Journal of Inclusion Phenomena and Macrocyclic Chemistry最新文献

In this study, based on BODIPY molecule, new calix-like structures with significant electrical and optical properties were designed. These calix-like compounds containing BODIPY seems to be highly probable and appear to be thermodynamically stable. After structural optimization, absence of imaginary frequencies and the values of cohesive energies were studied which two important evidences about their stability were obtained. Decreasing the values of E_g and improvement of optical properties as the result of enlarging the oligomers size is considerable result. Between designed structures the calix[8]BODIPY is have smallest value of E_g and is more optically active molecule which has intense absorptions in visible region of light. Two separate computational methods were used to confirm the accuracy of the obtained data. Finally, it was shown that by increasing the number of BODIPY units in calix[n]BODIPY structure, the strength of hydrogen bond in the lower rims of it increase. Although the designed compounds have not yet been synthesized, they are highly probable due to the high stability of the compounds containing BODIPY and appear to be good synthetic chemical targets.

Schiff base imine condensations are a useful tool for macrocycle synthesis and applications within supramolecular chemistry. Here we address the mixtures of products that can arise from template free synthesis using dicarbonylheterocycles and diamines, and look to develop metal-free template methods for selective macrocycle formation. A range of alkyl α,ω-diamines were combined with phenanthroline and pyridine heterocyclic dicarbaldehydes under standard literature conditions. The reaction conditions were modified to demonstrate a relationship between choice of solvent and product equilibria. It was observed that benzene and toluene could shift a mixture of products and unreacted starting materials to form predominantly one imine product for a number of systems. Once the macrocyclic products had been characterized in selected solvents, iodinated halogen bonding guest molecules were added to direct macrocycle assemblies using non-covalent interactions. Studies to investigate host – guest suitability and halogen bond interactions were conducted, and it was found that tetraiodoethylene had an influence on the formation of a phenanthroline based macrocycle. Proof of concept experiments were performed to show the influence of the guest molecule, tetraiodoethylene, on the macrocyclic products formed under competitive dynamic combinatorial chemistry conditions.

In this work, a new macrocyclic cadmium complex, [Cd(ACE)I]₂[CdI₄] (1); ACE: 1,3,6,10,12,15-hexaazatricyclo[13.3.1.1^6,10]eicosane, was prepared by template method and characterized by elemental analysis, FT-IR spectroscopy and single-crystal X-ray diffraction. Structural analysis of the complex 1 revealed an ionic complex containing two cadmium atoms with tetrahedral (in anionic portion) and square-pyramidal (in cationic portion) geometries. Using the DFT calculations, thermodynamic stability of the first-row and group 12 metal complexes containing ACE ligand was investigated and then validated by comparing with the CSD analogues. Charge distribution pattern of ACE ligand was compared with cationic unit of 1 by NBO analysis to study of the charge variation of ligand after complexation.

Graphical abstract

Cancer is one of the leading causes of death worldwide, and the limited success of currently used anticancer drugs is a driving force for the search for new compounds with anticancer potential. Calixarenes make up a fascinating class of macrocycles that find a wide range of biological applications in supramolecular chemistry. Especially in recent years, the anticancer activity of various calixarene derivatives has been reported by many researchers. The aim of this review article is to find relatively simple, efficient, and synthetic methods for the preparation of macrocyclic compounds containing various pharmacophoric groups to produce new and effective anticancer materials in cancer research and to investigate the usability of calixarene-based supramolecular in cancer research.

The crystal structures are reported for 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-6,17-dione, (C₁₂H₂₂N₂O₆), (I), dibenzo[e,q][1,4,10,13,7,16] tetraoxadiazacyclooctadecine-6,13-dione, (C₂₀H₂₂N₂O₆), (II) and 1,4-dioxa-10,13-dithia-7,16-diazacyclooctadecane-8,15-dione, (C₁₂H₂₂N₂O₄S₂), (III). Solid-state structures show different types of hydrogen bonding for all three structures. In I, there are two intermolecular hydrogen bonds between an amide and carbonyl [N–H···O = 2.8206(11) Å and 2.8637(11) Å] and two intermolecular hydrogen bonds between an amide and ether [N–H···O = 2.9570(11) Å and 3.0067(11) Å]. There are two intramolecular hydrogen bonds between amide and ether oxygens [N–H···O = 2.589(3) Å and 2.623(4) Å] in II. Molecule III has a mixture of intramolecular hydrogen bonds between an amide and thioether [N–H···S = 3.0501(18) Å] and intermolecular hydrogen bonds between an amide and carbonyl [N–H···O = 2.835(2) Å].

Calixarene derivatives are excellent host compounds for ionic species in liquid–liquid extraction. However, many studies using calixarene derivatives have been conducted using highly toxic chloroform as a solvent because of their poor solubility in typical hydrocarbons. In the present study, aromatic ethers were developed as solvents for calixarene derivatives to enhance their industrial applicability. The solubility of the calix[6]arene carboxylic acid derivative ^tOct[6]CH₂COOH in 1-octoxybenzene (OB) and 1-butoxybenzene (BB) was 11.3 mM and 24.9 mM, respectively. The cationic guest molecule tryptophan methyl ester was extracted using the ^tOct[6]CH₂COOH host in OB and BB. The cationic lysine-rich protein cytochrome c was also extracted using ^tOct[6]CH₂COOH in BB as shown for ^tOct[6]CH₂COOH in chloroform in previous studies. However, cytochrome c was not extracted using ^tOct[6]CH₂COOH in OB and instead, precipitated. As ^tOct[6]CH₂COOH stabilizes the ammonium group of biomolecules because of its suitable cavity size, the extraction of the tryptophan ester and cytochrome c using ^tOct[6]CH₂COOH was much higher than those using the corresponding calix[4]arene and calix[8]arene derivatives. These results confirm that aromatic ethers are potential solvents for calixarene derivatives for the extraction of biomolecules.

This review introduces the synthesis, properties and applications of Co^IIIcorroles. The synthesis methods are containing A₂B type, A₃ type, ABC type, Hangman H₃corrole and H₃biscorrole synthesis and their metal-inserting reactions. Also, the spectroscopic and electrochemical properties of Co^IIIcorroles were also described. However, the most important part of this paper is about the application of Co^IIIcorroles, including the development of sustainable and pollution-free chemical energy sources, the degradation of environmentally harmful organochlorides, and the oxidation of alkanes.

Facing the dual pressure of increasing global energy demand and heavy task in carbon emission reduction on schedule, nuclear renaissance is being seriously discussed as transitive choice before full renewable energy supply, yet there is a crucial concern about radioactive safety. The treatment of radioactive iodine is particularly important and challenging because of its high ratio in fission product, extremely long radioactive periods up to several millions of years, as well as easy diffusion in the whole ecosystem. Given that several challenge including easy sublimation, high water solubility, diverse existing species of I₂, I⁻, I_2n+1⁻ and organic iodine, biocompatibility and strong aggregation in thyroid, rapid capture and permanent storage of iodine is requested. Comparing to inorganic adsorbents of zeolite and inorganic–organic hybrid MOFs, pure organic porous solid are emerging as new and promising iodine capture material. Their high iodine affinity and adsorption capacity, good stability in various environments, facile modification and functionalization, intrinsic structural flexibility guaranteed the outstanding performance in iodine capture. Four main categories of organic cages, supramolecular framework connected by weak interaction, covalent organic frameworks and polymers with intrinsic microporosity were summarized and discussed, from the viewpoints of design principles, iodine capture performance, and adsorbent-iodine interactions. As the main prospect, we hope this work will attracting more researchers to study porous organic materials and address the challenge of effective capture of radioactive iodine.

A new acyclic cucurbit[n]uril (CB[n]) dimer is synthesized by copper-catalyzed azide-alkyne cycloaddition or “click” reaction. The acyclic CB[n] dimer possesses two cavities, and is able to encapsulate two guest molecules simultaneously. This dimer is discovered to be high affinity host molecule for a wide variety of dyes, pharmaceutical drugs and guest molecules.

The directed synthesis of asymmetrically substituted porphyrins—tetraphenylporphyrine derivatives containing amino acid residues as a functional group, which can be used as “anchor” groups, for incorporation into the structure of a protein molecule, was carried out. The obtained compounds were characterized by a number of spectral methods confirming their structure and purity. Their base and acid ionization constants in the AN–HClO₄ and DMSO–potassium cryptate (KOH[222])—systems were measured by spectrophotometric titration. It was found that the asymmetric substitution architecture contributed to the stabilization of the protonated forms of porphyrins. This allowed, for the first time, to extract and spectrally characterize the mono- and doubly-protonated forms (H₃P⁺ and H₄P²⁺) of each ligands in the AN–HClO₄ system. The analysis of the spectral changes of the monoamino derivative led to identify three stages of the protonation, which first involves the nitrogen atom of the periphery substituent (pK_b = 13.26) and then the central nitrogen atoms of the macrocycle (pK_b1 = 11.50; pK_b2 = 9.65; pK_b1,2 = 21.15). The relative stability of the first intermediate is assumed to be caused by charge delocalization. The electron-donor nature of the solvent in the DMSO–KOH [222] system led to the leveling of the ionization constants for the first and second stages, which allowed us to determine only the total values for the porphyrins studied. The successive stages of acid–base interactions were analyzed in the article.

Graphical abstract