In this paper, 1-tosyl-3-hydroxyl-1,5,8-triazacyclodecane (2) was prepared in optimized conditions. The structure of title compound 2 was established on the basis of spectroscopic data. The binding of compounds 2, 3, 4 to DNA was investigated with melting temperature measurements and molecular-modeling calculations. The results showed that the introduction of hydroxyl and tosyl groups into triazacyclicamines may enhance the interaction between the compound 2 and DNA. The free macrocyclic ligand 2 could catalyze cleavage supercoiled pBR322 DNA to the nicked and the linear form at the same time at near neutral conditions and 37 degrees C without any metal ions aid. In addition, compound 2 showed selectively inhibition to lung cancer cells. Thus, this leading compound might be useful as artificial restriction enzymes and may be usefully applied in the development of anti-tumor drug.

Schiff bases were synthesized from salicylaldehyde and m-phenyldiamine,o-amino-p-methylphenol,o-aminobenzylalcohol and o-aminoanisole,respectively.The reaction condition carried out in the solution with pH from 7 to 8,and the solvent was anhydrous ethanol.The favorable conditions of synthesizing the Schiff bases were found after a series of experiments,and the Schiff bases were characterized by elemental analysis, UV,IR,()~1H NMR and()~(13)C NMR.

Two intermediates and four new Schiff bases were synthesized. The two intermediates were prepared from vanillin and 1-burylbromide or 2-chloroacetic acid, respectively. Condensation of 3-methoxy- 4-butoxybenzaldehyde with 2-amino-4-methylphenol or 2-aminophenylmethanol and 3-methoxy-4-carboxy- methylbenzaldehyde with aminoacetic acid or 2-amino-4-methylphenol gave the four Schiff bases. All of the compounds were characterized by element analysis, UV, IR, 1H NMR and 13C NMR. Copyright CJI.

NMR technique is undertaken to study the chiral recognition between mandelic acid and chiral dioxocyclen synthesized by ourselves. Different chemical shifts are shown in the 1 HNMR. From the NMR results, the methine of madelic acid gives the biggest chemical shift while mixed with chiral dioxocyclen comparing with other complexes formed by host-guest molecules with different molar ratio. It reveals that the mandelic and dioxocyclen form a supramolecular complex with chemical equivalent 1∶1.The chiral dioxocyclen shows discriminated supramolecular abilities to madelic acid and may be used as chiral selector in resolution.

Several acyclic and macrocyclic polyamines were evaluated for their ability to cleave DNA. 1,7-Dimethyl-1,4,7,10-tetraazacyclododecane (DMC) could hydrolyze double-strand DNA at a concentration of 25microM. pH 7.2 was the optimal condition to cleave DNA in the presence of DMC. Supercoiled DNA hydrolytic cleavage by DMC was supported by the evidence from free radical quenching and T4 ligase ligation.

Chiral recognition,an important and special recognition,is the basic model of molecular recognition in the bio-system and chemical research.The choice and application of chiral selectors are the key factors to the success in the chiral recognition and resolution.Some important kinds of chiral selectors and their characteristics were reviewed,including cyclodextrin,polysaccharides,protein,antibiotics and synthesized chiral macrocycles.

In the presence of anhydrous potash,N,N′,N″-tri(isopropyl)-1,4,7-triazacyclononane was obtained by using 1,4,7-triazacyclononane and 2-bromo-propane as starting material.Compared with literature method,the new method was simple and gave high yield.

A novel macrocyclic molecule, cucurbit[7]uril (CB[7]) was for the first time employed as an additive in capillary electrophoresis (CE). In similarity to other macrocyclic molecules, such as crown ethers, cyclodextrins (CDs) and calixarenes, CB[7] can form inclusion complexes with a variety of guest molecules due to its inner cavity. Thus, it can be used like other macrocyclic molecules to manipulate selectivities in CE. During the running process, CB[7] bears a positive charge under the studied pH range (pH 2.5–7) and can be adsorbed onto the inner wall of a fused‐silica capillary, leading to a reversal of the electroosmotic flow (EOF). Electrophoretic behaviors of nitrotoluene, nitrophenol, nitroaniline, and methylaniline isomers were studied under various conditions. The electrophoretic separations of the isomers can be accomplished with a buffer containing CB[7]. Furthermore, a probable separation mechanism in the presence of CB[7] was also proposed.

Three methods were employed to synthesize title compound 3,13-dihydroxyl-1,5,8,11,15,18-hexaazacyclicamines (5). A detailed study of the preparation of [2+2] condensation product 5 was made by means of the reaction of 1, 3-dichloro-2-propanol (1) with N-tosyl diethylenetriamine (2). The reported synthesis procedure is simple and convenient, and the yield was raised. The product was easily isolated and purified.

Three novel macrocyclic polyamines and an unexpected macrocycle have been synthesized by the one-step condensation of diethylenetriamine ( or triethylenetetraamine) with formaldehyde and rigid diphenylglycoluril. The X-ray crystal structure of the unexpected macrocycle is provided.

The first supramolecular adduct (H3O)2[Cu(H2O)4](SO4)2·2(C30H30N20O10)·24(H2O) based on cucurbit[5]uril was synthesized and characterized by single crystal X-ray diffraction analysis. In the adduct, copper ion is coordinated by four oxygen atoms from H2O. The latter links two cucurbit[5]uril molecules due to a complicated hydrogen bonding containing lattice water molecules.

1 H-NMR spectroscopic analysis indicates that cucurbit[7]uril can form a stable inclusion complex with 1,6-hexanediamine, while cucurbit[5]uril cannot form pseudorotaxane with 1,6-hexanediamine under our experimental conditions. This was confirmed by the crystal structure of the complex. The cavity of cucurbit[8]uril seems to be large for binding 1,6-hexanediamine efficiently. And a simple, mild, high-yield (>80%) method has been described for the synthesis of rotaxanes through the self-assembly of pseudorotaxanes of cucurbit[ n ]uril ( n =6, 7)/1, 6-hexanediamine and sodium tetraphenylborate. The obtained rotaxanes are held intact solely by noncovalent interactions, and are characterized by elemental analysis, 1 H-NMR, ESI-MS and MALDI-TOF MS.

用核磁共振氢谱和紫外-可见光谱滴定法考察了葫[n]环联脲(Cucurbit[n]uril, n=5,6,7,8)与对甲苯重氮氟硼酸盐和4,4′-联苯二重氮氟硼酸盐的配位情况, 并用曲线拟合求得形成的包结配合物的稳定常数.结果表明, 不同空腔的葫[n]环联脲对不同尺寸的重氮氟硼酸盐具有很显著的选择性包结作用.在相同条件下, 与葫[6]环联脲相比, 葫[7]环联脲更易于容纳苯环.同时, 随着酸性的增强, 葫[n]环联脲上的脲羰基质子化程度加大, 使得其配位能力有所减弱.

The interaction between plasmid DNA (pBR322 DNA) and Ni (II), Ca (II), Co (II), Cu(II) coordination systems of 3-hydroxyl-1,5,8-triaazacyclic amine (L1) and 3,13-dihydroxyl-1,5,8, 11, 15, 18-hexaazacyclic amine (L2) with several molar ratios were investigated by agarose gel electrophoresis. The results suggested that M-L1, M-L2 and 2M-L2 systems could catalyze the cleavage of supercoiled pBR322 DNA to the nicked and the linear form at the same time under near neutral conditions at 37 degreesC. The efficiency of DNA cleavage decreased in the order 2M-L2>M-L2, because there was probably cooperativity between two metal ions in 2M-L2 systems which catalyzed the cleavage of DNA. The little cleavage was found under a comparable conditions by the metal ions or receptor alone. The antitumor activities of two receptors, metal ions and their metal coordination systems were all measured against BEL-7402 cell lines by using MTT assay. The metal ions have cytotoxicity to cells at 10(-3) mol/L; but when it was diluted to 10(-4) mol/L, the percentage inhibition decreased sharply. On the contrary, the metal coordination systems still kept their antitumor activities even at 10(-5) mol/L. Thus, these coordination systems may be useful as artificial restriction enzymes and may be usefully applied to the development of antitumor drug.

甘脲分子具有刚性的凹形结构、四个易于取代的NH基团以及两个可以形成氢键的脲羰基,因而使之被广泛地用作为分子和超分子主体的构筑单元.许多不同形状的含甘脲结构单元的主体分子表现了对客体分子具有特异的选择性,葫环联脲(cucurbit[n]urils)就是这类主体分子中引起广泛关注的主体之一.

Four pyrazoles and their new heterocyclic acylamide derivatives, which are 3,5-dimethylpyrazole (1), 5-methyl-3-phenylpyrazole (2), 3,5-diphenylpyrazole (3), 5-methyl-3-ferrocenylpyrazole (4), 2,6-bis(3,5-dimethylpyrazolyl-1-carbonyl)pyridine (5), 2,6-bis(5-methyl-3-phenylpyrazolyl-1-carbonyl)pyridine (6), 2,6-bis(3,5-diphenylpyrazolyl-1-carbonyl) pyridine (7) and 2,6-bis(5-methyl-3-ferrocenylpyrazolyl-1-carbonyl) pyridine (8), have been synthesized, and characterized by elemental analysis, Fr-IR, H-1 NMR and C-13 NMR Spectra.

A novel supramolecular adduct [(H3O)2 (PtCl6)]3 (C42H42N28O14)2·H2O (1) was synthesized by mixing [PtCl6]2− and cucurbit [7] uril in solution of hydrochloric acid. The crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to orthorhombic system and space group F dd2 with cell dimensions:a=4. 705 33 (5) nm,b=7. 153 80 (6) nm,c=1. 894 61 (2) nm,Z=16,V=63, 7744 (11) nm3,D c =1.534 g/cm3, μ=3. 007 mm−1,F(000)=29 120,R 1=0.070 7,wR 2=0. 169 2. In crystal, the cucurb [7] uril molecules from two zig-zag chains.