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in- and out-Cyclophanes Bearing Non-Hydrogen Bridgehead Substituents.

The syntheses of several cyclophanes containing a triaryl(element) "top" poised above a trisubstituted benzene "base" were carried out to install a non-hydrogen atom as a substituent on a bridgehead with an inwardly directed geometry. Most significantly, the tribenzo 6-fluoro-6-sila-2,10,19-trithia[5(6,14)][11]metacyclophane 2 was prepared by condensation of tris[2-(bromomethyl)phenyl]fluorosilane and 1,3,5-tris(mercaptomethyl)benzene in 0.4% yield. The X-ray structure of 2 shows that the cyclophane adopts an in-configuration; i.e., the fluorine atom is on the interior of the macrocycle and only 2.8 Å from the center of the basal aromatic ring. Compound 2 is one of only a very few molecules to contain a non-hydrogen in-atom, and the in-fluorosilane of 2 is the largest in-functional group to have been installed in any molecule. Similar attempts to prepare an in-phosphine oxide were unsuccessful, although the corresponding in-phosphines were prepared, and an attempt to prepare an in-methylsilane led instead to the corresponding out-isomer.

Journal Article↗

Fe(II) in different macrocycles: electronic structures and properties.

A theoretical comparative study of complexes of porphyrin (P), porphyrazine (Pz), phthalocyanine (Pc), porphycene (Pn), dibenzoporphycene (DBPn), and hemiporphyrazine (HPz) with iron (Fe) has been carried out using a density functional theory (DFT) method. The difference in the core size and shape of the macrocycle has a substantial effect on the electronic structure and properties of the overall system. The ground states of FeP and FePc were identified to be the 3A2g [(d(xy))2(d(z)2)2(d(pi))2] state, followed by 3E(g) [(d(xy))2(d(z)2)1(d(pi))3]. For FePz, however, the 3E(g)-3A2g energy gap of 0.02 eV may be too small to distinguish between the ground and excited states. When the symmetry of the macrocycle is reduced from D4h to D2h, the degeneracy of the d(pi) (d(xz), d(yz)) orbitals is removed, and the ground state becomes 3B2g [(d(xy))2(d(z)2)1(d(yz))2(d(xz))1] or 3B3g [...(d(yz))1(d(xz))2] for FePn, FeDBPn, and FeHPz. The calculations also show how the change of the macrocycle can influence the axial ligand coordination of pyridine (Py) and CO to the Fe(II) complexes. Finally, the electronic structures of the mono- and dipositive and -negative ions for all the unligated and ligated iron macrocycles were elucidated, which is important for understanding the redox properties of these compounds. The differences in the observed electrochemical (oxidation and reduction) properties between metal porphycenes (MPn) and metal porphyrins (MP) can be accounted for by the calculated results (orbital energy level diagrams, ionization potentials, and electron affinities).

Iron↗

Novel synergism of two antifungal agents, copiamycin and imidazole.

Copiamycin, a macrocyclic lactone antifungal antibiotic, was found to potentiate the antifungal effect of imidazole compounds, ketoconazole in particular. The potentiation of two nominally fungistatic agents in vitro was substantiated by a marked reduction of the minimum inhibitory and minimum fungicidal concentrations when the drugs were used in combination. The effectiveness of this synergistic combination was also demonstrated in experimental murine candidosis. Evidence is presented to suggest that this combined effect is due, at least in part, to the ionophoretic property of copiamycin. Whereas amphotericin B induces a marked increase in cellular permeability, this antibiotic does not possess the ionophoretic action of copiamycin, indicating that the enhancement of copiamycin activity and significant reduction of amphotericin B activity by ketoconazole pretreatment can be ascribed not only to changes in membrane permeability of the test organisms, but also to the different action mechanisms of copiamycin and amphotericin B. It is thus plausible that the strong synergism of copiamycin with imidazole compounds is related to the ionophoretic activity of the antibiotic. Further studies on the biochemical mechanism of this synergistic effect are being conducted together with an assessment of the clinical significance of this drug combination.

Amphotericin B↗

[A mid-infrared spectra study of a series of benzocrown ether and macrocyclic polyether diester].

With a Nicolet 20 SX B Fourier Transform infrared spectrometer, the mid-infrared spectra in region of 4000-400 cm-1 were observed for a series of benzocrown ether and macrocyclic polyether diester. A difference in the wavelength of absorption of the ether bond was found between benzocrown ether and macrocyclic polyether diester. The wavelength of absorption of the ether bond of the compounds I-IV moved down about 25 cm-1, as compared with that of the compounds V-IX.

Ethers, Cyclic↗

Synthesis, aggregation, and adsorption phenomena of shape-persistent macrocycles with extraannular polyalkyl substituents.

The synthesis of shape-persistent macrocycles based on the phenyl-ethynyl backbone containing various extraannular alkyl side chains is described. Although compound solubility increases with increasing size of the side groups, decreasing the solvent polarity induces aggregation of the rings by nonspecific interactions. This was investigated by proton NMR spectroscopy. The magnitude of aggregation can be varied by using solvent mixtures of different hexane content, supporting the model of a solvophobic effect. From 1,2,4-trichlorobenzene solution the macrocycle 1c adsorbs at the surface of highly oriented pyrolitic graphite (HOPG). The two-dimensional order of the structure was investigated by scanning tunneling microscopy (STM) revealing the formation of a two-dimensional lattice of p1(2)mm symmetry with lattice parameters A = 3.6 nm, B = 5.7 nm, and Gamma = 74 degrees.

Journal Article↗

Structural investigations of pyridin-4-yl indolizine modified beta-cyclodextrin derivatives as fluorescent chemosensors for organic guest molecules.

In order to investigate the substituent effects on their conformations and spectroscopic properties, a series of pyridin-4-ylindolizine modified beta-cyclodextrin derivatives were studied by 2D NMR (ROESY spectra) in D2O, circular dichroïsm, and fluorescence spectroscopy. It was found that the linked indolizin-beta-cyclodextrin compounds exhibited two types of conformations, as a function of the substituent, in which fluorescent moieties formed either an intramolecular complex or were not included in the hydrophobic cavity of the macrocycle. Under addition of organic guest species in a phosphate buffer at neutral pH, the variation of emission fluorescence intensity showed that these compounds are of significance for detection of volatile organic molecules and adamantane derivatives and might be used as molecular chemosensor.

Circular Dichroism↗

Accurate mass measurement of low molecular weight compounds by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

We report the application of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) for the accurate measurement of mass of low molecular weight compounds (smaller than 1500 Da), a linear peptide, two types of cyclic depsipeptides, a polyhydroxy-macrocyclic lactone, and two prenylated flavonoids, with delayed extraction in the reflector mode. The performance of the MALDI-TOF instrument was less than those of fast atom bombardment and Fourier-transform ion cyclotron resonance mass spectrometry instruments and insufficient to give acceptable accuracy for literature reporting. Nevertheless, when combined with NMR spectrometry and/or amino acid analysis to give information on the numbers of carbon atoms and index of hydrogen deficiency, MALDI was useful for determination of the elemental composition of the low molecular weight compounds available in small quantities.

Angiotensin II↗

Pores Formed by Bis-macrocyclic Bola-amphiphiles in Vesicle and Planar Bilayer Membranes.

A new series of bis-macrocyclic bola-amphiphiles were prepared, and their transport activities in vesicle and planar bilayer membranes were evaluated. From vesicle experiments, the apparent kinetic order in transporter indicates that aggregates are the kinetically active species. Step-conductance changes observed in planar bilayer membranes indicate that the compounds act as channels. Multiple copies of the same channel form in which the conductance is controlled by the macrocyclic portions of the structures. The pores are ion-selective in the sequence Cs(+) > K(+) > Na(+) > Cl(-), controlled by the polar head-groups of the structures. The data are consistent with a model involving the formation of active dimers.

Journal Article↗

Strongly coupled porphyrin arrays featuring both pi-cofacial and linear-pi-conjugative interactions.

A combination of metal-catalyzed cross-coupling and metal-templated cycloaddition reactions have been utilized to establish multiporphyrin compounds 5-(5'-[15',15' '-bis(10' ',20' '-di[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]ethyne)-6-[(5' "-10' ",20' "-di[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]indane (1) and 5,6-bis(5'-15',15' '-bis[(10',20'-di[4-(3-methoxy-3-methylbutoxy)phenyl]porphinato)zinc(II)]ethyne)indane (2). Compounds 1 and 2 feature a covalently bridged cofacial bis(porphinato)metal core; ethyne bridging moieties conjugate directly one and two respective peripheral (porphinato)zinc(II) substituents to the macrocyclic framework of their corresponding face-to-face porphyrin units. Optical spectroscopy and electrochemical studies demonstrate substantive electronic interactions between the porphyrin subunits of these compounds. Notably, structural and (1)H NMR analyses verify that 1 and 2 possess open conformations necessary for binding small molecules within their respective cofacial (porphinato)metal cores.

Journal Article↗

Ditopic hexaazamacrocycles containing pyridine: synthesis, protonation and complexation studies.

Structural studies of metal complexes of five ditopic hexaazamacrocycles containing two pyridine rings ([n]py2N4 n= 18, 20, 22, 24 and 26) have been carried out. The synthesis of macrocycles [22]- to [26]-py2N4 are also reported. The protonation constants of the last three compounds and the stability constants of their complexes with Ni2+, Cu2+, Zn2+, and Pb2+ were determined at 25 degrees C in 0.10 mol dm(-3) KNO3 in aqueous solution. Our results with [22]py2N4 show significant differences from those described previously, while [24]py2N4 has not been studied before and [26]py2N4 is a new compound. Mononuclear and dinuclear complexes of the divalent metal ions studied with [22]- to [26]-py2N4 were found in solution. The stability constants for the ML complexes of the three ligands follow the Irving-Williams order: NiL2+ < CuL2+ >> ZnL2+ > PbL2+, however for the dinuclear complexes the values for Pb2+ complexes are higher than the corresponding values for the Ni2+ and the Zn2+ complexes. The X-ray single crystal structures of the supramolecular aggregates [Cu2([20]py2N4)(H2O)4][Cu(H2O)6](SO4)3 x 3H2O and [Cu(2)([20]py(2)N4)(CH3CN)4][Ni([20]py2N4)]2(ClO4)8 x H2O, which are composed of homodinuclear [Cu2([20]py2N4])(H2O)4]4+ and [Cu2([20]py2N4])(CH3CN))4]4+, and mononuclear species, [Cu(H2O)6]2+ and [Ni([20]py2N4)]2+, respectively, assembled by an extensive network of hydrogen bonds, are also reported. In both homodinuclear complexes the copper centres are located at the end of the macrocycle and display distorted square pyramidal coordination environments with the basal plane defined by three consecutive nitrogen donors and one solvent molecule, water in and acetonitrile in . The macrocycle adopts a concertina-type conformation leading to the formation of macrocyclic cavities with the two copper centres separated by intramolecular distances of 5.526(1) and 5.508(7) A in 1a and 2a, respectively. The mononuclear complex [Ni([20]py2N4])]2+ displays a distorted octahedral co-ordination environment with the macrocycle wrapping the metal centre in a helical shape. EPR spectroscopy of the copper complexes indicated the presence of mono- and dinuclear species.

Journal Article↗

trans-2,4,4,6,8,8-Hexamorpholino-2,6-bis(n-propylamino)cyclo-2lambda5,4lambda5,6lambda5,8lambda5-tetraphosphazatetraene.

The title compound, C(30)H(64)N(12)O(6)P(4), consists of a centrosymmetric chair-shaped cyclic tetrameric phosphazene ring with six bulky morpholino and two n-propylamino side groups. The two n-propylamino side groups are in trans positions. The bulky substituents mainly determine the eight-membered-ring conformation. The endocyclic N-P-N angles around the P atoms having different substituents are not the same as the P-N-P angles of the macrocyclic ring.

Aza Compounds↗

Variable-temperature spectroelectrochemical study of horseradish peroxidase.

The reduction potentials of the compound II/ferric and compound I/compound II couples have been studied, using potassium hexachloroiridate as a mediator titrant, by thin-layer spectroelectrochemistry. Compound I, which is 2 equiv more oxidized than the ferric (i.e., resting) form of the enzyme, was reversibly formed via a compound II intermediate; no evidence for a ferric porphyrin pi-cation radical intermediate was obtained. At 25 degrees C, E degrees' (compound I/compound II) = 897.9 +/- 3 mV (NHE) and E degrees'-(compound II/ferric) = 869.1 +/- 2 mV. Redox thermodynamic parameters, obtained from the temperature dependences of the reduction potentials of both couples, are reported. The reaction entropies (delta S degrees rc) for the compound II/ferric and compound I/compound II couples are 19.8 +/- 3.9 and 12.1 +/- 3.7 eu, respectively. This result indicates that the reorganization energy for the macrocycle-centered couple is lower than that for the metal-centered one. Together with our observation that E degrees' for the former is ca. 30 mV greater than that for the latter, these results suggest that compound I is more reactive toward outer-sphere reductants than compound II. In particular, the electron self-exchange rates for the compound I/compound II and compound II/ferric couples are estimated to be 4.4 x 10(-1) and 4.9 x 10(-4) M-1 s-1, respectively. Surprisingly, the formation of compound I from ferric HRP is accompanied by an almost zero standard entropy (delta S degrees') change.

Electrochemistry↗

Figure-eight tetrathiaoctaphyrin and dihydrotetrathiaoctaphyrin.

The acid-catalyzed condensation of pyrrole and 2,5-bis(p-tolylhydroxymethyl)thiophene yields two novel giant heteroporphyrins: 5,10,15,20,25,30, 35,40-octa(p-tolyl)-41,43,45,47-tetrathia[36]octaphyrin(1.1.1.1.1.1.1.1) (S4OP) and 5,10,15,20,25,30,35,40-octa(p-tolyl)-dihydro-41,43,45,47-tetrathia[38]octaphyrin(1.1.1.1.1.1.1.1) (S4OPH2). These tetrathiaoctaphyrins are interconvertible through dihydrogenation or dehydrogenation processes. Both compounds possess helical figure-eight geometry with two thiophene rings for S4OP or two pyrrole rings for S4OPH2 in the ribbon-crossing center as shown by NOESY experiments. The synthesis of the figure-eight tetrathiaoctaphyrin implies a prearrangement process to form helical M or P dithiatetrapyrromethanes. The P-P or M-M condensation leads to the figure-eight molecule in competition with an intramolecular ring closure. Two dithiaporphyrin-like pockets of S4OP or S4OPH2 behave as independent proton acceptors. The stepwise process yields symmetric or asymmetric cationic species that depends on whether an even or odd number of NH protons are added. Dihydrotetrathiaoctaphyrin contains 38 pi electrons in its conjugation pathway, which corresponds to the formal [4n + 2] Hückel type pi-electron formulation that is consistent with a modest diatropic ring current effect in their 1H NMR spectra. The formal 4n type pi-electron formulation for tetrathiaoctaphyrin accounts for the residual paratropic shifts. A figure-eight conveyor-belt-like movement of the whole macrocyclic ring without a racemization step is proposed to account for the dynamic properties of S4OP. The molecule shuttles between two degenerate configurations. A S4OP-S4OPH2 couple may be considered as a molecular element which, while preserving the overall figure-eight geometry, "chooses" pyrrole or thiophene rings as spacers as a function of the macrocyclic oxidation state.

Heterocyclic Compounds, 4 or More Rings↗

Pharmacokinetics, tissue distribution, and metabolism of 17-(dimethylaminoethylamino)-17-demethoxygeldanamycin (NSC 707545) in CD2F1 mice and Fischer 344 rats.

PURPOSE: 17-(Dimethylaminoethylamino)-17-demethoxygeldanamycin (17DMAG) is an analogue of the benzoquinone ansamycin compound 17-(allylamino)-17-demethoxygeldanamycin (17AAG), which is currently being evaluated in clinical trials. Studies were performed in mice and rats to: (1) define the plasma pharmacokinetics, tissue distribution, and urinary excretion of 17DMAG after i.v. delivery; (2) define the bioavailability of 17DMAG after i.p. and oral delivery; (3) characterize the biliary excretion of 17DMAG after i.v. delivery to rats; and (4) characterize, if possible, any metabolites of 17DMAG observed in plasma, tissue, urine, or bile. MATERIALS AND METHODS: Studies were performed in female, CD2F1 mice or male Fischer 344 rats. In preliminary toxicity studies and subsequent i.v. pharmacokinetic studies in mice, 17DMAG i.v. bolus doses of 33.3, 50, and 75 mg/kg were used. In bioavailability studies, i.p. and oral 17DMAG doses of 75 mg/kg were used. In preliminary toxicity studies in rats, i.v. bolus doses of 10 and 20 mg/kg were used, and in i.v. pharmacokinetic studies 10 mg/kg was used. Compartmental and noncompartmental analyses were applied to the plasma concentration versus time data. In mice and rats, concentrations of 17DMAG were determined in multiple tissues. Urine was collected from mice and rats treated with each of the i.v. doses of 17DMAG mentioned above, and drug excretion was calculated until 24 h after treatment. Biliary excretion of 17DMAG and metabolites was studied in bile duct-cannulated rats given a 10 mg/kg i.v. bolus dose of 17DMAG. 17DMAG metabolites were identified with LC/MS. RESULTS: A 75 mg/kg dose of 17DMAG caused no changes in appearance, appetite, waste elimination, or survival of treated mice as compared to vehicle-treated controls. Bolus i.v. delivery of 17DMAG at 75 mg/kg produced "peak" plasma 17DMAG concentrations between 18 and 24.2 microg/ml in mice killed at 5 min after injection. Sequential reduction in the 17DMAG dose to 50 and 33.3 mg/kg resulted in "peak" plasma 17DMAG concentrations between 9.4 and 14.4, and 8.4 and 10.5 microg/ml, respectively. Plasma 17DMAG AUC increased from 362 to 674 and 1150 microg/ml x min when the 17DMAG dose increased from 33.3 to 50 and 75 mg/kg, respectively, corresponding to a decrease in 17DMAG CLtb from 92 ml/min per kg to 75 and 65 ml/min per kg. Plasma 17DMAG concentration versus time data were best fit by a two-compartment open linear model. No potential 17DMAG metabolites were observed in plasma. 17DMAG bioavailability was 100% and 50% after i.p. and oral delivery, respectively. In rats, an i.v. bolus dose of 10 mg/kg produced peak plasma 17DMAG concentrations between 0.88 and 1.74 microg/ml. Plasma 17DMAG concentrations had fallen below the lower limit of quantitation by 180 min and were best fit by a one-compartment open linear model. The plasma 17DMAG AUC was 104 microg/ml x min, corresponding to a 17DMAG CLtb of 96 ml/min per kg. 17DMAG distributed rapidly to all mouse and rat tissues except brain and testes. Only mouse liver contained materials consistent with potential metabolites of 17DMAG, but their concentrations were below the limit of quantitation of the HPLC assay used. Within the first 24 h after delivery, urinary excretion of 17DMAG by mice and rats accounted for 10.6-14.8% and 12.5-16%, respectively, of the delivered dose. By 15 min after i.v. delivery of 10 mg/kg of 17DMAG, rat bile contained 11 new materials with absorbance similar to that of 17DMAG. Four of these proposed metabolites had an Mr of 633, indicating addition of an oxygen. Two of these proposed metabolites had an Mr of 603, implying the loss of one methyl group, and one had an Mr of 589, implying the loss of two methyl groups. The remaining four proposed metabolites had an Mr of 566, 571, 629, and 645, respectively. Biliary excretion of 17DMAG and metabolites accounted for 4.7 +/- 1.4% of the delivered dose, with 17DMAG accounting for 50.7 +/- 3.4% of the biliary excretion. CONCLUSIONS: 17DMAG has excellent bioavailability when given i.p. and good bioavailability when given orally. 17DMAG is widely distributed to tissues and is quantitatively metabolized much less than is 17AAG. The pharmacokinetic and metabolite data generated should prove relevant to the design of additional preclinical studies as well as to contemplated clinical trials of 17DMAG and could be useful in their interpretation.

Animals↗

Synthesis, structures and antitumor activity of the first crown ester-linked bipyridyl platinum complexes.

Three new crown ester-linked bipyridine homologs with three, four or five ethylene glycol units, which are bulky and soluble in both hydrophilic and lipophilic media, were synthesized. The reaction of the appropriate macrocycles with K2PtCl4 in water gave yellow cisplatin analogs in good yield. These complexes were converted to carboplatin analogs by exchange of the leaving group. All the compounds were characterized by elemental analysis and various spectroscopic methods. Carboplatin analogs showed good solubility in both hydrophilic and lipophilic media. The crystal structure of 2c, the carboplatin analog with macrocycles containing five ethylene glycol units, was determined by X-ray diffraction: space group P1, a = 9.798(1), b = 12.580(3), c = 13.945(2) A, alpha = 108.61(2), beta = 94.59(1), gamma = 97.42(2) degrees, Z = 2, R = 0.0618. Some of platinum complexes showed a moderate cytotoxic effect on both murine leukemia L1210 and P388 even though they do not have any NH proton.

2,2'-Dipyridyl↗

Synthesis, crystal structures, and magnetic properties of cyano-bridged honeycomblike layers M(V)-Cu(II) (M = Mo, W) chelated by a macrocyclic ligand.

Two cyano-bridged Cu(II)-M(V) [M = Mo (2), W (3)] complexes formed by self-assembly of octacyanometalates [M(CN)8]3- (M = Mo, W) with a new molecular precursor [Cu(L2)]2+ (1) (L2 = a macrocyclic ligand) in a 2:3 ratio have been investigated in terms of structures and magnetic behaviors. The M2Cu3 repeating unit of both bimetallic compounds is extended to a two-dimensional honeycomblike layered structure. The pendant ethyl groups on L2 noticeably influence the structural parameters around the Cu center. Compared with the system composed of a macrocycle without a side group, Cu-N(ax) (ax = axial) distances become shorter and the Cu-N(ax)-C(ax) angles are more bent for 2 and 3. The magnetic data denote that the Cu(II) and M(V) spins undergo explicit ferromagnetic interactions via CN bridges. From a structural and magnetic point of view, given that the Cu-N(ax) bond length in the tetragonally distorted octahedral Cu(II) environment is long enough, the overall ferromagnetic character remains despite the variation of Cu-N(ax)-C(ax) angle in this system.

Journal Article↗