Influenza virus poses a significant threat to global public health,causing serious repercussions on human life and social well-being.Over the past decades,various antiviral drugs targeting either the virus itself or i...Influenza virus poses a significant threat to global public health,causing serious repercussions on human life and social well-being.Over the past decades,various antiviral drugs targeting either the virus itself or its host were identified.However,the emergence of drug-resistant influenza virus strains has posed a critical challenge to the effectiveness of these existing anti-influenza agents .Consequently,there is an urgent need to develop novel molecules with new chemical frameworks.Macrocyclic natural products serve as a crucial resource for validating targets and discovering lead compounds.However,the number of naturlly crring macrocyclic natural products is limited due to inherent biosynthetic pathways,which restricts the development of macrocyclic drugs.In contrast,artificially synthesized pseudonatural products show enhanced availability and greater structural diversity,while possessing similar biological functions[5]and have attracted significant interest from medicinal chemists.Hence,it is valuable to develop effective synthetic methods to expedite the discovery of macrocyclic lead compounds.展开更多
Purpose: The oxidative stress (OS) hypothesis of overtraining syndrome argues that increased production of free radicals through exercise cause muscle fatigue and damage resulting in lower athletic performance. Severa...Purpose: The oxidative stress (OS) hypothesis of overtraining syndrome argues that increased production of free radicals through exercise cause muscle fatigue and damage resulting in lower athletic performance. Several studies have investigated OS immediately before and after exercise bouts in a training macrocycle. Our study aimed to compare OS of endurance athletes between a competition macrocycle and the immediate post-season recovery macrocycle. In addition, we aimed to identify athletes who experienced an unexplainable drop in athletic performance during the competition season in order to compare their OS to those who experienced no drop in performance. Methods: Fifteen members of the University of Alaska Fairbanks cross country ski team volunteered for this study. Blood samples were taken in early February (“mid-season”) and late April (“post-season”). Participants completed questionnaires regarding physical activity and athletic performance at the time of the blood draws. Plasma was analyzed for 4-hydroxynonenal<sup> </sup>(HNE), nitrotyrosine,<sup> </sup>nitric oxide (NOX), and superoxide dismutase (SOD). Significance was determined by Wilcoxon and Mann-Whitney tests. Results: Participants displayed significantly higher (p Conclusion: Signs of oxidative stress and mitigation during the post-season recovery macrocycle were higher in athletes who reported experiencing a drop in athletic performance during the competition season macrocycle.展开更多
The development of innovative strategies and methods to provide natural product-like macrocycles not accessible by biosynthesis, but endowed with novel bioactivities and simplified structure, is highly desirable. Insp...The development of innovative strategies and methods to provide natural product-like macrocycles not accessible by biosynthesis, but endowed with novel bioactivities and simplified structure, is highly desirable. Inspired by the key scaffolds of rapamycin and FR252921, herein, we report a Rh(III)-catalyzed C–H alkylation macrocyclization, which enables access to CF_(3)-substituted macrolides. DFT calculations reveal that the chemoselectivity between C–H alkylation and olefination macrocyclization was highly controllable. Moreover, the unique CF_(3)-substituted macrolides showed potent anti-inflammation activities against TNF-α, IL-6 and CCL2 m RNA expression.展开更多
Individual hydrocarbons identified to be macrocyclic alkanes in a torbanite from the Sydney Basin(Australia)were successfully isolated from its extracts using preparative gas chromatography and analyzed by NMR.Saturat...Individual hydrocarbons identified to be macrocyclic alkanes in a torbanite from the Sydney Basin(Australia)were successfully isolated from its extracts using preparative gas chromatography and analyzed by NMR.Saturated cyclic structures were confirmed by single peaks in the NMR~1H and~(13)C spectra indicating single forms of H and C atoms exist in these biomarker molecules.This is consistent with the methylene unit in a ring system assignment of the macrocyclic alkanes and accounts for a formula of(CH2)n.The unusual molecular structures of these compounds are consistent with those that were identified from previous GC retention index data and co-injection with a standard supports the previous research.The mass spectral fragmentation behaviors of representative cyclic alkanes were further investigated by comparing them with the mass spectra of isolated individual macrocyclic alkanes.The characteristic fragment ions in the macrocyclic alkanes of(M–28)+and base peaks of m/z 97,111,125,etc.,can be assigned as being generated by simple a-/i-cleavage and hydrogen rearrangement.These fragmentation pathways combined with retention indices should assist in differentiating these compounds from monounsaturated alkenes and alkylated monocyclics having similar mass spectral characteristics in other geological samples.展开更多
Macrocyclic arylene ether ketone was characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrum(MALDI-TOF MS)combining with nuclear magnetic resonance(NMR)spectra.No any more fragment io...Macrocyclic arylene ether ketone was characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrum(MALDI-TOF MS)combining with nuclear magnetic resonance(NMR)spectra.No any more fragment ionization peaks except for the molecular ion peak from the mass spectrum.The structure of macrocyclic dimmer was further affirmed by the NMR spectra through the analysis of chemical shifts.The MALDI-TOF MS combining with NMR technique was found an important tool to characterized Macrocyclic aromatic oligomers.展开更多
The novel macrocyclic dilactams with redox-switched disulfide linkage were synthesized. These compounds were obtained from 2,2′-dithiodibenzoyl chloride in the macrocyclization step by fast addition method in moderat...The novel macrocyclic dilactams with redox-switched disulfide linkage were synthesized. These compounds were obtained from 2,2′-dithiodibenzoyl chloride in the macrocyclization step by fast addition method in moderate yields.展开更多
A new macrocyclic diterpenoid,named kansuinine J(1),was isolated from the roots of Euphorbia kansui.Its structure was characterized on the basis of spectroscopic analysis.
The title compound (13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.1^11,15]-triaconta-1 (29),2,9,11,13,15(30), 16,23,25,27- decaene-29,30-diol-N^3, N^6, N^9, O^29, O^30)-bis (nitrato-O,O')-europium (...The title compound (13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.1^11,15]-triaconta-1 (29),2,9,11,13,15(30), 16,23,25,27- decaene-29,30-diol-N^3, N^6, N^9, O^29, O^30)-bis (nitrato-O,O')-europium (Ⅲ) nitrate hydrate ([EuL(NO3)2](NO3)·H2O, L denotes the macrocyclic ligand) was prepared and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structure was determined by X-ray diffraction. The crystal crystallized in the monoclinic system, space group C2/c with a=2.3757 (4) nm, b=1.4302(3) nm, c=1.9584(3) nm, β=91.654(5)°, M=818.60, V=6.651(2) nm^3, Z=8, D=1.635 g/cm, F(000)=3312, R=0.0542, wR=0.1045. The central ion Eu^3+ was nine-coordinated in the coordinaton geometry of a distorted tricapped trigonal prism. The macrocycle was coordinated through two oxygen and three nitrogen atoms. Two nitrate are chelate in the opposite positions of the macrocycle, the third nitrate being ionic. At room temperature, excitation of the title complex gave rise to the characteristic emissions of the Eu^3+ ion.展开更多
Five new aza-crown ethers have been prepared by the condensation of 2,6-bis[(2-formylphenyl)oxymethyl] pyridine with different diamino compounds in hot methanol, the bis-Schiff bases without isolation were reduced wit...Five new aza-crown ethers have been prepared by the condensation of 2,6-bis[(2-formylphenyl)oxymethyl] pyridine with different diamino compounds in hot methanol, the bis-Schiff bases without isolation were reduced with NaBH4 to afford the corresponding aza-crown ethers. The liquid membrane transport or alkali cations using the five new macrocycles as the ion-carriers was also studied.展开更多
The title compound, [NiL]5[V34O82·8H2O (1, L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane), has been synthesized under hydrothermal conditions and structurally characterized by EA, IR, XPS, TG an...The title compound, [NiL]5[V34O82·8H2O (1, L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane), has been synthesized under hydrothermal conditions and structurally characterized by EA, IR, XPS, TG and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c with a=33.061(4), b=15.3457(17), c=33.902(4), β=101.930(2)°, Mr=4904.08, V=16828(3)3 , Z=4, Dc=1.936 g/cm3 , F(000)=9832, μ=2.425 mm-1 , the final R=0.0402 and wR=0.0969. The mixed valence vanadium clusters of [V34O82]10- bridges [NiL]2+ to form a one-dimensional chain in 1. To the best of our knowledge, the title complex is the first example of organic-inorganic hybrid material involving the largest vanadium cluster of [V34O82]10-.展开更多
The activities of the catalytic hydrolysis of phosphate diester (BNPP) [bis(p-nitrophenyl)phosphate diester] and plasmid DNA (pUC 18) by mononuclear macrocyclic polyamine metal complexes have been investigated i...The activities of the catalytic hydrolysis of phosphate diester (BNPP) [bis(p-nitrophenyl)phosphate diester] and plasmid DNA (pUC 18) by mononuclear macrocyclic polyamine metal complexes have been investigated in this paper. The results showed that the highest activity in hydrolysis of BNPP was obtained with le--Zn(II) complex (composed of lipophilic group) as catalyst. The hydrolysis rate enhancement is up to 3.64 × 10^4 fold. These metal complexes could effectively promote the cleavage of plasmid DNA (pUC18) at physiological conditions.展开更多
Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien,...Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid) have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595(5), b = 23.1498(11), c = 17.2558(8) and =101.2530(10)°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214(8), b = 20.6566(14), c = 18.4126(13) and = 92.6770(10)°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.展开更多
Two pyrazine-containing macrocyclic polyazomethines 2 and 3 were synthesized by direct [2 + 2] and [3 + 3] condensation reactions between 2,21-[pyrazine-2,3-diylbis(oxy)]dibenzaldehyde (1) and hydrazine. Both 2 ...Two pyrazine-containing macrocyclic polyazomethines 2 and 3 were synthesized by direct [2 + 2] and [3 + 3] condensation reactions between 2,21-[pyrazine-2,3-diylbis(oxy)]dibenzaldehyde (1) and hydrazine. Both 2 and 3 were characterized by NMR, HRMS, and their structures were determined via X-ray crystal diffraction studies.展开更多
The reaction of salicylic chloride and salicylic amide at 170 ℃ gave benzoxazine and a new macrocyclic polyester 3, whose crystal structure has been determined by single-crystal X-ray diffraction analysis. Compound 3...The reaction of salicylic chloride and salicylic amide at 170 ℃ gave benzoxazine and a new macrocyclic polyester 3, whose crystal structure has been determined by single-crystal X-ray diffraction analysis. Compound 3: C28H16O8, Mr = 480.41, monoclinic, space group P21/n, a = 15.353(3), b = 14.196(3), c = 21.147(4) ? b = 103.32(3), V = 4485(2) ?, Z = 8, F(000) = 1984, Dc = 1.423 g/cm3 and m = 0.106 mm-1. The final R = 0.0535 and wR = 0.1275 for 7903 observed reflections (I ≥ 2(I)). In the asymmetric unit of the compound there exist two independent molecules which are connected by weak aromatic CH…O hydrogen bonding between C(47)?H(47) and atom O(7) of the carbonyl group.展开更多
The structure of a new macrocyclic compound, clemochinenoside A obtained from Clematis chinensis was identified by NMR, FAB-MS, NOE and chemical hydrolysis.
The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, ...The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?展开更多
The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distribut...The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distributions of the deprotonated and protonated compounds in the pH range from 2 to 12 aqueous solutions were also described.展开更多
A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesi...A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesized by the NaBH4 reduction of the Schiff-base obtained from the [2+2] condensation between diethylenetriamine and diformyl -p-cresol. The structure was characterized by elemental analysis, 1HNMR and FAB-MS. The synthetic method was also discussed.展开更多
The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: ...The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: C20H36N10Ni, monoclinic, space group P21/c, a = 9.632(2), b = 11.833(2), c = 10.613(2) ? b = 93.46(3), V = 1207.4(4) ?, Mr = 475.30, Z = 2, Dc = 1.307 g/cm3, F(000) = 508, m(MoKa) = 0.831 mm-1, R = 0.0446 and wR = 0.1274 for 2423 observed reflections with I > 2s(I). The center nickel ion is coordinated by six nitrogen atoms, four from the macrocyclic ligand teta and the other two from two dicyanamides. The dicyanamide is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.展开更多
A series of novel aromatic-linked polyamine macrocyclic derivatives have been synthesized. Their structures were confirmed by MS and ^1H NMR. These compounds exhibited potent anti-HIV-1 activities.
基金supported by the Natural Science Foundation of Jiangsu Province(No.BK20201332).
文摘Influenza virus poses a significant threat to global public health,causing serious repercussions on human life and social well-being.Over the past decades,various antiviral drugs targeting either the virus itself or its host were identified.However,the emergence of drug-resistant influenza virus strains has posed a critical challenge to the effectiveness of these existing anti-influenza agents .Consequently,there is an urgent need to develop novel molecules with new chemical frameworks.Macrocyclic natural products serve as a crucial resource for validating targets and discovering lead compounds.However,the number of naturlly crring macrocyclic natural products is limited due to inherent biosynthetic pathways,which restricts the development of macrocyclic drugs.In contrast,artificially synthesized pseudonatural products show enhanced availability and greater structural diversity,while possessing similar biological functions[5]and have attracted significant interest from medicinal chemists.Hence,it is valuable to develop effective synthetic methods to expedite the discovery of macrocyclic lead compounds.
文摘Purpose: The oxidative stress (OS) hypothesis of overtraining syndrome argues that increased production of free radicals through exercise cause muscle fatigue and damage resulting in lower athletic performance. Several studies have investigated OS immediately before and after exercise bouts in a training macrocycle. Our study aimed to compare OS of endurance athletes between a competition macrocycle and the immediate post-season recovery macrocycle. In addition, we aimed to identify athletes who experienced an unexplainable drop in athletic performance during the competition season in order to compare their OS to those who experienced no drop in performance. Methods: Fifteen members of the University of Alaska Fairbanks cross country ski team volunteered for this study. Blood samples were taken in early February (“mid-season”) and late April (“post-season”). Participants completed questionnaires regarding physical activity and athletic performance at the time of the blood draws. Plasma was analyzed for 4-hydroxynonenal<sup> </sup>(HNE), nitrotyrosine,<sup> </sup>nitric oxide (NOX), and superoxide dismutase (SOD). Significance was determined by Wilcoxon and Mann-Whitney tests. Results: Participants displayed significantly higher (p Conclusion: Signs of oxidative stress and mitigation during the post-season recovery macrocycle were higher in athletes who reported experiencing a drop in athletic performance during the competition season macrocycle.
基金the"100 Talent Program of Chinese Academy of Sciences""1000-Youth Talents Plan"+3 种基金ShanghaiYouth Talent,National Science&Technology Major Project"Key New Drug Creation and Manufacturing Program"China(No. 2018ZX09711002–006)Science and Technology Commission of Shanghai Municipality (No. 18431907100)ShanghaiTechnology Innovation Action Plan (No. 18JC1415300)the Research Grants Council of Hong Kong (No. HKUST 16302418) for financial support of this research。
文摘The development of innovative strategies and methods to provide natural product-like macrocycles not accessible by biosynthesis, but endowed with novel bioactivities and simplified structure, is highly desirable. Inspired by the key scaffolds of rapamycin and FR252921, herein, we report a Rh(III)-catalyzed C–H alkylation macrocyclization, which enables access to CF_(3)-substituted macrolides. DFT calculations reveal that the chemoselectivity between C–H alkylation and olefination macrocyclization was highly controllable. Moreover, the unique CF_(3)-substituted macrolides showed potent anti-inflammation activities against TNF-α, IL-6 and CCL2 m RNA expression.
基金the financial support from The Strategic Priority Research Program of the Chinese Academy of Sciences(XDA14010102)Chinese National Science Foundation grants(4197306941673045)。
文摘Individual hydrocarbons identified to be macrocyclic alkanes in a torbanite from the Sydney Basin(Australia)were successfully isolated from its extracts using preparative gas chromatography and analyzed by NMR.Saturated cyclic structures were confirmed by single peaks in the NMR~1H and~(13)C spectra indicating single forms of H and C atoms exist in these biomarker molecules.This is consistent with the methylene unit in a ring system assignment of the macrocyclic alkanes and accounts for a formula of(CH2)n.The unusual molecular structures of these compounds are consistent with those that were identified from previous GC retention index data and co-injection with a standard supports the previous research.The mass spectral fragmentation behaviors of representative cyclic alkanes were further investigated by comparing them with the mass spectra of isolated individual macrocyclic alkanes.The characteristic fragment ions in the macrocyclic alkanes of(M–28)+and base peaks of m/z 97,111,125,etc.,can be assigned as being generated by simple a-/i-cleavage and hydrogen rearrangement.These fragmentation pathways combined with retention indices should assist in differentiating these compounds from monounsaturated alkenes and alkylated monocyclics having similar mass spectral characteristics in other geological samples.
文摘Macrocyclic arylene ether ketone was characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrum(MALDI-TOF MS)combining with nuclear magnetic resonance(NMR)spectra.No any more fragment ionization peaks except for the molecular ion peak from the mass spectrum.The structure of macrocyclic dimmer was further affirmed by the NMR spectra through the analysis of chemical shifts.The MALDI-TOF MS combining with NMR technique was found an important tool to characterized Macrocyclic aromatic oligomers.
文摘The novel macrocyclic dilactams with redox-switched disulfide linkage were synthesized. These compounds were obtained from 2,2′-dithiodibenzoyl chloride in the macrocyclization step by fast addition method in moderate yields.
基金supported by grants from the Ministry of Science and Technology(Nos.2009CB940900 and 2009CB522300)
文摘A new macrocyclic diterpenoid,named kansuinine J(1),was isolated from the roots of Euphorbia kansui.Its structure was characterized on the basis of spectroscopic analysis.
基金supported by the National Natural Science Foundation of China (20671075)the Natural Science Foundation of Hubei Province (2005ABA021)China Postdoctoral Science Foundation (20060390858)
文摘The title compound (13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.1^11,15]-triaconta-1 (29),2,9,11,13,15(30), 16,23,25,27- decaene-29,30-diol-N^3, N^6, N^9, O^29, O^30)-bis (nitrato-O,O')-europium (Ⅲ) nitrate hydrate ([EuL(NO3)2](NO3)·H2O, L denotes the macrocyclic ligand) was prepared and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structure was determined by X-ray diffraction. The crystal crystallized in the monoclinic system, space group C2/c with a=2.3757 (4) nm, b=1.4302(3) nm, c=1.9584(3) nm, β=91.654(5)°, M=818.60, V=6.651(2) nm^3, Z=8, D=1.635 g/cm, F(000)=3312, R=0.0542, wR=0.1045. The central ion Eu^3+ was nine-coordinated in the coordinaton geometry of a distorted tricapped trigonal prism. The macrocycle was coordinated through two oxygen and three nitrogen atoms. Two nitrate are chelate in the opposite positions of the macrocycle, the third nitrate being ionic. At room temperature, excitation of the title complex gave rise to the characteristic emissions of the Eu^3+ ion.
基金We are gr ateful to the Natural Sc ience Foundation of Shandong Province for financial support ofthiswork (Q97B03123).
文摘Five new aza-crown ethers have been prepared by the condensation of 2,6-bis[(2-formylphenyl)oxymethyl] pyridine with different diamino compounds in hot methanol, the bis-Schiff bases without isolation were reduced with NaBH4 to afford the corresponding aza-crown ethers. The liquid membrane transport or alkali cations using the five new macrocycles as the ion-carriers was also studied.
基金supported by the Science and Technology Planning Project of Hunan Province (2012FJ3050, 2012NK3067)the Construct Program of the Key Discipline in Hunan Province (2011–76)the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province (2012–318)
文摘The title compound, [NiL]5[V34O82·8H2O (1, L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane), has been synthesized under hydrothermal conditions and structurally characterized by EA, IR, XPS, TG and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c with a=33.061(4), b=15.3457(17), c=33.902(4), β=101.930(2)°, Mr=4904.08, V=16828(3)3 , Z=4, Dc=1.936 g/cm3 , F(000)=9832, μ=2.425 mm-1 , the final R=0.0402 and wR=0.0969. The mixed valence vanadium clusters of [V34O82]10- bridges [NiL]2+ to form a one-dimensional chain in 1. To the best of our knowledge, the title complex is the first example of organic-inorganic hybrid material involving the largest vanadium cluster of [V34O82]10-.
基金supported by the Science and Technology Department(No.04JY029-018)Education Department of Sichuan Province(No.2006ZD049).
文摘The activities of the catalytic hydrolysis of phosphate diester (BNPP) [bis(p-nitrophenyl)phosphate diester] and plasmid DNA (pUC 18) by mononuclear macrocyclic polyamine metal complexes have been investigated in this paper. The results showed that the highest activity in hydrolysis of BNPP was obtained with le--Zn(II) complex (composed of lipophilic group) as catalyst. The hydrolysis rate enhancement is up to 3.64 × 10^4 fold. These metal complexes could effectively promote the cleavage of plasmid DNA (pUC18) at physiological conditions.
基金supported by the National Natural Science Foundation of China(No.20771083)
文摘Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid) have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595(5), b = 23.1498(11), c = 17.2558(8) and =101.2530(10)°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214(8), b = 20.6566(14), c = 18.4126(13) and = 92.6770(10)°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.
基金Shanghai Commission for Science and Technology(Nos.06Pj14034,06DZ19002,and 10ZR1409700)Ministry of Education(No.106078) for financial support
文摘Two pyrazine-containing macrocyclic polyazomethines 2 and 3 were synthesized by direct [2 + 2] and [3 + 3] condensation reactions between 2,21-[pyrazine-2,3-diylbis(oxy)]dibenzaldehyde (1) and hydrazine. Both 2 and 3 were characterized by NMR, HRMS, and their structures were determined via X-ray crystal diffraction studies.
基金the National Natural Science Foundation of China (Grant No. 29872023)
文摘The reaction of salicylic chloride and salicylic amide at 170 ℃ gave benzoxazine and a new macrocyclic polyester 3, whose crystal structure has been determined by single-crystal X-ray diffraction analysis. Compound 3: C28H16O8, Mr = 480.41, monoclinic, space group P21/n, a = 15.353(3), b = 14.196(3), c = 21.147(4) ? b = 103.32(3), V = 4485(2) ?, Z = 8, F(000) = 1984, Dc = 1.423 g/cm3 and m = 0.106 mm-1. The final R = 0.0535 and wR = 0.1275 for 7903 observed reflections (I ≥ 2(I)). In the asymmetric unit of the compound there exist two independent molecules which are connected by weak aromatic CH…O hydrogen bonding between C(47)?H(47) and atom O(7) of the carbonyl group.
文摘The structure of a new macrocyclic compound, clemochinenoside A obtained from Clematis chinensis was identified by NMR, FAB-MS, NOE and chemical hydrolysis.
文摘The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?
基金the Robert A. Welch Foundation (A-0259) in the U.S and China Scholarship Council is gratefully acknowledged.
文摘The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distributions of the deprotonated and protonated compounds in the pH range from 2 to 12 aqueous solutions were also described.
文摘A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesized by the NaBH4 reduction of the Schiff-base obtained from the [2+2] condensation between diethylenetriamine and diformyl -p-cresol. The structure was characterized by elemental analysis, 1HNMR and FAB-MS. The synthetic method was also discussed.
基金The project was supported by the funds of the Key Laboratory of Organic Syntheses of Jiangsu province(KJS01018) and Funds of Young Teacher of Suzhou University
文摘The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: C20H36N10Ni, monoclinic, space group P21/c, a = 9.632(2), b = 11.833(2), c = 10.613(2) ? b = 93.46(3), V = 1207.4(4) ?, Mr = 475.30, Z = 2, Dc = 1.307 g/cm3, F(000) = 508, m(MoKa) = 0.831 mm-1, R = 0.0446 and wR = 0.1274 for 2423 observed reflections with I > 2s(I). The center nickel ion is coordinated by six nitrogen atoms, four from the macrocyclic ligand teta and the other two from two dicyanamides. The dicyanamide is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.
基金supported by the National Basic Research Program of China(973 project:No.2004CB518908)the National Natural Science Foundation of China(No.30472093)to SLthe 0utstanding 0verseas Chinese Scholars Fund of Chinese Academy of Sciences(No.2005-2-6)to S.J.
文摘A series of novel aromatic-linked polyamine macrocyclic derivatives have been synthesized. Their structures were confirmed by MS and ^1H NMR. These compounds exhibited potent anti-HIV-1 activities.