Crystal supramolecular motifs: columns of embracing Ph3PMe+ or Ph3PCI+ cations controlling formation of

The crystal structures of (Ph3PCl)2[Cu3Cl8] (1) (triclinic, space group P1, a = 9.480(6) A, b = 10.243(8) A, c = 11.232(6) A, alpha = 86.76(4) degrees, beta = 66.62(5) degrees, gamma = 83.92(4) degrees, Z = 1) and (Ph3PMe)2[Cu3Br8] (2) (triclinic, space group P1, a = 9.795(4) A, b = 10.472(4) A, c = 11.392(4) A, alpha = 86.67(3) degrees, beta = 66.67(3)degrees, gamma = 83.14(3) degrees, Z = 1), reported here, demonstrate a new supramolecular motif for cations of the type Ph3PY+ where Y is CH3 or Cl. The crystals contain columns of cations propagated by alternating 6-fold phenyl embraces (6PE) and pseudo-6PE: the pseudo-6PE described here contains four phenyl rings and two hetero groups (Cl or CH3), and is symbolized as 4P2Y. The zigzag sequence of cations engaged in ...6P...4P2Y...6P...4P2Y... is similar to the zigzag chain of infinite 6-fold phenyl embraces (ZZI6PE) frequently adopted by Ph4P+ cations in crystals. One-dimensionally nonmolecular anion chains with repeat unit [Cu3X8] run parallel to and between the columns of cations. The coordination geometry in the [Cu3X8(2-)]1 to infinity chain has not been observed in crystals with other cations, and it is postulated that the attractive interactions between cations in the pseudo-ZZI6PE crystal supramolecular motif control the geometry of the anions through the requirement for commensurability of cation columns and anion chains.     

Ordering the reductive and cytochrome P450 oxidative steps in demethylsterigmatocystin formation yields general insights into the biosynthesis of aflatoxin and related fungal metabolites

The biosynthesis of the potent environmental carcinogen aflatoxin B1 involves ca. 15 steps beyond the first polyketide intermediate. Central among these is the rearrangement of the anthraqinone versicolorin A to the xanthone demethylsterigmatocystin. Genetic evidence strongly suggests that two enzymes are required for this process, a cytochrome P450, AflN, and a probable NADPH-dependent oxidoreductase, AflM. Given the overall redox change evident in this skeletal rearrangement, two rounds of oxidation and a reduction necessarily occur. Earlier experiments indicated that reductive deoxygenation of versicolorin A is not the first step. In the present report we consider a mechanistic alternative that AflM-mediated reduction is instead the last of these three reactions prior to formation of the xanthone intermediate. To this end, 9-hydroxydihydrodemethylsterigmatocystin was prepared by total synthesis as was its 9-deoxy analogue, an established aflatoxin precursor. During the final isolation of the "angular" synthetic xanthone targets it was found that acid catalysis promoted their isomerization to thermodynamically favored "linear" xanthones. Whole-cell and ground-cell incubations of the 9-hydroxy- and 9-deoxyxanthones were conducted with a mutant strain of Aspergillus parasiticus blocked at the first step of the pathway and examined for their ability to support aflatoxin production. The 9-deoxyxanthone gave dramatically enhanced levels of the mycotoxin. The 9-hydroxyxanthone, on the other hand, afforded no detectable increase in aflatoxins above controls, indicating that reductive deoxygenation at C-9 of a xanthone precursor does not take place in aflatoxin biosynthesis. Constraints imposed by earlier studies and the experiments in this paper serve to eliminate simple and intuitive conversions of versicolorin A to demethylsterigmatocystin and lead inescapably to a more subtle reaction sequence of oxidation-reduction-oxidation. Previous puzzling observations of extensive A-ring hydrogen exchange in the course of the rearrangement of versicolorin A to demethylsterigmatocystin have now been explained by a new mechanism that is consistent with all extant data. We propose that P450-mediated aryl epoxidation (AflN) initially disrupts the aromatic A-ring of versicolorin A. Oxirane opening enables A-ring proton exchange, as does the subsequent AflM-mediated reductive step. A second cycle of P450 oxidation (AflN), this time a Baeyer-Villiger cleavage, enables decarboxylation and the formation of demethylsterigmatocystin. Mechanistic and stereoelectronic principles that underlie this proposal are described and may prove general as illustrated in biogenetic hypotheses for four other fungal anthraquinone --> xanthone transformations.     

Time-resolved C2 swan emission from short-pulse UV fragmentation of CO: evidence for two C2 formation mechanisms

We have studied C₂ Swan (d³Π → a³ Π_u) emission resulting from multiphoton UV excitation of CO. Population of d³Π proceeds through distinct early and late processes, the former giving rise only to normal Swan emission. The late process is responsible for v = 6 enhancement (high-pressure bands), and it dominates time-averaged emission in an bands for ? 10 Torr of CO.     

Photoinduced axial ligation and deligation dynamics of nonplanar nickel dodecaarylporphyrins

The ground- and excited-state metal-ligand dynamics of nonplanar nickel(II) 2,3,5,7,8,10,12,13,15,17,18,20-dodecaphenylporphyrin (NiDPP) and two fluorinated analogues (NiF(20)DPP and NiF(28)DPP) have been investigated using static and time-resolved absorption spectroscopy in toluene and in ligating media that differ in basicity, aromaticity, and steric encumbrance. Because of the electronic and steric consequences of nonplanarity, NiDPP does not bind axial ligands in the ground state, but metal coordination does occur after photoexcitation with multistep dynamics that depend on the properties of the ligand. Following the structural relaxations that occur in all nickel porphyrins within approximately 10 ps, ligand binding to photoexcited NiDPP is progressively longer in pyridine, piperidine, and 3,5-lutidine (25-100 ps) but does not occur at all in 2,6-lutidine in which the ligating nitrogen is sterically encumbered. The transient intermediate that is formed, which nominally could be either a five- or six-coordinate species, also has a ligand-dependent lifetime (200-550 ps). Decay of this intermediate occurs partially via ligand release to re-form the uncoordinated species, in competition with binding of the second axial ligand and/or conformational/electronic relaxations (of a six-coordinate intermediate) to give the ground state of the bis-ligated photoproduct. The finding that the photoproduct channel principally depends on ligand characteristics along with the time-evolving spectra suggests that the transient intermediate may involve a five-coordinate species. In contrast to NiDPP, the fluorinated analogues NiF(20)DPP and NiF(28)DPP do coordinate axial ligands in the ground state but eject them after photoexcitation. Collectively, these results demonstrate the sensitivity with which the electronic and structural characteristics of the macrocycle, substituents, and solvent (ligands) can govern the photophysical and photochemical properties of nonplanar porphyrins and open new avenues for exploring photoinduced ligand association and dissociation behavior.     

Preparation and crystal structure ofexo-2,exo-6-dihydroxy-2,6-dimethyl-9-oxabicyclo[3.3.1]nonane

In a further exploration of the structural factors causing alicyclic diols such asexo-2,exo-6-dihydroxy-2,6-dimethylbicyclo[3.3.1]nonane (1) to adopt the helical tubuland inclusion host structure, the title compound (8) has been synthesized and its crystal structure determined. This 9-oxa analogue of (1) has a totally different structure [C₁₀H₁₈O₃; orthorhombic;P2₁2₁2;a 18.989(4),b 19.064(3),c 14.256(3) Å;Z 20; with finalR 0.065] due to involvement of the ether oxygen atom in the hydrogen bonding network. The structure of the diol (8) approximatesP¯42₁ c symmetry, and 16 of the 20 molecules per cell create a hostlike structure of this symmetry, which consists of tightly bound hydrogen bonded pillars parallel toc. The remaining guestlike molecules occupy inequivalent pseudo ¯4 sites separated byc/2 to form weakly bound columns parallel toc. Hydrogen bonds also occur between the pillars and columns. An ordered structure with sensible intermolecular contacts can be formed inP2₁2₁2₁ with thec axis doubled. A difference betweena andb axial lengths correlates with a difference in occupancies of pseudo-¯4-related sites for the guest-like component of the structure.     

Tuning the optical properties of fluorinated indolylfulgimides

Photochromic fluorinated indolylfulgides have been identified as potential candidates for a wide range of applications including optical switches, photoregulators of biological processes, and optical memory media. In humid environments or biological systems, hydrolytic stability is essential. In an effort to improve hydrolytic stability, a series of indolylfulgimides has been synthesized from a parent trifluoromethyl-substituted indolylfulgide. The nitrogen of the succinimide moiety is linked to either a dimethyl amino or one of seven substituted phenyl groups. The phenyl groups feature substituents with increasing electron-withdrawing ability. The spectral characteristics of each compound have been examined, revealing that the wavelength absorption maxima of each form increases with increasing electron-withdrawing ability of the substituted N-phenyl ring. The quantum yields of the photoreactions have been determined with the N-(phenyl)fulgimide showing a ring closure value of nearly 0.30 in toluene. In addition, the hydrolytic, thermal, and photochemical stabilities of each compound have been measured. The fulgimides exhibit at least a 200-fold enhancement of hydrolytic stability for the Z-form and over a 1000-fold enhancement for the C-form in comparison to the same form of the parent fulgide. The N-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)fulgimide can undergo up to 3000 photochemical cycles (coloration followed by bleaching) before losing 20% of its initial absorbance at photostationary state.     

Helical tubulate inclusion compounds of ferrocene and squalene

The inclusion compounds of 2,8-dimethyltricyclo[5.3.1.1^3,9]dodecane-syn-2,syn-8-diol,3, with ferrocene and with squalene have been prepared. The crystal structures of these helical tubulate compounds: (3)₃·(ferrocene)_0.75 [P3₁21,a=b=13.7480(6),c=7.0312(5) Å,Z=1,R=0.038] and (3)₃·(squalene)_0.23 [P3₁21,a=b=13.677(1),c=7.0533(9) Å,Z=1,R=0.042] are described. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82151 (16 pages).     

NADH Electrooxidation Using Bis(1,10-phenanthroline-5,6-dione) (2,2'-bipyridine)ruthenium(II)-Exchanged Zirconium Phosphate Modified Carbon Paste Electrodes

We present a carbon paste electrode (CPE) modified using the electron mediator bis(1,10‐phenanthroline‐5,6‐dione)(2,2′‐bipyridine)ruthenium(II) ([Ru(phend)₂bpy]²⁺) exchanged into the inorganic layered material zirconium phosphate (ZrP). X‐Ray powder diffraction showed that the interlayer distance of ZrP increases upon [Ru(phend)₂bpy]²⁺ intercalation from 10.3 Å to 14.2 Å. The UV‐vis and IR spectroscopies results showed the characteristic peaks expected for [Ru(phend)₂bpy]²⁺. The UV‐vis spectrophotometric results indicate that the [Ru(phend)₂bpy]²⁺ concentration inside the ZrP layers increased as a function of the loading level. The exchanged [Ru(phend)₂bpy]²⁺ exhibited luminescence even at low concentration. Modified CPEs were constructed and analyzed using cyclic voltammetry. The intercalated mediator remained electroactive within the layers (E°′=–38.5 mV vs. Ag/AgCl, 3.5 M NaCl) and electrocatalysis of NADH oxidation was observed. The kinetics of the modified CPE shows a Michaelis–Menten behavior. This CPE was used for the oxidation of NADH in the presence of Bakers' yeast alcohol dehydrogenase. A calibration plot for ethanol is presented.     

p-aminophenyl phosphate: an improved substrate for electrochemical enzyme immnoassay

An alternative substrate is described for enzyme immunosaasay with electrochemical detection. Alkaline phosphatase (EC.3.1.3.1) activity is determined by using p-aminophenyl phosphate as the enzyme substrate. Enzyme-generated p-aminophenol is detected amperometrically at a glassy carbon electrody by liquid chromatography with electrochemical detection. The oxidation potential obtained for the detectionof p-aminophenol is lower than that for phenol, the previously used substrate product. The detection limit for p-aminophenol is 0.20pmol. A detection limit of 30 pg ml^-1 for digoxin and a 5-min incubationtime for the enzyme reaction were obtained with the new system.     

Constructing banking networks under decreasing costs of link formation

The structure of networks plays a central role in the behavior of financial systems and their response to policy. Real-world networks, however, are rarely directly observable: banks’ assets and liabilities are typically known, but not who is lending how much and to whom. This paper adds to the existing literature in two ways. First, it shows how to simulate realistic networks that are based on balance-sheet information. To do so, we introduce a model where links cause fixed-costs, independent of contract size; but the costs per link decrease the more connected a bank is (scale economies). Second, to approach the optimization problem, we develop a new algorithm inspired by the transportation planning literature and research in stochastic search heuristics. Computational experiments find that the resulting networks are not only consistent with the balance sheets, but also resemble real-world financial networks in their density (which is sparse but not minimally dense) and in their core-periphery and disassortative structure.