Three new napelline-type C20-diterpenoid alkaloids,named aconicarmichinium A and B trifluoroacetates（1 and 2） and aconicarmichinium C chloride（3）,were isolated from an aqueous extract of ＂fu zi＂,the lateral root...Three new napelline-type C20-diterpenoid alkaloids,named aconicarmichinium A and B trifluoroacetates（1 and 2） and aconicarmichinium C chloride（3）,were isolated from an aqueous extract of ＂fu zi＂,the lateral roots of Aconitum carmichaelii.Their structures were elucidated by extensive spectroscopic data analysis.Compounds 1-3 represent the first examples of napelline-type C20 diterpenoid alkaloid alcohol iminiums,of which the structures were fully characterized.In addition,transformation and equilibration between the alcohol iminiums（1-3） and the aza acetals la-3a were investigated by measurements of the NMR spectra in protic and aprotic deuterium solvents including alkali pyridine-d5,along with evaporation under reduced pressure and gradual additions of TFA,AcOH,and HC1.The results demonstrated that the transformation and equilibration were solvent-,base-,and acid-dependent.Especially,in aqueous biological fluid,these C20-diterpenoid alkaloids would more likely exist as the alcohol iminiums accompanied by anion counterparts in biosystems to increase their solubility, bioavailability, transportations, and functions.The absolute configurations of 1-3 were confirmed by X-ray crystallographic analysis of 2a.展开更多
Background An increasing incidence of Crohn' s disease has been found in China in recent years. Our study has been focused on evaluating the diversity of the clinical manifestations of Crohn' s disease in orde...Background An increasing incidence of Crohn' s disease has been found in China in recent years. Our study has been focused on evaluating the diversity of the clinical manifestations of Crohn' s disease in order to improve early diagnostic accuracy and therapeutic efficacy.Methods Thirty patients with active Crohn's disease were enrolled and their clinical data, including diagnostic and therapeutic results, were analyzed. Endoscopy combined with histological examination of biopsy specimens provided characteristic features of the disease. Transabdominal bowel sonography (TABS) was used for detecting intestinal complications. Nutritional supportive therapy was given to 20 subjects with active cases of the disease.Results Most patients were young adults with a higher proportion of females to males (ratio: 1.14: 1). The disease affects any segment or a combination of segments along with the alimentary tract (from the mouth to the anus). In this study, the colon and small bowel were the major sites involved. Recurrent episodes of abdominal pain in the right lower quadrant and watery diarrhea were the most common symptoms. Granulomas were identifiable in nearly one-third (30.8%) of all biopsy specimens. In moderate cases of the disease, remission was achieved more quickly through the use of oral prednisone therapy than with SASP or 5-ASA. Beneficial effects on the host's nutritional status were observed. Immunosuppressives were used on an individual basis and showed variable therapeutic effects. Sixteen patients had surgery due to intestinal obstruction or failure to respond to drug therapies. Rapid improvement after surgery was reported.Conclusion Endoscopy (with biopsy) and TABS were both crucial procedures for diagnosis. SASP (or 5-ASA) and prednisone were effective as inductive therapies. Azathioprine has demonstrable benefits after induction therapy with prednisone. Surgery, as an alternative treatment, provided another effective choice in selected patients.展开更多
This study examined the photostabilization of Azadirachtin-A （Aza-A） when exposed to ultraviolet light in the presence of some natural absorbers. Aza-A extract solutions with and without natural UV light absorbers i...This study examined the photostabilization of Azadirachtin-A （Aza-A） when exposed to ultraviolet light in the presence of some natural absorbers. Aza-A extract solutions with and without natural UV light absorbers in methanol were applied onto the surface of glass slides. At particular intervals, the remaining concentration of Aza-A was analyzed by HPLC. Using first-order kinetic equation, the dissipation half-life values （DT^0） for the degradation of Aza-A under ultraviolet radiation were obtained. It indicated that the addition of ferulic acid, gallic acid, and rutin provided moderate degree of photostabilization of Aza-A and that addition of aloin provided the best photostabilization of Aza-A, among these UV absorbers studied. Photostabilization of Aza-A by different UV light absorbers appears to be due to the competitive energy absorption of UV photons by the absorbers molecules. The dissipation half-life values of Aza-A after irradiation under ultraviolet light suggested that the addition of aloin （in 1 ： 1 mol ratio） can provide better photostabilization of azadirachtin molecule.展开更多
Thirteen new 2 alkylaminoimidazolones (4) were rapidly synthesized by a new solution phase parallel synthetic method, which includes aza Wittig reaction of iminophosphorane (1) with aromatic isocyanate to give carb...Thirteen new 2 alkylaminoimidazolones (4) were rapidly synthesized by a new solution phase parallel synthetic method, which includes aza Wittig reaction of iminophosphorane (1) with aromatic isocyanate to give carbodi imide (2) and subsequent reaction of 2 with various aliphatic primary amine in a parallel fashion. The products were confirmed by 1H NMR, MS, IR and X ray crystallographic analysis. The unusual selectivity of the cyclization was probably due to the geometry of the guanidine intermediate.展开更多
Calix[4] (aza) crowns containing amide groups 3a—d were synthesized by the reactions of calix[4]arene (la) or p-tert-butylcalix[4]arene (1b) with N, N′-ethylenebis(2-chloroacetamide) (2a) or N, N′- 1,2-ethylenebis ...Calix[4] (aza) crowns containing amide groups 3a—d were synthesized by the reactions of calix[4]arene (la) or p-tert-butylcalix[4]arene (1b) with N, N′-ethylenebis(2-chloroacetamide) (2a) or N, N′- 1,2-ethylenebis (2-chloroacetamide) (2b) by one step procedure in yields of 85—-90%. Calix[4]-(aza) crowns 4a—b could be obtained by the reduction of 3a—b with LiAlH4 in yields of 51 and 67%, respectively. The nitration of 3a or 3c afforded new chromogenic calix[4]arenes 5a bearing two nitrophenol moieties and 5c bearing one nitro-phenol and one quinone moiety, respectively. The ipso-nitration's of 3b and 3d were also studied. Both gave the products containing one nitro phenol and one quinine moiety. Moreover, a very interesting calix[4]arene derivative 5d containing one cyclohexadienone moiety was also separated as the main product when 3d was ipso-nitrated.展开更多
Four new complexes of rare earths with a triaza crown ether (L) derived from N 3O 2 macro cycle 1,12,15 triaza 3, 4: 9,10 dibenzo 5, 8 dioxacycloheptadecane were synthesized and characterized by elemental ana...Four new complexes of rare earths with a triaza crown ether (L) derived from N 3O 2 macro cycle 1,12,15 triaza 3, 4: 9,10 dibenzo 5, 8 dioxacycloheptadecane were synthesized and characterized by elemental analysis, IR, molar conductance, TG DTA analysis and fluorescence spectra. The composition of the complexes determined as [RE(NO 3) 3L·3H 2O]·H 2O (RE=Sm, Eu, Tb and Dy). It is found that Sm 3+ , Eu 3+ , Tb 3+ and Dy 3+ complexes all show strong fluorescence emission in the solid state. Among these complexes, Tb 3+ complex has the strongest luminescence intensity. It shows that the ligand L triplet state energy matches 5D 4 energy level of Tb 3+ . In the Eu 3+ complex, η ( 5D 0→ 7F 2/ 5D 0→ 7F 1) is 2.6, which indicates that Eu 3+ locates at the asymmetric coordination field.展开更多
The synthesis of a new type of selena aza crown ether 6 (4 nitrobenzyl) 1,4,7,10 selenatriazacyclododecane (L) derivated from phenylalanine , and its platinum(Ⅱ) complex was described. The catalytic activity of...The synthesis of a new type of selena aza crown ether 6 (4 nitrobenzyl) 1,4,7,10 selenatriazacyclododecane (L) derivated from phenylalanine , and its platinum(Ⅱ) complex was described. The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.展开更多
A series of selena aza crown ether is condensed by 1,5 bis(p tosylsulphonylamino) 3 selena pentane with ditosylates or dihalides in K 2CO 3/DMF or NaH/DMF. The yields are about 30% 60%.
基金Financial support from the National Natural Science Foundation of China (NNSFC Nos. 21132009, 30825044)the National Science and Technology Project of China (Nos. 2012ZX09301002002, 2011ZX0 9307-002-01)
文摘Three new napelline-type C20-diterpenoid alkaloids,named aconicarmichinium A and B trifluoroacetates（1 and 2） and aconicarmichinium C chloride（3）,were isolated from an aqueous extract of ＂fu zi＂,the lateral roots of Aconitum carmichaelii.Their structures were elucidated by extensive spectroscopic data analysis.Compounds 1-3 represent the first examples of napelline-type C20 diterpenoid alkaloid alcohol iminiums,of which the structures were fully characterized.In addition,transformation and equilibration between the alcohol iminiums（1-3） and the aza acetals la-3a were investigated by measurements of the NMR spectra in protic and aprotic deuterium solvents including alkali pyridine-d5,along with evaporation under reduced pressure and gradual additions of TFA,AcOH,and HC1.The results demonstrated that the transformation and equilibration were solvent-,base-,and acid-dependent.Especially,in aqueous biological fluid,these C20-diterpenoid alkaloids would more likely exist as the alcohol iminiums accompanied by anion counterparts in biosystems to increase their solubility, bioavailability, transportations, and functions.The absolute configurations of 1-3 were confirmed by X-ray crystallographic analysis of 2a.
文摘Background An increasing incidence of Crohn' s disease has been found in China in recent years. Our study has been focused on evaluating the diversity of the clinical manifestations of Crohn' s disease in order to improve early diagnostic accuracy and therapeutic efficacy.Methods Thirty patients with active Crohn's disease were enrolled and their clinical data, including diagnostic and therapeutic results, were analyzed. Endoscopy combined with histological examination of biopsy specimens provided characteristic features of the disease. Transabdominal bowel sonography (TABS) was used for detecting intestinal complications. Nutritional supportive therapy was given to 20 subjects with active cases of the disease.Results Most patients were young adults with a higher proportion of females to males (ratio: 1.14: 1). The disease affects any segment or a combination of segments along with the alimentary tract (from the mouth to the anus). In this study, the colon and small bowel were the major sites involved. Recurrent episodes of abdominal pain in the right lower quadrant and watery diarrhea were the most common symptoms. Granulomas were identifiable in nearly one-third (30.8%) of all biopsy specimens. In moderate cases of the disease, remission was achieved more quickly through the use of oral prednisone therapy than with SASP or 5-ASA. Beneficial effects on the host's nutritional status were observed. Immunosuppressives were used on an individual basis and showed variable therapeutic effects. Sixteen patients had surgery due to intestinal obstruction or failure to respond to drug therapies. Rapid improvement after surgery was reported.Conclusion Endoscopy (with biopsy) and TABS were both crucial procedures for diagnosis. SASP (or 5-ASA) and prednisone were effective as inductive therapies. Azathioprine has demonstrable benefits after induction therapy with prednisone. Surgery, as an alternative treatment, provided another effective choice in selected patients.
基金This project was supported by the National Natural Science Foundation of China(30500387)Natural Science Foundation of Jiangsu Province,China(BK2005008).
文摘This study examined the photostabilization of Azadirachtin-A （Aza-A） when exposed to ultraviolet light in the presence of some natural absorbers. Aza-A extract solutions with and without natural UV light absorbers in methanol were applied onto the surface of glass slides. At particular intervals, the remaining concentration of Aza-A was analyzed by HPLC. Using first-order kinetic equation, the dissipation half-life values （DT^0） for the degradation of Aza-A under ultraviolet radiation were obtained. It indicated that the addition of ferulic acid, gallic acid, and rutin provided moderate degree of photostabilization of Aza-A and that addition of aloin provided the best photostabilization of Aza-A, among these UV absorbers studied. Photostabilization of Aza-A by different UV light absorbers appears to be due to the competitive energy absorption of UV photons by the absorbers molecules. The dissipation half-life values of Aza-A after irradiation under ultraviolet light suggested that the addition of aloin （in 1 ： 1 mol ratio） can provide better photostabilization of azadirachtin molecule.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 0 10 2 0 0 1)
文摘Thirteen new 2 alkylaminoimidazolones (4) were rapidly synthesized by a new solution phase parallel synthetic method, which includes aza Wittig reaction of iminophosphorane (1) with aromatic isocyanate to give carbodi imide (2) and subsequent reaction of 2 with various aliphatic primary amine in a parallel fashion. The products were confirmed by 1H NMR, MS, IR and X ray crystallographic analysis. The unusual selectivity of the cyclization was probably due to the geometry of the guanidine intermediate.
基金Project (Nos. 29602010, 29772037) supported by the National Natural Science Foundation of China.
文摘Calix[4] (aza) crowns containing amide groups 3a—d were synthesized by the reactions of calix[4]arene (la) or p-tert-butylcalix[4]arene (1b) with N, N′-ethylenebis(2-chloroacetamide) (2a) or N, N′- 1,2-ethylenebis (2-chloroacetamide) (2b) by one step procedure in yields of 85—-90%. Calix[4]-(aza) crowns 4a—b could be obtained by the reduction of 3a—b with LiAlH4 in yields of 51 and 67%, respectively. The nitration of 3a or 3c afforded new chromogenic calix[4]arenes 5a bearing two nitrophenol moieties and 5c bearing one nitro-phenol and one quinone moiety, respectively. The ipso-nitration's of 3b and 3d were also studied. Both gave the products containing one nitro phenol and one quinine moiety. Moreover, a very interesting calix[4]arene derivative 5d containing one cyclohexadienone moiety was also separated as the main product when 3d was ipso-nitrated.
文摘Four new complexes of rare earths with a triaza crown ether (L) derived from N 3O 2 macro cycle 1,12,15 triaza 3, 4: 9,10 dibenzo 5, 8 dioxacycloheptadecane were synthesized and characterized by elemental analysis, IR, molar conductance, TG DTA analysis and fluorescence spectra. The composition of the complexes determined as [RE(NO 3) 3L·3H 2O]·H 2O (RE=Sm, Eu, Tb and Dy). It is found that Sm 3+ , Eu 3+ , Tb 3+ and Dy 3+ complexes all show strong fluorescence emission in the solid state. Among these complexes, Tb 3+ complex has the strongest luminescence intensity. It shows that the ligand L triplet state energy matches 5D 4 energy level of Tb 3+ . In the Eu 3+ complex, η ( 5D 0→ 7F 2/ 5D 0→ 7F 1) is 2.6, which indicates that Eu 3+ locates at the asymmetric coordination field.
文摘The synthesis of a new type of selena aza crown ether 6 (4 nitrobenzyl) 1,4,7,10 selenatriazacyclododecane (L) derivated from phenylalanine , and its platinum(Ⅱ) complex was described. The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.
文摘A series of selena aza crown ether is condensed by 1,5 bis(p tosylsulphonylamino) 3 selena pentane with ditosylates or dihalides in K 2CO 3/DMF or NaH/DMF. The yields are about 30% 60%.
