The use of cooperative vibronic spectroscopy to measure coordination numbers of the ligands surrounding rare earth ions in solutions was proposed and demonstrated. It is shown that the time-resolved cooperative vibron...The use of cooperative vibronic spectroscopy to measure coordination numbers of the ligands surrounding rare earth ions in solutions was proposed and demonstrated. It is shown that the time-resolved cooperative vibronic spectroscopy is a very useful technique for the determination of the ligand type and ligand number for different coordination groups. Coordination configuration of arginine with Tb3+ in solutions with different pH values was studied. It demonstrates that the carboxy1 of arginine can replace H2O to coordinate with Tb3+ and the coordination number of carboxyl increases with the increase of pH value of the solutions.展开更多
Nine C2-symmetric chiral disulfonamldes were designed and synthesized from L-valine, L-phenylalanine and L-leucine respectively via one-pot ring opening of aziridines. The application of these disulfonamides as cataly...Nine C2-symmetric chiral disulfonamldes were designed and synthesized from L-valine, L-phenylalanine and L-leucine respectively via one-pot ring opening of aziridines. The application of these disulfonamides as catalyst in the addition of diethyl zinc to benzaldehyde in three reagent systems: Ligand-Ti(OiPr)4-Et2Zn; Ligand-Ti(OiPr)4-H2O-Et2Zn; Ligand-Et2Zn was also described.展开更多
We suggest a mathematical route which has the capability to obtain quantitative information of solid residues on a substrate of aluminum, in which the evaporation of the deposited micro-drops has the form of coffee ri...We suggest a mathematical route which has the capability to obtain quantitative information of solid residues on a substrate of aluminum, in which the evaporation of the deposited micro-drops has the form of coffee rings. In this job, the glycine aminoacid was used as probe molecule. We suppose that the number of moles present on the study sample is proportional to the Raman signal and to the experimental parameters of the used Raman system. Then, the mass and the number of molecules can be determined with these data. We showed that the mathematical expression is simple and elegant for its implementation. On the other hand, we have applied and demonstrated that the technique of principal component analysis (PCA) can be used to obtain quantitative information of the sample. Our results show quantitative analysis of glycine residues between 10-11 to 10-15 g.展开更多
The title complex of [(Yb(Pro)2(H2O)5Cl3]n has been synthesized. Its IR spectrum from 4000 to 400 cm-1 has been measured and the possible structure of the complex was proposed. The molecular and crystal structure has ...The title complex of [(Yb(Pro)2(H2O)5Cl3]n has been synthesized. Its IR spectrum from 4000 to 400 cm-1 has been measured and the possible structure of the complex was proposed. The molecular and crystal structure has been determined by four-circle X-ray diffractometer. The crystal is monoclinic with space group P21. The unit cell parameters are as follows: a=0.8268(l) nm, b=1.0980(3) nm, c =1.1965(4) nm, β=106.97(2)°, V=1.04120(5) nm3, z=2. Positicnal and anisotropic thermal parameters have been corrected by least sqare method and the final deviation R is 0.0812. The prolines exist in two forms in the complex. One form of proline serves as bridging group connecting neighboring Yb atoms, so that the complex form a one-dimensional chain of infinitive length. Another form of proline coordinates with Yb atom through one oxygen atom of the carboxyl group. In addition there are five water moleculers coordinating to each Yb atoms. The coordination number of Yb is eight, forming a distorted trigonal-dodecahedral arrangement. The three Cl-anions are in the neighbourhood of NH+2 cations.展开更多
Binary and ternary complexes of Cd(II) involving pyrazine 2,3-dicarboxylic acid (pzdca) and various biologically relevant ligands containing different functional groups are investigated at 25 ℃, I = 0.10 M (NaNO...Binary and ternary complexes of Cd(II) involving pyrazine 2,3-dicarboxylic acid (pzdca) and various biologically relevant ligands containing different functional groups are investigated at 25 ℃, I = 0.10 M (NaNO3) and in 20% (v/v) ethanol-water media. The ligands (L) used are amino acids, dicarboxylic acids and peptides. The results showed the formation of Cd (pzdca) (L) complexes with amino acids and dicarboxylic acids. Peptides form both Cd (pzdca) (L) complexes and the corresponding deprotonated amide species Cd (pzdca) (LH-1). The relative stabilities of ternary complexes are compared with those of the corresponding binary complexes in terms of AlogK values. The concentration distribution of the complexes in solution was evaluated.展开更多
AIM To study the effects of electro acupuncture (EA) on 5 HT, NOS, NO and gastric mucosa in stress rats. METHODS By biochemical methods, the changes of 5 HT and NOS in gastric mucosa, NO and 5 HT in serum were ...AIM To study the effects of electro acupuncture (EA) on 5 HT, NOS, NO and gastric mucosa in stress rats. METHODS By biochemical methods, the changes of 5 HT and NOS in gastric mucosa, NO and 5 HT in serum were ana_ lysed and the gastric mucosa was examined pathohistologically in stress rats with gastric mucosa damage after EA. The changes before and after stress by EA were compared. RESULTS EA decreased gastric mucosa damage index in the stress rats (2 71±0 40 to 1 86±0 69, P <0 01). EA normalized NOS level in gastric mucosa to the control group. The changes before stress by EA was more obvious than the EA after stress; EA lowered the 5 HT contents of gastric mucosa (μg/g wet weight, 6 91±3 08 to 4 51±1 62, P <0 01). EA recovered the NO level in serum of the stress rats (μmol/L, 5 78±1 49 to 7 91±1 11, P <0 05), and increased the contents of 5 HT and 5 HIAA in serum continuously. CONCLUSION EA stimulation normalizes the NOS and NO levels in gastric mucosa in stress rats, lowers the high 5 HT contents and induces NO releases.展开更多
The crystal structure of gadolinium L-proline (Pro) complex [Gd2-(C5H9NO2)6 (H2O)6] (ClO4)6 has been determined. The complex crystallizes in the triclinic space group PI with following crystal data: a = 9. 906(3), b=1...The crystal structure of gadolinium L-proline (Pro) complex [Gd2-(C5H9NO2)6 (H2O)6] (ClO4)6 has been determined. The complex crystallizes in the triclinic space group PI with following crystal data: a = 9. 906(3), b=13. 052(5), c = 13.703(5) A. α=109. 63(3), β=110.31(2), γ=100. 73(3)°, V=1470.3(9) A3.Mr=1710. 1, F(000) = 854,μ=26. 30 cm-1, Dc = 1. 931 g/cm3, Z=1.The structure was refined to the final R of 0. 048 for 3804 reflections. The structure is of one-dimensional chain, in which each gadolinium ion lies at the center of a distorted square antiprism of the eight oxygen atoms provided by four bridging carboxylate groups from four Pro ligands, a terminal carboxylate group from one terminal Pro ligand and three water molecules and the two neighbouring gadolinium ions are linked to each other through the two bridging carboxylate groups from the two Pro ligands. The prolines exist in the form of H2 CCH2CH2(+NH2)CHCOO-, and the complexions in the crystal are linked together by the net of hydrogen bonds between theClO4- , NH2+ and the coordinated water molecules.展开更多
INTRODUCTIONAmino acid consumption test (AACT) has a highsensitivity and specificity in evaluating exocrinepancreatic insufficiency,but its diagnostic valueto exocrine pancreatic insufficiency in Chinese hasnot been w...INTRODUCTIONAmino acid consumption test (AACT) has a highsensitivity and specificity in evaluating exocrinepancreatic insufficiency,but its diagnostic valueto exocrine pancreatic insufficiency in Chinese hasnot been well understood.In this study,the oralreagent stimulating pancreatic secretion (O-AACT)was used instead of cerulein(I-AACT) for amidoacid consumption test and the dignostic efficiency ofO-AACT was evaluated and compared with I-AACTon the exocrine pancreatic insufficiency in Chinese.展开更多
The compositions of two kinds of ants (Formica cunicu Laria and Polyrhachis vicina Roger) were determined with modern apparatuses. The result was that content of crude protein, fat, vitamin E, formic acid were 43.95%,...The compositions of two kinds of ants (Formica cunicu Laria and Polyrhachis vicina Roger) were determined with modern apparatuses. The result was that content of crude protein, fat, vitamin E, formic acid were 43.95%, 22.90%, 15.61 mg / Kg, 4.2% respectively forFormica cunicu Laria, and 42.56%, 21 .90%, 131 .2 mg / Kg, 3.8% respectively for Polyrhachlk vicina Roger.展开更多
High-resolution terahertz absorption and Raman spectra of glutamine in the frequency region 0.2 THz-2.8 THz are obtained by using THz time domain spectroscopy and low-frequency Raman spectroscopy. Based on the experim...High-resolution terahertz absorption and Raman spectra of glutamine in the frequency region 0.2 THz-2.8 THz are obtained by using THz time domain spectroscopy and low-frequency Raman spectroscopy. Based on the experimental and the computational results, the vibration modes corresponding to the terahertz absorption and Raman scatting peaks are assigned and further verified by the theoretical calculations. Spectral investigation of the periodic structure of glutamine based on the sophisticated hybrid density functional B3LYP indicates that the vibrational modes come mainly from the inter-molecular hydrogen bond in this frequency region.展开更多
Designing and stereoselectively constructing chiral mechanically interlocked molecules(MIMs)is a goal that many chemists are pursuing due to their potential in the development of functional molecular machines involved...Designing and stereoselectively constructing chiral mechanically interlocked molecules(MIMs)is a goal that many chemists are pursuing due to their potential in the development of functional molecular machines involved in catalysis,sensing,and chiroptical switching.However,the synthesis of enantiopure supramolecular entities with crystallographic structures remains challenging.Herein,the stereoselective self-assembly of chiral metalla[2]catenanes interlocked by two D-shaped macrocycles was realized by combining long binuclear half-sandwich organometallic Cp*Rh^(III)(Cp*=η^(5)-pentamethylcyclopentadienyl)clip and ditopic monodentate ligand incorporating L-leucine residues.The resulting metalla[2]catenane displayed unique co-conformational mechanical helical chirality characteristics arising from the chirality transfer of the chiral ligand.Furthermore,decreasing the length of the binuclear Cp*Rh^(III)clip and adjusting the steric hindrance of the amino-acid side chains(L-alanine and L-phenylalanine)in the ligands resulted in two lemniscular macrocycles with left-handed(M)-twisted conformational chirality.To the best of our knowledge,the synthesized macrocycles are the first family of homochiral abnormal lemniscate-shaped organometallic macrocycles featuring figure-eight geometries.Metalla[2]catenanes and macrocycles with opposite chirality were also generated by employing corresponding D-amino acid ligands,as evidenced by single-crystal X-ray diffraction,nuclear magnetic resonance,mass,and circular dichroism spectroscopies.Our present study demonstrates that homochiral MIMs can be accessed readily using amino acid–containing ligands through rational molecular design.展开更多
A series of succinate-derived macrocyclic amides 1 were synthezized using ring-closing metathesis in the key step. The substrate scope includes rings of 11 to 14 members. The cyclic dicarboxylic acids 1 represent a fa...A series of succinate-derived macrocyclic amides 1 were synthezized using ring-closing metathesis in the key step. The substrate scope includes rings of 11 to 14 members. The cyclic dicarboxylic acids 1 represent a family of new model compounds for potential zinc metalloprotease inhibitors. The metathesis precursors were provided by amide coupling of tert-butyl 3-carboxyhex-5-enoate 2 with numerous side chain alkenylated amino acid esters of general type 3 derived from L-tyrosine and L-cysteine.展开更多
Awide spectrum of Androgen insensitivity syndrome (AIS) occur due to mutations in the androgen receptor(AR). The clinical presentation of AIS ranges from a typically male phenotype with decreased body hair and/ or...Awide spectrum of Androgen insensitivity syndrome (AIS) occur due to mutations in the androgen receptor(AR). The clinical presentation of AIS ranges from a typically male phenotype with decreased body hair and/ or oligospermia to a typically female phenotype with primary amenorrhea and without pubic and axillary hair;展开更多
基金the Natural Science Foundation of Guangdong Province!980278, 960036the National Natural Science Foundation of China!29705004
文摘The use of cooperative vibronic spectroscopy to measure coordination numbers of the ligands surrounding rare earth ions in solutions was proposed and demonstrated. It is shown that the time-resolved cooperative vibronic spectroscopy is a very useful technique for the determination of the ligand type and ligand number for different coordination groups. Coordination configuration of arginine with Tb3+ in solutions with different pH values was studied. It demonstrates that the carboxy1 of arginine can replace H2O to coordinate with Tb3+ and the coordination number of carboxyl increases with the increase of pH value of the solutions.
文摘Nine C2-symmetric chiral disulfonamldes were designed and synthesized from L-valine, L-phenylalanine and L-leucine respectively via one-pot ring opening of aziridines. The application of these disulfonamides as catalyst in the addition of diethyl zinc to benzaldehyde in three reagent systems: Ligand-Ti(OiPr)4-Et2Zn; Ligand-Ti(OiPr)4-H2O-Et2Zn; Ligand-Et2Zn was also described.
文摘We suggest a mathematical route which has the capability to obtain quantitative information of solid residues on a substrate of aluminum, in which the evaporation of the deposited micro-drops has the form of coffee rings. In this job, the glycine aminoacid was used as probe molecule. We suppose that the number of moles present on the study sample is proportional to the Raman signal and to the experimental parameters of the used Raman system. Then, the mass and the number of molecules can be determined with these data. We showed that the mathematical expression is simple and elegant for its implementation. On the other hand, we have applied and demonstrated that the technique of principal component analysis (PCA) can be used to obtain quantitative information of the sample. Our results show quantitative analysis of glycine residues between 10-11 to 10-15 g.
文摘The title complex of [(Yb(Pro)2(H2O)5Cl3]n has been synthesized. Its IR spectrum from 4000 to 400 cm-1 has been measured and the possible structure of the complex was proposed. The molecular and crystal structure has been determined by four-circle X-ray diffractometer. The crystal is monoclinic with space group P21. The unit cell parameters are as follows: a=0.8268(l) nm, b=1.0980(3) nm, c =1.1965(4) nm, β=106.97(2)°, V=1.04120(5) nm3, z=2. Positicnal and anisotropic thermal parameters have been corrected by least sqare method and the final deviation R is 0.0812. The prolines exist in two forms in the complex. One form of proline serves as bridging group connecting neighboring Yb atoms, so that the complex form a one-dimensional chain of infinitive length. Another form of proline coordinates with Yb atom through one oxygen atom of the carboxyl group. In addition there are five water moleculers coordinating to each Yb atoms. The coordination number of Yb is eight, forming a distorted trigonal-dodecahedral arrangement. The three Cl-anions are in the neighbourhood of NH+2 cations.
文摘Binary and ternary complexes of Cd(II) involving pyrazine 2,3-dicarboxylic acid (pzdca) and various biologically relevant ligands containing different functional groups are investigated at 25 ℃, I = 0.10 M (NaNO3) and in 20% (v/v) ethanol-water media. The ligands (L) used are amino acids, dicarboxylic acids and peptides. The results showed the formation of Cd (pzdca) (L) complexes with amino acids and dicarboxylic acids. Peptides form both Cd (pzdca) (L) complexes and the corresponding deprotonated amide species Cd (pzdca) (LH-1). The relative stabilities of ternary complexes are compared with those of the corresponding binary complexes in terms of AlogK values. The concentration distribution of the complexes in solution was evaluated.
文摘AIM To study the effects of electro acupuncture (EA) on 5 HT, NOS, NO and gastric mucosa in stress rats. METHODS By biochemical methods, the changes of 5 HT and NOS in gastric mucosa, NO and 5 HT in serum were ana_ lysed and the gastric mucosa was examined pathohistologically in stress rats with gastric mucosa damage after EA. The changes before and after stress by EA were compared. RESULTS EA decreased gastric mucosa damage index in the stress rats (2 71±0 40 to 1 86±0 69, P <0 01). EA normalized NOS level in gastric mucosa to the control group. The changes before stress by EA was more obvious than the EA after stress; EA lowered the 5 HT contents of gastric mucosa (μg/g wet weight, 6 91±3 08 to 4 51±1 62, P <0 01). EA recovered the NO level in serum of the stress rats (μmol/L, 5 78±1 49 to 7 91±1 11, P <0 05), and increased the contents of 5 HT and 5 HIAA in serum continuously. CONCLUSION EA stimulation normalizes the NOS and NO levels in gastric mucosa in stress rats, lowers the high 5 HT contents and induces NO releases.
文摘The crystal structure of gadolinium L-proline (Pro) complex [Gd2-(C5H9NO2)6 (H2O)6] (ClO4)6 has been determined. The complex crystallizes in the triclinic space group PI with following crystal data: a = 9. 906(3), b=13. 052(5), c = 13.703(5) A. α=109. 63(3), β=110.31(2), γ=100. 73(3)°, V=1470.3(9) A3.Mr=1710. 1, F(000) = 854,μ=26. 30 cm-1, Dc = 1. 931 g/cm3, Z=1.The structure was refined to the final R of 0. 048 for 3804 reflections. The structure is of one-dimensional chain, in which each gadolinium ion lies at the center of a distorted square antiprism of the eight oxygen atoms provided by four bridging carboxylate groups from four Pro ligands, a terminal carboxylate group from one terminal Pro ligand and three water molecules and the two neighbouring gadolinium ions are linked to each other through the two bridging carboxylate groups from the two Pro ligands. The prolines exist in the form of H2 CCH2CH2(+NH2)CHCOO-, and the complexions in the crystal are linked together by the net of hydrogen bonds between theClO4- , NH2+ and the coordinated water molecules.
基金the Science Fund of Department of Health,Sichuan Province,No.9241-920054
文摘INTRODUCTIONAmino acid consumption test (AACT) has a highsensitivity and specificity in evaluating exocrinepancreatic insufficiency,but its diagnostic valueto exocrine pancreatic insufficiency in Chinese hasnot been well understood.In this study,the oralreagent stimulating pancreatic secretion (O-AACT)was used instead of cerulein(I-AACT) for amidoacid consumption test and the dignostic efficiency ofO-AACT was evaluated and compared with I-AACTon the exocrine pancreatic insufficiency in Chinese.
文摘The compositions of two kinds of ants (Formica cunicu Laria and Polyrhachis vicina Roger) were determined with modern apparatuses. The result was that content of crude protein, fat, vitamin E, formic acid were 43.95%, 22.90%, 15.61 mg / Kg, 4.2% respectively forFormica cunicu Laria, and 42.56%, 21 .90%, 131 .2 mg / Kg, 3.8% respectively for Polyrhachlk vicina Roger.
基金supported by the National Basic Research Program of China (Grant No. 2007CB310408)the Beijing Natural Science Foundation of China (Grant No. KZ201110028035)
文摘High-resolution terahertz absorption and Raman spectra of glutamine in the frequency region 0.2 THz-2.8 THz are obtained by using THz time domain spectroscopy and low-frequency Raman spectroscopy. Based on the experimental and the computational results, the vibration modes corresponding to the terahertz absorption and Raman scatting peaks are assigned and further verified by the theoretical calculations. Spectral investigation of the periodic structure of glutamine based on the sophisticated hybrid density functional B3LYP indicates that the vibrational modes come mainly from the inter-molecular hydrogen bond in this frequency region.
基金the National Science Foundation of China(grant nos.22031003 and 21720102004)the Shanghai Science Technology Committee,China(grant no.19DZ2270100)the Shanghai Post-doctoral Excellence Program,China(grant no.2022009).
文摘Designing and stereoselectively constructing chiral mechanically interlocked molecules(MIMs)is a goal that many chemists are pursuing due to their potential in the development of functional molecular machines involved in catalysis,sensing,and chiroptical switching.However,the synthesis of enantiopure supramolecular entities with crystallographic structures remains challenging.Herein,the stereoselective self-assembly of chiral metalla[2]catenanes interlocked by two D-shaped macrocycles was realized by combining long binuclear half-sandwich organometallic Cp*Rh^(III)(Cp*=η^(5)-pentamethylcyclopentadienyl)clip and ditopic monodentate ligand incorporating L-leucine residues.The resulting metalla[2]catenane displayed unique co-conformational mechanical helical chirality characteristics arising from the chirality transfer of the chiral ligand.Furthermore,decreasing the length of the binuclear Cp*Rh^(III)clip and adjusting the steric hindrance of the amino-acid side chains(L-alanine and L-phenylalanine)in the ligands resulted in two lemniscular macrocycles with left-handed(M)-twisted conformational chirality.To the best of our knowledge,the synthesized macrocycles are the first family of homochiral abnormal lemniscate-shaped organometallic macrocycles featuring figure-eight geometries.Metalla[2]catenanes and macrocycles with opposite chirality were also generated by employing corresponding D-amino acid ligands,as evidenced by single-crystal X-ray diffraction,nuclear magnetic resonance,mass,and circular dichroism spectroscopies.Our present study demonstrates that homochiral MIMs can be accessed readily using amino acid–containing ligands through rational molecular design.
文摘A series of succinate-derived macrocyclic amides 1 were synthezized using ring-closing metathesis in the key step. The substrate scope includes rings of 11 to 14 members. The cyclic dicarboxylic acids 1 represent a family of new model compounds for potential zinc metalloprotease inhibitors. The metathesis precursors were provided by amide coupling of tert-butyl 3-carboxyhex-5-enoate 2 with numerous side chain alkenylated amino acid esters of general type 3 derived from L-tyrosine and L-cysteine.
文摘Awide spectrum of Androgen insensitivity syndrome (AIS) occur due to mutations in the androgen receptor(AR). The clinical presentation of AIS ranges from a typically male phenotype with decreased body hair and/ or oligospermia to a typically female phenotype with primary amenorrhea and without pubic and axillary hair;