- group protection.
