Aim L-Arginine· L-aspartate, a double salt, has been recently reported toinhibit platelet aggregation and thrombosis, but its action mechanism is not clear yet. This studywas conducted to investigate its effect o...Aim L-Arginine· L-aspartate, a double salt, has been recently reported toinhibit platelet aggregation and thrombosis, but its action mechanism is not clear yet. This studywas conducted to investigate its effect on FITC-PAC-1, an anti-glycoprotein IIb/IIIa monoclonalantibody binding to activated platelets, and on correlative autacoid levels in plasma or inplatelets in order to explore its potential pathway of inhibiting platelet aggregation andthrombosis. Methods Monoclonal antibody binding to activated platelets was assayed by flowcytometry; NO was assessed by colorimetric method. cAMP, TXB_2 or 6-keto-PGF_(1α) levels wereassessed by radioimmunoassay. Results Gavaged 30 mg·kg^(-1) of L-arginine·L-aspartate increasedboth concentration of NO in plasma and 6-keto-PGF_(1) in incubated supernatant of aortic segment ofrats ex vivo (P < 0.05), but it did not influence cAMP content in platelets and the level of TXB_2or 6-keto-PGF_(1) in plasma of rats, whereas ASA significantly lowered TXB_2 or 6-keto-PGF_(1α) inplasma. Both 100 μmol-L^(-1) of L-arginine ·L-aspartate and ASA inhibited FITC-PAC-1 binding toactivated platelets in vitro. Conclusion The increase in NO and PGI_2 release from endo-thelialcells and consequent inhibition of platelet activation may contribute to the inhibition of plateletaggregation and thrombosis by L-arginine· L-aspartate; whereas arachidonic acid or cAMP metabolicpathway is not closely correlative with the studied effect.展开更多
Five novel ternary complexes of rare earth ions with L-Aspartic acid (Asp) and o-phenanthroline (Phen) were synthesized in ethanol aqueous solution. Their compositions were characterized by elemental analysis, molar c...Five novel ternary complexes of rare earth ions with L-Aspartic acid (Asp) and o-phenanthroline (Phen) were synthesized in ethanol aqueous solution. Their compositions were characterized by elemental analysis, molar conductance, FT-IR, Raman, UV-VIS and TG-DTA. The compositions of the complexes were confirmed to be: RE( Asp)3PhenCl3·3H2O (RE: Ce3+ , Pr3+ , Nd3+ , Sm3+ , Er3+ ). The antibacterial activity test shows that all these complexes exhibit excellent antibacterial ability against Escherichia coli, Staphylococcus aureus and Candida albicans. The antimicrobial spectrum of the complexes are broad.展开更多
The electrocatalytic oxidation of dopamine(DA)was studied by electrochemical approaches at a carbon ionic liquid electrode(CILE)modified with the composite film of nafion and L-aspartic acid(NL-CILE).The CILE was fabr...The electrocatalytic oxidation of dopamine(DA)was studied by electrochemical approaches at a carbon ionic liquid electrode(CILE)modified with the composite film of nafion and L-aspartic acid(NL-CILE).The CILE was fabricated by replacing non-conductive organic binders with a room-temperature hydrophobic ionic liquid,1-butyl-3-methyl-imidazolium hexafluorophosphate.The composite film of NL was used as matrix to adsorb DA and catalyze the oxidation of DA in phosphate buffer solution(PBS).The electrochemical response of DA was investigated at the NL-CILE,the traditional carbon paste electrode(TCPE),CILE and the nafion modified CILE(N-CILE)in 0.1M PBS(pH 7.4),respectively.The results showed the superiority of NL-CILE to N-CILE,CILE and TCPE in terms of provision of higher sensitivity,faster electron transfer and better reversibility.Under optimum condition,the oxidation peak current was rectilinear with DA concentration range from 0.1μM to 0.1mM,with a detection limit of 0.03μM(S/N=3)by differential pulse voltammetry.The proposed method was applied to determine DA in samples successfully.展开更多
L-aspartic acid (Asp) pillared hydrotalcites were prepared by direct reaction of the L-Asp anion with layered double hydroxides (LDHs). The obtained samples were characterized by X-ray diffractometry (XRD), Four...L-aspartic acid (Asp) pillared hydrotalcites were prepared by direct reaction of the L-Asp anion with layered double hydroxides (LDHs). The obtained samples were characterized by X-ray diffractometry (XRD), Fourier transform infrared (FTIR), and thermogravimetric and differential thermal analysis (TG/DTA). The results show that the initial interlayer carbonate ions can be completely replaced by the L-Asp anion under the controlled conditions. The pillared hydrotalcites have a crystallized supramolecular structure and thermal stability. The L-Asp pillared LDHs were used in the enantiosorption of enantiopure phenylalanine (Pile), the results suggest that L-Asp pillared LDHs exhibit an excellent enantiosorption capability for D-Phe, and the adsorption isotherm fits Freundlich equation.展开更多
A new ternary complex of nickel(II) with L-aspartate (L-Asp) and 1, 10-phenan- throline(Phen), [Ni3(L-Asp)(Phen)5(H2O)3](ClO4)4?4.75H2O, has been synthesized in a mixed sol- vent of H2OC2H5OH at the pH value of 3. I...A new ternary complex of nickel(II) with L-aspartate (L-Asp) and 1, 10-phenan- throline(Phen), [Ni3(L-Asp)(Phen)5(H2O)3](ClO4)4?4.75H2O, has been synthesized in a mixed sol- vent of H2OC2H5OH at the pH value of 3. It crystallizes in triclinic, space group P1 with a = 11.861(2), b = 18.384(4), c = 19.746(3) ?, α = 107.68(1), β = 105.94(1), γ = 103.41(2)°, V = 3703.6(11) ?3, Mr = 1745.66, Z = 2, Dc =1.565 g/cm3, μ = 0.989 mm-1, F(000) = 1791, R = 0.0643 and wR = 0.1611. The complex contains two cations, binuclear [Ni2(L-Asp)(Phen)3(H2O)]2+ and mononu- clear [Ni(Phen)2(H2O)2]2+. All the nickel ions in the complex are six-coordinated with a distorted octahedral geometry, but the coordination environments for them are different. There exist hydrogen bonds and π-π stacking interactions in the complex.展开更多
The interaction of L-Aspartic acid (Asp) with Vctoria Green S (VGS) in pH 6.0 Britton-Robinson buffer solution has been investigated by UV/Vis spectropbotometry and resonance light scattering (RLS) technique. Th...The interaction of L-Aspartic acid (Asp) with Vctoria Green S (VGS) in pH 6.0 Britton-Robinson buffer solution has been investigated by UV/Vis spectropbotometry and resonance light scattering (RLS) technique. The non-covalent interactions such as hydrogen bond, salt linkage and hydrophobic bond were proposed to explain the interaction between VGS and Asp. It indicated that Asp could link each other to form a long chain by salt linkages and hydrogen bonds in aqueous medium. Then the long chain surrounded the hydrophobic groups of VGS via hydrophobic interaction and reacted with VGS by salt linkages and hydrogen bonds to form a macromolecular aggregation. The aggregation was much bigger than VGS itself. So the color became deeper and the system's absorption and RLS intensity increased. The increase in the absorbance at 617nm was proportional to the concentration of Asp, providing a basis for the quantitative determination of Asp. This method was simple and efficient than the ordinary methods and had been applied to the direct determination of Asp with satisfactory results.展开更多
Molecularly imprinted polymers selective for L-aspartic acid (LAA) have been prepared using the carboxy-betaine polymer bearing zwitterionic centres along the backbone. LAA is well known to promote good me-tabolism, t...Molecularly imprinted polymers selective for L-aspartic acid (LAA) have been prepared using the carboxy-betaine polymer bearing zwitterionic centres along the backbone. LAA is well known to promote good me-tabolism, treat fatigue and depression along with its significance in accurate age estimation in the field of forensic science and is an important constituent of ‘aspartame’, the low calorie sweetener. In order to study the intermolecular interactions in the prepolymerization mixture between the monomer and the template (LAA)/non-template (DAA), a computational approach was developed. It was based on the binding energy of the complex between the template and functional monomer. The results demonstrate that electrostatic in-teractions primarily guide the imprinting protocol. The MIP was able to selectively and specifically take up LAA from aqueous solution, human blood serum and certain pharmaceutical samples quantitatively. Hence, a facile, specific and selective technique to detect the amino acid, LAA in the presence of various interfer-rants, in different kinds of matrices is presented.展开更多
Biodegradable poly(alc-alt-Asp) was synthesized by ring-opening polymerization of the monomer 3-(S)-[(benzyloxycarbonyl)methyl] -morpholine-2, 5-dione and subsequent catalytic hydrogenation. Copolymers of the monomer ...Biodegradable poly(alc-alt-Asp) was synthesized by ring-opening polymerization of the monomer 3-(S)-[(benzyloxycarbonyl)methyl] -morpholine-2, 5-dione and subsequent catalytic hydrogenation. Copolymers of the monomer with glycolide, D,L-lactide and L-lactide were also prepared.展开更多
Polyelectrolyte complex micelles were prepared by self-assembly of polypeptide-based triblock copolymer as a new drug carrier for cancer chemotherapy.The triblock copolymer,poly(L-aspartic acid)-b-poly(ethylene glycol...Polyelectrolyte complex micelles were prepared by self-assembly of polypeptide-based triblock copolymer as a new drug carrier for cancer chemotherapy.The triblock copolymer,poly(L-aspartic acid)-b-poly(ethylene glycol)-b-poly(L-aspartic acid)(PLD-b-PEG-b-PLD),spontaneously self-assembled with doxorubicin(DOX)via electrostatic interactions to form spherical micelles with a particle size of 60e80 nm(triblock ionomer complexes micelles,TBIC micelles).These micelles exhibited a high loading capacity of 70%(w/w)at a drug/polymer ratio of 0.5 at pH 7.0.They showed pH-responsive release patterns,with higher release at acidic pH than at physiological pH.Furthermore,DOX-loaded TBIC micelles exerted less cytotoxicity than free DOX in the A-549 human lung cancer cell line.Confocal microscopy in A-549 cells indicated that DOX-loaded TBIC micelles were transported into lysosomes via endocytosis.These micelles possessed favorable pharmacokinetic characteristics and showed sustained DOX release in rats.Overall,these findings indicate that PLDb-PEG-b-PLD polypeptide micelles are a promising approach for anti-cancer drug delivery.展开更多
Hepatic encephalopathy(HE)is a reversible syndrome of impaired brain function and represents one of the many complications of portal hypertension and decompensated liver disease.Although ammonia is clearly implicated ...Hepatic encephalopathy(HE)is a reversible syndrome of impaired brain function and represents one of the many complications of portal hypertension and decompensated liver disease.Although ammonia is clearly implicated in the pathogenesis of HE,the pathogenesis of HE is multifactorial with numerous mechanisms that results in functional impairment of neuronal cells.The initial management of HE focuses on supportive care and stabilization which includes providing appropriate nutritional support.Thereafter,focus should be on identifying and treating the precipitating factors.There are many therapeutic agents available for the management of HE,most of which are directed towards lowering the gut nitrogen load and thus the serum ammonia level.This review aims to provide an update on the conventional and emerging treatment options for HE.展开更多
L-aspartic acid zinc was synthesized by a rapid and convenient method in high yield under microwave conditions, and its single crystal structure was analyzed by X-ray diffraction. The structure unit of the title compo...L-aspartic acid zinc was synthesized by a rapid and convenient method in high yield under microwave conditions, and its single crystal structure was analyzed by X-ray diffraction. The structure unit of the title compound is [Zn(L-Asp)(H2O)2]·H2O, which is a bicyclo-complex forming a spiral linear polymer via coordination bonds. The spiral linear polymers are assembled as a three-dimensional supramolecule by intermolecular hydrogen bonds. The crystal belongs to the orthorhombic crystal system, P2(1)2(1)2(1) space group, a=0.7830(3) nm, b=0.9369(4) nm, c=11.599(5) nm, α=β=γ=90.00°, V=0.8509(6) nm3, Z=4, Dc=1.955 g/cm3, F(000)=512, μ=2.289. The toxicity of the title compound is lower than that of glutamic acid zinc and zinc sulfate. Keywords L-aspartic acid - zinc - microwave - supramolecule - toxicity展开更多
Aspartate 4-decarboxylase(ASD)has been modified to obtain the catalytic ability of the unnatural substrate l-3-methylaspartate.However,the mechanism remains to be clarified.In the present study,the semi-rational modif...Aspartate 4-decarboxylase(ASD)has been modified to obtain the catalytic ability of the unnatural substrate l-3-methylaspartate.However,the mechanism remains to be clarified.In the present study,the semi-rational modification was used to identify key residues of importance for the activity towards l-3-methylasparte.The ASD from Pseudomonas dacunhae 21192(PdASD)was used as a template,which showed better activity than the other two ASDs.Four residues proved to be critical for the activity towards l-3-methylasparte,with three located in the active site and one on the surface.Combinatorial variants were constructed to analyze the role of each mutation.The enzymatic properties of the combined variants were determined and compared.The residue at the 17th position was a member of the substrate entrance gate and contributed to the activity by reducing the steric hindrance.The residue at the 37th position was necessary for activity.Two mutations,I288 and V382,exhibited strong epistatic interactions on the activity of ASD.Structural changes in the active site were analyzed by molecular dynamics simulations,and it is proposed that the increased activity of PdASD variants is related to a suitable binding pocket for the substrate.These results provide new evidence for the mechanism ofβ-decarboxylation,which lays the foundation for enhancing the activity of ASD.展开更多
L-Aspartateβ-decarboxylase from Acinetobacter radioresistens(ArASD)has been modifed to convert 3-methylaspartic acid into 2-aminobutyric acid,which activated a novel process for biosynthesis of 2-aminobutyric acid.Ho...L-Aspartateβ-decarboxylase from Acinetobacter radioresistens(ArASD)has been modifed to convert 3-methylaspartic acid into 2-aminobutyric acid,which activated a novel process for biosynthesis of 2-aminobutyric acid.However,the process is limited by the low activity of the ArASD.Here,the activity of ArASD was signifcantly improved by modifcation based on sequence alignment and structural analysis.The 38th residue of ArASD is speculated to be the key residue for regulating the conformation of the internal aldimine,and site-directed mutagenesis on R38 residue was carried out.A variant,K18A/R38K/V287I,with 2.2 times higher specifc activity was isolated.Molecular dynamics simulation indicated that the torsion angle of the imine bond of the variant decreased,which was benefcial to the protonation of the internal aldimine and the increase in the initial energy of the enzyme.Therefore,the energy barrier of the transition state was reduced,resulting in improved catalytic activity toward 3-methylaspartic acid.These results provide a reference and a new point of view for enzyme modifcation by increasing the energy of the initial state.展开更多
文摘Aim L-Arginine· L-aspartate, a double salt, has been recently reported toinhibit platelet aggregation and thrombosis, but its action mechanism is not clear yet. This studywas conducted to investigate its effect on FITC-PAC-1, an anti-glycoprotein IIb/IIIa monoclonalantibody binding to activated platelets, and on correlative autacoid levels in plasma or inplatelets in order to explore its potential pathway of inhibiting platelet aggregation andthrombosis. Methods Monoclonal antibody binding to activated platelets was assayed by flowcytometry; NO was assessed by colorimetric method. cAMP, TXB_2 or 6-keto-PGF_(1α) levels wereassessed by radioimmunoassay. Results Gavaged 30 mg·kg^(-1) of L-arginine·L-aspartate increasedboth concentration of NO in plasma and 6-keto-PGF_(1) in incubated supernatant of aortic segment ofrats ex vivo (P < 0.05), but it did not influence cAMP content in platelets and the level of TXB_2or 6-keto-PGF_(1) in plasma of rats, whereas ASA significantly lowered TXB_2 or 6-keto-PGF_(1α) inplasma. Both 100 μmol-L^(-1) of L-arginine ·L-aspartate and ASA inhibited FITC-PAC-1 binding toactivated platelets in vitro. Conclusion The increase in NO and PGI_2 release from endo-thelialcells and consequent inhibition of platelet activation may contribute to the inhibition of plateletaggregation and thrombosis by L-arginine· L-aspartate; whereas arachidonic acid or cAMP metabolicpathway is not closely correlative with the studied effect.
基金Project supported by Shanghai Technology Committee Research Fund (0552nm036)Shanghai Leading Academic Discipline Project (T0402)+1 种基金Shanghai-Unilever Research and Development Fund (200406)Shanghai Education Committee Research Fund (05DZ19)
文摘Five novel ternary complexes of rare earth ions with L-Aspartic acid (Asp) and o-phenanthroline (Phen) were synthesized in ethanol aqueous solution. Their compositions were characterized by elemental analysis, molar conductance, FT-IR, Raman, UV-VIS and TG-DTA. The compositions of the complexes were confirmed to be: RE( Asp)3PhenCl3·3H2O (RE: Ce3+ , Pr3+ , Nd3+ , Sm3+ , Er3+ ). The antibacterial activity test shows that all these complexes exhibit excellent antibacterial ability against Escherichia coli, Staphylococcus aureus and Candida albicans. The antimicrobial spectrum of the complexes are broad.
基金supported by the National Natural Science Foundation of China(No.20875076)the Scientific Initializing Foundation of Northwest University(No.PR09036)+1 种基金the Science Foundation of Northwest University(No.09NW02)the NWU Doctorate Dissertation of Excellence Funds(No.08YYB06).
文摘The electrocatalytic oxidation of dopamine(DA)was studied by electrochemical approaches at a carbon ionic liquid electrode(CILE)modified with the composite film of nafion and L-aspartic acid(NL-CILE).The CILE was fabricated by replacing non-conductive organic binders with a room-temperature hydrophobic ionic liquid,1-butyl-3-methyl-imidazolium hexafluorophosphate.The composite film of NL was used as matrix to adsorb DA and catalyze the oxidation of DA in phosphate buffer solution(PBS).The electrochemical response of DA was investigated at the NL-CILE,the traditional carbon paste electrode(TCPE),CILE and the nafion modified CILE(N-CILE)in 0.1M PBS(pH 7.4),respectively.The results showed the superiority of NL-CILE to N-CILE,CILE and TCPE in terms of provision of higher sensitivity,faster electron transfer and better reversibility.Under optimum condition,the oxidation peak current was rectilinear with DA concentration range from 0.1μM to 0.1mM,with a detection limit of 0.03μM(S/N=3)by differential pulse voltammetry.The proposed method was applied to determine DA in samples successfully.
基金Project(20376085) supported by the National Natural Science Foundation of ChinaProject(05C053) supported by Education Department of Hunan Province, China
文摘L-aspartic acid (Asp) pillared hydrotalcites were prepared by direct reaction of the L-Asp anion with layered double hydroxides (LDHs). The obtained samples were characterized by X-ray diffractometry (XRD), Fourier transform infrared (FTIR), and thermogravimetric and differential thermal analysis (TG/DTA). The results show that the initial interlayer carbonate ions can be completely replaced by the L-Asp anion under the controlled conditions. The pillared hydrotalcites have a crystallized supramolecular structure and thermal stability. The L-Asp pillared LDHs were used in the enantiosorption of enantiopure phenylalanine (Pile), the results suggest that L-Asp pillared LDHs exhibit an excellent enantiosorption capability for D-Phe, and the adsorption isotherm fits Freundlich equation.
基金This work was supported by the Natural Science Foundation of Guangxi Province (No. 9912044)
文摘A new ternary complex of nickel(II) with L-aspartate (L-Asp) and 1, 10-phenan- throline(Phen), [Ni3(L-Asp)(Phen)5(H2O)3](ClO4)4?4.75H2O, has been synthesized in a mixed sol- vent of H2OC2H5OH at the pH value of 3. It crystallizes in triclinic, space group P1 with a = 11.861(2), b = 18.384(4), c = 19.746(3) ?, α = 107.68(1), β = 105.94(1), γ = 103.41(2)°, V = 3703.6(11) ?3, Mr = 1745.66, Z = 2, Dc =1.565 g/cm3, μ = 0.989 mm-1, F(000) = 1791, R = 0.0643 and wR = 0.1611. The complex contains two cations, binuclear [Ni2(L-Asp)(Phen)3(H2O)]2+ and mononu- clear [Ni(Phen)2(H2O)2]2+. All the nickel ions in the complex are six-coordinated with a distorted octahedral geometry, but the coordination environments for them are different. There exist hydrogen bonds and π-π stacking interactions in the complex.
基金Acknowledgements: This work was supported by the Natural Science Foundation of Anhui Province (No. 2006K J128B) and the Young Teacher Natural Science Foundation of Anhui Province Commission (No. 2006jp 1139).
文摘The interaction of L-Aspartic acid (Asp) with Vctoria Green S (VGS) in pH 6.0 Britton-Robinson buffer solution has been investigated by UV/Vis spectropbotometry and resonance light scattering (RLS) technique. The non-covalent interactions such as hydrogen bond, salt linkage and hydrophobic bond were proposed to explain the interaction between VGS and Asp. It indicated that Asp could link each other to form a long chain by salt linkages and hydrogen bonds in aqueous medium. Then the long chain surrounded the hydrophobic groups of VGS via hydrophobic interaction and reacted with VGS by salt linkages and hydrogen bonds to form a macromolecular aggregation. The aggregation was much bigger than VGS itself. So the color became deeper and the system's absorption and RLS intensity increased. The increase in the absorbance at 617nm was proportional to the concentration of Asp, providing a basis for the quantitative determination of Asp. This method was simple and efficient than the ordinary methods and had been applied to the direct determination of Asp with satisfactory results.
文摘Molecularly imprinted polymers selective for L-aspartic acid (LAA) have been prepared using the carboxy-betaine polymer bearing zwitterionic centres along the backbone. LAA is well known to promote good me-tabolism, treat fatigue and depression along with its significance in accurate age estimation in the field of forensic science and is an important constituent of ‘aspartame’, the low calorie sweetener. In order to study the intermolecular interactions in the prepolymerization mixture between the monomer and the template (LAA)/non-template (DAA), a computational approach was developed. It was based on the binding energy of the complex between the template and functional monomer. The results demonstrate that electrostatic in-teractions primarily guide the imprinting protocol. The MIP was able to selectively and specifically take up LAA from aqueous solution, human blood serum and certain pharmaceutical samples quantitatively. Hence, a facile, specific and selective technique to detect the amino acid, LAA in the presence of various interfer-rants, in different kinds of matrices is presented.
文摘Biodegradable poly(alc-alt-Asp) was synthesized by ring-opening polymerization of the monomer 3-(S)-[(benzyloxycarbonyl)methyl] -morpholine-2, 5-dione and subsequent catalytic hydrogenation. Copolymers of the monomer with glycolide, D,L-lactide and L-lactide were also prepared.
基金This research was supported by the National Research Foundation of Korea(NRF)grant funded by the Ministry of Education,Science and Technology(No.2012R1A2A2A02044997 and No.2012R1A1A1039059).
文摘Polyelectrolyte complex micelles were prepared by self-assembly of polypeptide-based triblock copolymer as a new drug carrier for cancer chemotherapy.The triblock copolymer,poly(L-aspartic acid)-b-poly(ethylene glycol)-b-poly(L-aspartic acid)(PLD-b-PEG-b-PLD),spontaneously self-assembled with doxorubicin(DOX)via electrostatic interactions to form spherical micelles with a particle size of 60e80 nm(triblock ionomer complexes micelles,TBIC micelles).These micelles exhibited a high loading capacity of 70%(w/w)at a drug/polymer ratio of 0.5 at pH 7.0.They showed pH-responsive release patterns,with higher release at acidic pH than at physiological pH.Furthermore,DOX-loaded TBIC micelles exerted less cytotoxicity than free DOX in the A-549 human lung cancer cell line.Confocal microscopy in A-549 cells indicated that DOX-loaded TBIC micelles were transported into lysosomes via endocytosis.These micelles possessed favorable pharmacokinetic characteristics and showed sustained DOX release in rats.Overall,these findings indicate that PLDb-PEG-b-PLD polypeptide micelles are a promising approach for anti-cancer drug delivery.
文摘Hepatic encephalopathy(HE)is a reversible syndrome of impaired brain function and represents one of the many complications of portal hypertension and decompensated liver disease.Although ammonia is clearly implicated in the pathogenesis of HE,the pathogenesis of HE is multifactorial with numerous mechanisms that results in functional impairment of neuronal cells.The initial management of HE focuses on supportive care and stabilization which includes providing appropriate nutritional support.Thereafter,focus should be on identifying and treating the precipitating factors.There are many therapeutic agents available for the management of HE,most of which are directed towards lowering the gut nitrogen load and thus the serum ammonia level.This review aims to provide an update on the conventional and emerging treatment options for HE.
基金This work was supported by the National Natural Science Foundation of China(Grant No.20371040)the Foundation of Gansu Province(Grant No.021-23)and the Foundation of Northwest Normal University(Grant No.02-18).
文摘L-aspartic acid zinc was synthesized by a rapid and convenient method in high yield under microwave conditions, and its single crystal structure was analyzed by X-ray diffraction. The structure unit of the title compound is [Zn(L-Asp)(H2O)2]·H2O, which is a bicyclo-complex forming a spiral linear polymer via coordination bonds. The spiral linear polymers are assembled as a three-dimensional supramolecule by intermolecular hydrogen bonds. The crystal belongs to the orthorhombic crystal system, P2(1)2(1)2(1) space group, a=0.7830(3) nm, b=0.9369(4) nm, c=11.599(5) nm, α=β=γ=90.00°, V=0.8509(6) nm3, Z=4, Dc=1.955 g/cm3, F(000)=512, μ=2.289. The toxicity of the title compound is lower than that of glutamic acid zinc and zinc sulfate. Keywords L-aspartic acid - zinc - microwave - supramolecule - toxicity
基金the National Natural Science Foundation of China(21878125).
文摘Aspartate 4-decarboxylase(ASD)has been modified to obtain the catalytic ability of the unnatural substrate l-3-methylaspartate.However,the mechanism remains to be clarified.In the present study,the semi-rational modification was used to identify key residues of importance for the activity towards l-3-methylasparte.The ASD from Pseudomonas dacunhae 21192(PdASD)was used as a template,which showed better activity than the other two ASDs.Four residues proved to be critical for the activity towards l-3-methylasparte,with three located in the active site and one on the surface.Combinatorial variants were constructed to analyze the role of each mutation.The enzymatic properties of the combined variants were determined and compared.The residue at the 17th position was a member of the substrate entrance gate and contributed to the activity by reducing the steric hindrance.The residue at the 37th position was necessary for activity.Two mutations,I288 and V382,exhibited strong epistatic interactions on the activity of ASD.Structural changes in the active site were analyzed by molecular dynamics simulations,and it is proposed that the increased activity of PdASD variants is related to a suitable binding pocket for the substrate.These results provide new evidence for the mechanism ofβ-decarboxylation,which lays the foundation for enhancing the activity of ASD.
基金This work was supported by National Key R&D Program of China(2017YFE0129600)the National Natural Science Foundation of China(21878125)the Priority Academic Program Development of Jiangsu Higher Education Institutions,the 111 Project(No.111-2-06).
文摘L-Aspartateβ-decarboxylase from Acinetobacter radioresistens(ArASD)has been modifed to convert 3-methylaspartic acid into 2-aminobutyric acid,which activated a novel process for biosynthesis of 2-aminobutyric acid.However,the process is limited by the low activity of the ArASD.Here,the activity of ArASD was signifcantly improved by modifcation based on sequence alignment and structural analysis.The 38th residue of ArASD is speculated to be the key residue for regulating the conformation of the internal aldimine,and site-directed mutagenesis on R38 residue was carried out.A variant,K18A/R38K/V287I,with 2.2 times higher specifc activity was isolated.Molecular dynamics simulation indicated that the torsion angle of the imine bond of the variant decreased,which was benefcial to the protonation of the internal aldimine and the increase in the initial energy of the enzyme.Therefore,the energy barrier of the transition state was reduced,resulting in improved catalytic activity toward 3-methylaspartic acid.These results provide a reference and a new point of view for enzyme modifcation by increasing the energy of the initial state.