Inclusion Complexes of Gossypol with 2-Pentanone, 3-Pentanone,and 2-Hexanone

Inclusion complexes of gossypol with 2-pentanone, 3-pentanone, and 2-hexanone were prepared by crystallization from the corresponding ketone and hexane, and their structures were determined by low-temperature X-ray diffraction. All three compounds crystallize in monoclinic systems and have a 2:1 gossypol-to-solvent molar ratio. Both gossypol–pentanone complexes crystallize in C2/c space groups, and the solvent cavities in these structures have C₂ symmetry. The 3-pentanone molecule, which has C₂ symmetry, sits symmetrically within the cavity, while the 2-pentanone molecule, which lacks C₂ symmetry, takes two equally probable orientations within the cavity. Both structures are similar to previously reported gossypol inclusion complexes formed with small esters and 3-hexanone. The distal positioning of the carbonyl group in 2-hexanone does not allow it to fit into the same solvent cavity that exists in the pentanone structures. In the gossypol-2-hexanone complex, the solvent cages are skewed, and the C₂ site symmetry is lost. As a result, the structure crystallizes in a Cc space group and has a larger asymmetric unit and unit cell. Although the 2-hexanone structure retains many of the features of the gossypol–pentanone complexes, this is the first report of a gossypol inclusion compound with this extended structure.This revised version was published online in July 2005 with a corrected issue number.     

X-Ray Crystal Structure of Four Inclusion Complexes of the Novel Host Gossindane: An Oxidation Product of Gossypol

Gossindane, the oxidation product of gossypol, demonstrates inclusion properties towards four solvents chosen accidentally. The crystal data of these complexes with ethanol (I), ethylacetate (II), dichloromethane (III) and water (IV) are: (I): C26H30O6· 2C2H5OH, monoclinic, P2/c, a = 8.687(2) Å, b = 10.986(3) Å, c = 14.778(3) Å = 110.94° V = 1317 Å3, Z = 2, R = 0.069, N = 1368; (II): C26H30O6· 0.5C4H8O2, monoclinic, P21/c, a = 8.960(2) Å, b = 21.937(5) Å, c = 14.712(3) Å, = 111.98(2)°, V = 2681 Å3, Z = 4, R = 0.083, N = 2653; (III): C26H30O6· CH2Cl2, monoclinic, P21/c, a = 8.886(2) Å, b = 21.778(6) Å, c = 14.996(4) Å, = 111.31(3)°, V = 2704 Å3, Z = 4, R = 0.131, N = 1580; (IV): C26H30O6·2H2O, monoclinic, C2/c, a = 29.422(9) Å, b = 6.720(2) Å, c = 27.525(9) Å, = 117.43(2)°, V = 4830 Å3, Z = 8. R = 0.096, N = 2240.In the solvates H-bonded host molecules form bilayers with very similar structures and a nearly hydrophobic surface. Guest molecules are placed in channels formed between these bilayers and may be H- bonded to host molecules (ethanol). In the hydrate two water molecules using their H-bonding capacity incorporate gossindane molecules into bilayers.     

Inclusion Complexes of Coenzyme Q10 with Polyamine‐Modified β‐Cyclodextrins: Characterization,Solubilization, and Inclusion Mode

The inclusion‐complexation behavior of coenzyme Q10 (CoQ10) with the three polyamine‐modified β‐cyclodextrins (CDs) 1 – 3 was investigated in both solution and the solid state by means of NMR, XRD, and FT‐IR spectroscopy. The results showed that the apparent solubility of CoQ10 increased linearly upon addition of hosts 1 – 3 , giving A_L‐type phase‐solubility curves. These hosts 1 – 3 were able to solubilize CoQ10 to high levels, up to 1.35, 1.52, and 1.44 mg/ml (calculated as CoQ10), respectively. The host 2 with a moderate‐length chain is the most suitable for inclusion complexation of CoQ10. Accroding to the ROESY experiments, the MeO groups of CoQ10 and the tether of 2 can be co‐included into the cavity of β‐CD through the induced‐fit interaction between host and guest. The binding ability of modified β‐CDs 1 – 3 upon complexation with CoQ10 are discussed from the viewpoints of the size/shape‐matching relationship and the induced‐fit concept between host CDs and guest CoQ10 molecule.     

Structure and Kinetics of Desolvation of 2-Hexanone Inclusion Compounds of the Hexapedal Hosts, Hexakis(3-hydroxy-3,3-diphenyl-2-propynyl)benzene and 1,2,3,5,6,7-Hexakis(3-hydroxy-3,3-diphenyl-2-propynyl)naphthalene

The 2-hexanone inclusion compounds of hexakis(3-hydroxy-3,3-diphenyl-2-propynyl)benzene and 1,2,3,5,6,7-hexakis(3-hydroxy-3,3-diphenyl-2-propynyl)naphthalene have been prepared and characterised by single crystal X-ray diffraction and thermal analysis. The kinetic parameters and mechanisms for the desolvation reaction have also been determined for both compounds.     

Studies on the Intramolecular Inclusion Complexes of Functionalized Calixarenes with CH_3X (X=CN, NO_2)

ＩｎｔｒｏｄｕｃｔｉｏｎＯｎｅｏｆｔｈｅｍｏｓｔａｔｔｒａｃｔｉｖｅｆｅａｔｕｒｅｓｏｆｃａｌｉｘ[4]ａｒｅｎｅｓｉｓｔｈｅｉｒｃｕｐｌｉｋｅｓｔｒｕｃｔｕｒｅ ,ｗｈｉｃｈｗａｓｏｂｓｅｒｖｅｄｂｏｔｈｉｎｓｏｌ ｉｄｓｔａｔｅａｎｄｉｎｓｏｌｕｔｉｏｎ .Ｔｈｅｃａｖｉｔｙｄｅｆｉｎｅｄｂｙｔｈｅｃｏｎｅｃｏｎｆｏｒｍｅｒｏｆｔｈｉｓｍａｃｒｏｃｙｃｌｅｗａｓｅｘｔｅｎｓｉｖｅｌｙｅｍｐｌｏｙｅｄａｓａｂｉｎｄｉｎｇｓｉｔｅｆｏｒｔｈｅｒｅｃｏｇｎｉｔｉｏｎｏｆｎｅｕｔｒａｌｇｕｅｓｔｓｈａｖｉｎ…     

γ-环糊精对二甲戊灵的包合作用

以γ-环糊精(γ-CD)为主体, 采用饱和水溶液法对客体二甲戊灵进行包合. 采用紫外光谱以等摩尔连续变化法确定包合物的包合比为1∶1; 红外光谱证明二甲戊灵的部分苯环结构可能进入了γ-CD的空腔; 热分析结果证明包合作用提升了二甲戊灵的熔点; 粉末X射线衍射谱图中新衍射峰的出现说明形成了新物相; 扫描电镜则直观展现了包合物的外观. 以上结果均表明形成了γ-CD-二甲戊灵包合物, 其包合平衡常数K=1123.99 L/mol. 包合作用使二甲戊灵的熔点从54 ℃升至75 ℃, 溶解度提高了约11.5倍, 包合物热贮稳定性达标, 为进一步将其加工成其它水基化农药剂型提供了可能.     

包结法拆分1,1'-联-2-萘酚:包结物的晶体结构及CD光谱

以D/L-缬氨醇为原料,通过二步反应得到价廉易得的拆分剂碘化(R)/(S)-N,N,N-三甲基-1-羟基-3-甲基-2-丁铵,采用包结拆分法,成功实现了对1,1′-联-2-萘酚(BINOL)的拆分.对具有(R)-构型的季铵盐与(R)-BINOL在甲醇中所形成包结物的晶体结构分析结果表明:I-离子桥联主体(拆分剂)的醇羟基和客体(BINOL)的酚羟基形成O-H…I-氢键,以及相邻层的主客体分子之间的C-H…O氢键相互作用是在包结物中实现手性识别的关键.同时对两个包结物的溶液和固体圆二色(CD)光谱进行了研究.     

Synthesis,Spectral, Characterization,and Anticancer Activity of Some Binary and Mixed Ligand Complexes of 4-Methyl-2-Pentanone Thiosemicarbazone and Some Amino Acids

The Schiff base ligand 4-methyl-2-pentanone thiosemicarbazone (MPTSC) (HL) has been synthesized by the interaction of 4-methyl-2-pentanone (MP) and thiosemicarbazone (TSC). The Ni(II), Cu(II), and Fe(III) binary complexes of this ligand have been prepared. The ternary complexes of VO(IV) and Mn(II) ions with HL and glutamine (Glu) as a secondary ligand, in addition to VO(IV), Mn(II), and La(III) with HL and glycine (Gly) as a secondary ligand, have also been synthesized. The binary and ternary complexes have been characterized based on elemental analysis, IR, UV-VIS, molar conductance, mass spectra, magnetic moment, and ESR measurements. The magnetic moment, UV, and ESR studies suggest that Ni(II) and Cu(II) complexes are square planar, whereas Fe(III), Mn(II), and La(III) complexes have octahedral geometry, but VO(IV) ternary complexes have square pyramidal geometry. The analytical data indicate that the metal-to-ligand ratio in binary complexes is 1:1, except HL-Cu(II) chloride complex where the metal-to-ligand to secondary ligand ratio in ternary complexes is 1:1:1. The anticancer studies showed that the anticancer activity is in the decreasing order: ternary complexes > binary complexes > free ligand (HL).

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Study of Inclusion Complexes of Cyclodextrins with Orange II

Inclusion reactions of - and -CD with Orange IIwere measured by means of a stopped-flow method and UV-spectra. The forward rate constants (k₊), backward rateconstants (k_-) and the equilibrium constants (K) for the inclusion reactions were determined. Theinclusion processes of CD with Orange II follow a one-step reaction mechanism. The value of the forward rate constantat neutral and alkaline conditions for Orange II binding to -CD cavity was large. This suggests that thenaphthalene side is partially included in the final complex form. In the case of -CD, only marginal differenceis shown.It is probable that inclusion covers the whole naphthalene group and part of the azo group as well,resulting ina small effect from the pH variation. The results show that the equilibrium constant at pH 7 for the binding ofOrange II to -CD is the largest because the included part of Orange II matches the cavity of -CD well.     

Inclusion Complexes of Cyclodextrins with 4-Amino-1,8-Naphthalimides

The formation of inclusion complexes between 4-amino-1,8-naphthalimides and cyclodextrins (CDs) was investigated. The naphthalimides used in the study were 4-amino-1,8-naphthalimide (I) and4-(2-phosphonoethylamino)-N-(2-phosphonoethyl)-1,8-naphthalimide,tetraethylester (II). The CDs employed were -CD, -CD, -CD, HP--CD, HP--CD andHP--CD (HP = hydroxypropyl). Evidence for complex formation was obtained from the changes in the fluorescence spectra of the dyes in the presence of increasing amounts of the CDs. The most striking changes were observed with HP--CD and HP--CD. Treatment of the data using Benesi–Hildebrand plotswas consistent with a 1:1 inclusion model. The determined stabilityconstants were (K_eq, M^-1): 106 (I:HP--CD, pH = 2.0), 193 (I:HP--CD, pH = 7.0), 113 (I:HP--CD, pH = 7.0), 155(II:HP--CD, pH = 2.0), 121 (II:HP--CD,pH = 7.0), 301 (II:HP--CD, pH = 7.0). It can beconcluded that compound I forms a more stable complex with HP--CD than with HP--CD. Compound II, on the other hand, forms a more stable complex with HP--CD than with HP--CD.     

聚合β-环糊精包结二甲酚橙修饰碳糊铬(Ⅵ)电极的研制和应用

1 引言 用环糊精包结物作电化学传感器的敏感物质报道很少.本文研究了交联β-环糊精对二甲酚橙的包结能力,并用制备的包结物对碳糊电极进行修饰,制成了一种电位型铬化学传感器,在相应活化液中活化后,对?&有灵敏线性响应.响应斜率为23.83/p Cr(Ⅵ),线性范围为1.0×10-1～1.0×10-6 mol/L,响应时间为40 s～2 min,检出限为6.31×10-7 mol/L铬(Ⅵ).电极具有性能稳定、使用寿命长、重现性好的优点,用于样品中铬(Ⅵ)的测定,回收率符合分析要求.     

A Convenient Synthesis of 5-Bromo-2-Pentanone

During a series of studies aimed at the total synthesis of pentacyclic triterpenes¹ we have examined the reaction of enollactones of type 1 with a variety of Grignard reagents. ^1c,2 In one of our problems we required the organometallic reagent 2a derived from the title compound 2b. A previous literature report for the preparation of this compound involved the reaction of α-acetylbutyrolactone 3 with aqueous HBr followed by steam distillation.³ In our hands the yields of 2b via this route were non-reproducible and at best, less than 15%.     

Formation of Inclusion Complexes between Cyclodextrins and Carbaryl and Characterization of the Complexes

The solubility of carbaryl increased with increasing concentrations of-CD, G₂--CD, and M--CD. The result suggests theformation of soluble inclusion complex. Solubility increase was highestin M--CD-carbaryl, being 18.4 fold higher than that of carbaryl when 100 mM M--CD was used. The apparent formation constant for the complex calculated from phase solubility diagram was 223.18 M^-1. The preparation of the complex in solid form for characterization was successful by kneading andfreeze-drying. The DSC curves for kneading and freeze-drying mixture didnot show the endothermic peak characteristic of carbaryl, but a small new endothermic peak was observed. FTIR analysis showed a shift of the major peak of carbonyl group in carbaryl molecule from 1717 to 1744 and 1734 cm^-1 in kneading and freeze-dried mixtures, respectively. M--CD-carbaryl complex demonstrated higher dissolution rate, higher thermal and UV stability but lower toxicity than its parent carbaryl compound.     

Inclusion Complexes of Cyproterone Acetate with Cyclodextrins in Aqueous Solution

Cyproterone acetate (CPA) is a steroidal antiandrogen with a progestogenic activity. Given that this molecule has a very poor water solubility (2.1 g/mL), different cyclodextrins (CDs) were tested to form inclusion complexes and to increase solubility. Two different techniques were compared to study the affinity between CPA and CDs: phase-solubility studies and NMR spectroscopy. The stoichiometry and the stability constant could be determined for most complexes with the aid of phase-solubility studies. The greatest increase in solubility was achieved with the methylated -CDs, but hydroxypropylated - and -CDs also gave enhanced solubilities. ¹H-NMR studies showed a solubility increase similar to that found with phase-solubility studies. The proof of inclusion in the2,6-dimethyl--CD (DIMEB) was shown by ¹H-NMR and t-ROESY spectra.     

环糊精包结物的制备与研究方法

环糊精是由6,7,8个葡萄糖基构成的环状化合物,分别叫做α,β,γ-CD。它们具有亲水的外围及疏水的内腔,可与多种物质形成包结物,而改变物质的特性,因而被广泛应用于各行各类,为了更好地研究环糊精包结物,在查阅大量文献的基础上,总结出环糊精包结物的多种制备方法及研究方法。     

Preparation and Properties of Inclusion Compounds of Cyclodextrins with Organotransition Metal Complexes

Inclusion compounds of transition metal complexes of cycloocta-1,5-diene (cod) and norbornadiene (nbd) with cyclodextrins were prepared. Two-to-one (cyclodextrin:guest) inclusion compounds were obtained in high yields by the treatment of β-cyclodextrin (β-CD) with [(L)RhCl]₂ (L = nbd or cod) and 1:1 inclusion compounds were obtained by the reaction of β-CD with (cod)PtX₂ (X = Cl, Br, or I) in high yields, while γ-CD formed 1:1 inclusion compounds with (cod)PtX₂ (X = Br or I). The formation of inclusion compounds is selective. α-CD did not form inclusion compounds with any transition-metal complexes with cycloocta-1,5-diene. Thermogravimetric measurements show that the complexes are stabilized by inclusion in cyclodextrin cavities. The inclusion compounds were characterized by ¹ H-NMR, IR, UV, and circular dichroism spectra.     

Studies on the Intramolecular Inclusion Complexes of Functionalized Calix[4]arenes with CH3X (X = CN,NO2)

Two functionalized calix[4]arenes in cone conformation L_2–3 have been synthesized and their intramolecular inclusion complexes (1:1) with organic neutral molecules CH₃CN and CH₃NO₂ have been prepared and characterized, respectively. The X‐ray crystallographic analysis shows that L₂ in L₂·CH₃CN. C₂H₅OH has C₄ symmestry and L₃ in L₃.CH₃NO₂ exhibits C₂ symmestry. The CH‐π aromatic interactions between the CH group of the guest and the phenyl rings of the calix backbond have been proved to be able to stabilize the intramolecular inclusion complexes formed. The interaction is directional, but it is independent of the acidity of the guest. To gain information on CH‐s interactions, suitable geometrical parameters have been calculated from the crystal data of intramolecular inclusion complexes. The results show that L₃.CH₃NO₂ with L₃ in C₂ symmestry can also be bound stably in the intramolecular inclusion complex, being consistent with the thermal analysis. The geometrical parameters and the results of the thermal analysis of L₁.CH₃CN and L₁.CH₃NO₂ were also given and discussed.     

环糊精与乙烯和三十烷醇包结物的研究

本文报道在常压下制备了α-环糊精-乙烯包结物的微细晶体,和环糊精与三十烷醇的溶胶与粉末包结物,以增加长链烷基醇的溶解度。其溶胶在室温下放置半年不凝聚。还用X-射线粉未衍射法、1~H核磁共振及差热-热重分析等方法研究了包结物的形成。