ZHONG Shi-an; HUANG Ke-long; LEI Qi-fu; XIANG Hai-yan
A molecularly imprinting polymer (MIP) was synthesized via bulk polymerization under different conditions using anti-ague drug cinchonine (CN) as template. Infrared spectra (IR) results show that the template CNand functional monomer α-methyl acrylic acid (MAA) formed complexes before polymerization and the structure of complexes was simulated by Hyperchem. The results indicate that there are hydrogen bond or ionic bond between functional monomer and template molecule in acetonitrile solution. The MIP made in cold-initiated photo-polymerization has higher separation performance than that in the therm-initiated polymerization. The separation of the isomers CN and cinchonidine (CD) can be successfully obtained when its separate factor α reaches 1.82. Scatchard analysis suggests that the MIP recognizing CN with two classes of binding sites. The partition coefficient Kd, 1 and apparent maximum number nmax, 1 of binding sites with high affinity are 131.43 μmol/L and 58. 90 μmol/g, respectively,while Kd, 2 and nmax, 2 of binding sites with low affinity are 2.32 mmol/L and 169.08 mmol/g, respectively.
Wesełucha-Birczyńska, A.; Oleksyn, B. J.; Śliwiński, J.; Goslar, J.; Hilczer, W.; Hoffmann, S. K.
The crystal structure of (C 19H 24N 2O 2+) 2(CdCl 4) 2-(Cd 0.5Cu 0.5Cl 4) 2- has been determined by X-ray diffraction at 295 K. The compound crystallises in orthorhombic P2 12 12 1 space group with unit cell parameters: a=12.7381(10), b=13.5394(10), c=25.6520(10) Å, and Z=4. Packing of molecules in the unit cell is determined by single and bifurcated hydrogen bonds between cinchoninium cation, (cinchonineH 2) 2+, CuCl42- and CdCl42- tetrahedral anions. Specific feature of the packing is a partial stacking of the quinoline rings of adjacent cinchoninium cations. There are eight sites for M=Cd or Cu in the crystal unit cell. In the four of them the CdCl 4 tetrahedra are located. In the others Cd or Cu can be located and an average geometry (Cd/CuCl 4) is described by the X-ray diffraction data. EPR allows to observe only the CuCl 4 complexes and we have proved that there is not a random distribution of individual Cd and Cu among the (Cd/CuCl 4) sites but they are coupled in dimers, so that asymmetric unit can be identified as (cinchonineH 2·MeCl 4) 2 moiety. Specific feature of the structure is that CuCl 4 tetrahedra are relatively weakly deformed from ideal tetrahedral geometry Td towards the D2 d symmetry (flattening angle 123.3°) and have relatively long Cu-Cl bonds (2.338 Å) at 295 K. Reflectance optical absorption band at 8700 cm -1 with a shoulder at 6200 cm -1 are assigned to ( x2- y2)→( z2) and ( x2- y2)→( xy) transitions, and they follow the well-known relationship between band positions and geometry of tetrachlorocuprates. EPR shows that the exchange coupling between Cu 2+ ions is very weak and an individual CuCl 4 gives separate lines in EPR spectrum. The spectrum below 200 K is characterised with parameters gx=2.047, gy=2.127, and gz=2.404 and above this temperature becomes dynamically averaged to g∥=2.299 and g⊥=2.065. This continuous type transition to the dynamic phase, without a thermal effect, is accompanied by the change in the crystal
Carroll, Anne-Marie; Kavanagh, David J.; McGovern, Fiona P.; Reilly, Joe W.; Walsh, John J.
Nature is a well-recognized source of compounds of interest, but access is often an issue. One pertinent example is the cinchona alkaloids from the bark of "Cinchona calisaya." In this experiment, students at the third-year undergraduate level undertake the selective isolation and characterization of two of the four main alkaloids present in the…
Jakubec, Pavol; Farley, Alistair J M
Summary The enantio- and diastereoselective Michael addition of a δ-valerolactone-derived pronucleophile to a substituted furanyl nitroolefin catalysed by a bifunctional cinchonine-derived thiourea has been used as the key stereocontrolling step in a new synthetic strategy to the heavily functionalised piperidine core of keramaphidin B. PMID:27340496
ZHANGZhengpu; HUANGJinxia; 等
In this paper,two kinds of PS-PTCs were synthesized using different methods by introducing cinchonine and quinine to the polymer support.Their catalytic properties for the alkylation of N-diphenylmethylene glycine t-butyl ester were also compared.
An efficient synthesis of cinchona alkaloid-derived ligands based on solvent-free microwave-assisted reaction was described. The coupling of 1,4-dichlorophthalazine or 3,6-dichloropyridazine with quinine, cinchonine or cinchonidine provide bis- or mono-cinchona alkaloid-derived ligands in moderate to good yields (52-89%) within 15 rain under optimum microwave conditions.
Yilmaz, Ali; Nyberg, Nils; Jaroszewski, Jerzy W.
of the well-known cinchona alkaloids quinine, cinchonine and cinchonidine without any apparent clustering. Signals from analogues were detected but not in substantial amounts. The main variation was related to the absolute amounts of extracted alkaloids, which was attributed to the evolution of the Cinchona...
Rapid and Green Analytical Method for the Determination of Quinoline Alkaloids from Cinchona succirubra Based on Microwave-Integrated Extraction and Leaching (MIEL Prior to High Performance Liquid Chromatography
Full Text Available Quinas contains several compounds, such as quinoline alkaloids, principally quinine, quinidine, cinchonine and cichonidine. Identified from barks of Cinchona, quinine is still commonly used to treat human malaria. Microwave-Integrated Extraction and Leaching (MIEL is proposed for the extraction of quinoline alkaloids from bark of Cinchona succirubra. The process is performed in four steps, which ensures complete, rapid and accurate extraction of the samples. Optimal conditions for extraction were obtained using a response surface methodology reached from a central composite design. The MIEL extraction has been compared with a conventional technique soxhlet extraction. The extracts of quinoline alkaloids from C. succirubra obtained by these two different methods were compared by HPLC. The extracts obtained by MIEL in 32 min were quantitatively (yield and qualitatively (quinine, quinidine, cinchonine, cinchonidine similar to those obtained by conventional Soxhlet extraction in 3 hours. MIEL is a green technology that serves as a good alternative for the extraction of Cinchona alkaloids.
Full Text Available 527], Cinchonine [CPD:C06528], Cinchonidine [CPD:C11379], Tannin, , Quinate [CPD:C00296] Cinchona succirubra...D07153 Crude, Drug Cinchona bark; Cinchona Quinine [CPD:C06526], Quinidine [CPD:C06..., Cinchona [TAX:43462], Rubiaceae [TAX:24966] Same as: E00257 Therapeutic category: 5100 Rubiaceae (madder f...amily) Cinchona bark Major component: Quinine [CPD:C06526] Therapeutic category of dru...gs in Japan [BR:br08301] 5 Crude drugs and Chinese medicine formulations 51 Crude drugs 510 Crude drugs 5100 Crude drugs D07153 Cinchona bark PubChem: 51091492 ...
Hansen, Frederik André; Hansen, Steen Honoré; Petersen, Nickolaj J.
the composition of alkaloids in Cinchona bark. One common problem for sheatless interfaces for CE-MS has been establishing a stable electric contact at the end of the separation capillary that does not induce band broadening or affect the spray stability. In our device the electric contact is generated through....... Furthermore, the increased conductivity of the buffer in the fracture generates field free pumping of the analytes towards the ESI spray tip. In this study the device was used to analyze the four major alkaloids (diastereomeric pairs of quinine/quinidine and cinchonine/cinchonidine) in Cinchona bark samples...
The optical α-amino acids were synthesized under room temperature by alkylation of N-(diphenyl methylene) glycine t-butyl ester under polymer-supported phase transfer conditions using polymer-supported cinchonine (or quinine) alkaloids as chiral phase transfer catalysts and dichloromethane as solvent, followed by hydrolysis of the above intermediates introduced to the final products-optical α-amino acids. This is a new method for the asymmetric synthesis of α-amino acids. The influences of catalyst,temperature, substrates, and organic solvents on the chemical yield and optical purities of products were studied.
Hahn, Konstanze R; Seitsonen, Ari P; Baiker, Alfons
The cinchona alkaloids cinchonidine and cinchonine belong to the most efficient chiral modifiers for the noble metal-catalyzed enantioselective hydrogenation of C=O and C=C bonds. Under reaction conditions these modifiers are coadsorbed on the noble metal surface with hydrogen. Using density functional theory, we studied the effect of coadsorbed hydrogen on the adsorption mode of cinchonidine and cinchonine on a Pt(111) surface at different hydrogen coverages. The theoretical study indicates that the presence of coadsorbed hydrogen affects both the adsorption geometry as well as the stability of the adsorbed cinchona alkaloids. At all hydrogen coverages the cinchona alkaloids are found to be adsorbed via anchoring of the quinoline moiety. In the absence of hydrogen as well as at low hydrogen coverage the quinoline moiety adsorbs nearly parallel to the surface, whereas at higher hydrogen coverage it becomes tilted. Higher hydrogen coverage as well as partial hydrogenation of the quinoline part of the cinchona alkaloid and hydrogen transfer to the C[double bond, length as m-dash]C double bond at 10, 11 position of the quinuclidine moiety destabilize the adsorbed cinchona alkaloid, whereas hydrogen transfer to the nitrogen atom of the quinoline and the quinuclidine moiety stabilizes the adsorbed molecule. The stability as well as the adsorption geometry of the cinchona alkaloids are affected by the coadsorbed hydrogen and are proposed to influence the efficiency of the enantiodifferentiating ability of the chirally modified platinum surface.
Liu, Yu; Li, Li; Zhang, Heng-Yi; Fan, Zhi; Guan, Xu-Dong
The inclusion complexation behavior of chiral members of cinchona alkaloid with beta- and gamma-cyclodextrins (1 and 2) and 6,6(')-trimethylenediseleno-bridged bis(beta-cyclodextrin) (3) was assessed by means of fluorescence and 2D-NMR spectroscopy. The spectrofluorometric titrations have been performed in aqueous buffer solution (pH 7.20) at 25.0 degrees C to determine the stability constants of the inclusion complexation of 1-3 with guest molecules (i.e., cinchonine, cinchonidine, quinine, and quinidine) in order to quantitatively investigate the molecular selective binding ability. The stability constants of the resulting complexes of 2 with guest molecules are larger than that of 1. As a result of cooperative binding, the stability constants of inclusion complexation of dimeric beta-cyclodextrin 3 with cinchonidine and cinchonine are higher than that of parent 1 by factor of 4.5 and 2.4, respectively. These results are discussed from the viewpoint of the size-fit and geometric complementary relationship between the host and guest.
Hisaki, Ichiro; Hiraishi, Eri; Sasaki, Toshiyuki; Orita, Hideo; Tsuzuki, Seiji; Tohnai, Norimitsu; Miyata, Mikiji
Quinine, one of Cinchona alkaloids, has been of great interest from medical, synthetic, and supramolecular viewpoints. However, unaccountably, the guest-free (GF) crystal of quinine containing no solvent or other molecules has not been reported for nearly three decades, although GF crystals of other Cinchona alkaloids, such as quinidine, cinchonidine, and cinchonine, are already known. In this study, we successfully revealed the crystal structure of quinine, which belongs to the P2(1) space group with the cell parameters of a=6.0587(1), b=19.2492(5), c=22.2824(7) Å, β=92.1646(11)°, and V=2596.83(12) Å(3). Interestingly, the crystal has three crystallographically independent molecules in the cell (Z'=3) that are connected through a N(quinoline)⋅⋅⋅H-O hydrogen bond to form a pseudo three-two-fold (3(2)) double-helical motif. The helical motif is completely different from those observed in GF crystals of other Cinchona alkaloids. Hierarchical comparison on the crystal structures of a series of Cinchona alkaloids including quinine clearly demonstrated that only small structural differences of a molecule, particularly the position of the vinyl group, cause a significant variety of assembly manner in the crystalline state. There have been no reports systematically demonstrating such steric effect in crystals of Cinchona alkaloids, and, therefore, the present system contributes to the design of desired functional crystal structures.
Zajoncová, L; Frébort, I; Luhová, L; Sebela, M; Galuszka, P; Pec, P
Kinetic properties of novel amine oxidase isolated from sainfoin (Onobrychis viciifolia) were compared to those of typical plant amine oxidase (EC 18.104.22.168) from lentil (Lens culinaris). The amine oxidase from sainfoin was active toward substrates, such as 1,5-diaminopentane (cadaverine) with K(m) of 0.09 mM and 1,4-diaminobutane (putrescine) with K(m) of 0.24 mM. The maximum rate of oxidation for cadaverine at saturating concentration was 2.7 fold higher than that of putrescine. The amine oxidase from lentil had the maximum rate for putrescine comparable to the rate of sainfoin amine oxidase with the same substrate. Both amine oxidases, like other plant Cu-amine oxidases, were inhibited by substrate analogs (1,5-diamino-3-pentanone, 1,4-diamino-2-butanone and aminoguanidine), Cu2+ chelating agents (diethyltriamine, 1,10-phenanthroline, 8-hydroxyquinoline, 2,2'-bipyridyl, imidazole, sodium cyanide and sodium azide), some alkaloids (L-lobeline and cinchonine), some lathyrogens (beta-aminopropionitrile and aminoacetonitrile) and other inhibitors (benzamide oxime, acetone oxime, hydroxylamine and pargyline). Tested by Ouchterlony's double diffusion in agarose gel, polyclonal antibodies against the amine oxidase from sainfoin, pea and grass pea cross-reacted with amine oxidases from several other Fabaceae and from barley (Hordeum vulgare) of Poaceae, while amine oxidase from the filamentous fungus Aspergillus niger did not cross-react at all. However, using Western blotting after SDS-PAGE with rabbit polyclonal antibodies against the amine oxidase from Aspergillus niger, some degree of similarity of plant amine oxidases from sainfoin, pea, field pea, grass pea, fenugreek, common melilot, white sweetclover and Vicia panonica with the A. niger amine oxidase was confirmed. PMID:10092944
许卓; 于健; 马建学
试样经碱熔分解，水提取，铁、锰、铺、镍元素量氢氧化物沉淀与钨、钼分离。在0．34moL／L硫酸-2g／L苯羟乙酸-24g／L氯酸钠-0．08g／L辛兜宁体系中，钨和锢均能产生灵敏的极谱催化波，峰电位约为-0．70V和-0．07V（对饱和日‘汞电极）。方法检出限为WO．29蚓g、Mo0．26μg／g，精密度（RSD，n=12）为W1．21％-10．1％、Mo2.7％～12．4％，准确度（RE，n=12）为W-3．7％-2．33％、Mo-4．79％～3．17％。适用于化探样品中钨钿厄索的连续测定。%The sample was melted with potassium hydroxide and extracted with water. Tungsten and molybdenum were separated from iron, manganese, cobalt and nickel with their hydroxides. In 0.34 moL/L sulfuric acid-2 g/L hydroxyphenylacetic acid-24 g/L sodium chlorate -0.08 g/L cinchonine system, tungsten and molybdenum were produced sensitive polarographic catalytic waves with peak potentials (with a saturated calomel electrode) at -0.70 V and-0.07 V, respectively. The detection limit of tungsten and molybdenum were 0.29/ag/g and 0.26μg/g, respectively. The RSD (n=12) of method were 1.21%-10.1% for W, 2.7 %~12.4 % for Mo. The RE (n=12) of method were -3.7 %-2.33 % for W,-4.79 %-3.17% for Mo. The method has been applied to the continuous determination of tungsten and molybdenum in geochemical exploration samples.