Cyclophanes—13: Crystal and molecular structure of [2.2][2,5]furano(1,4)naphthalenophane

The crystal and molecular structure of [2.2](2,5)furano(1,4)naphthalenophane (1) was determined by X-ray crystallography. The molecule exists in the anti-conformation and the study represents the first instance in which the structural features of a naphthalenoid ring within a cyclophane were determined. Crystals of cyclophane 1 are orthorhombic, space group Pbca, with a = 7.859(2). b = 11.482(3) and c = 28.818(8) Å. While the nonbridged portion of the naphthalenoid ring is planar, the portion which is bridged to the furanoid ring through its 1 and 4 C atoms is puckered and boat-shaped. These C atoms are positioned 14° out of the plane of the other four C atoms of this ring. The furanoid ring is essentially planar but is not parallel to the naphthalenoid ring. It is inclined 22° to the least squares plane of the bridged portion of the naphthalenoid ring. This angle of inclination staggers the atoms of the furanoid and bridged naphthalenoid ring and positions the 3 and 4 C atoms, the 2 and 5 C atoms and the 0 atom of the furanoid ring 3.4. 2.9 and 2.6 Å. respectively, from the least squares plane of the bridged portion of the naphthalenoid ring. While the internal angles around the bridging C atoms α- to the naphthalenoid ring are 109°, those α- to the furanoid ring are 113°. In addition unusually large bond angles ($\text{\$}\text{?}$137°) at the 2 and 5 C atoms of the furanoid ring, external to the ring, are also observed. The distortions are considered with respect to the strain within the cyclophane macrocycle and are compared with other similar systems.     

Mössbauer effect study of Y(Fe0.022 Co0.978)2 at temperatures between 0.15 and 4.2k

A³He-⁴He dilution refrigerator was constructed to perform Mössbauer measurements well below 4.2K. Results are reported here on the pseudobinary Laves-Phase system Y (Fe_1-x Co_x)₂ for x=0.978. We found that at low temperatures, the Fe ions undergo a disordered magnetic phase transition, with a Curie temperature of approximately 4K and a saturation field of 96K0e. The easy axis of magnetization appears to be the [111] direction. This study is an extension to very low temperatures of previous work on the system with 0X0.978.Supported by the NSF Grant No. DMR 73-07665 AO 3     

Boundaries of Anion/Naphthalenediimide Interactions: From Anion-π Interactions to Anion-Induced Charge-Transfer and Electron-Transfer Phenomena

The recent emergence of anion-π interactions has added a new dimension to supramolecular chemistry of anions. Yet, after a decade since its inception, actual mechanisms of anion-π interactions remain highly debated. To elicit a complete and accurate understanding of how different anions interact with π-electron-deficient 1,4,5,8-naphthalenediimides (NDIs) under different conditions, we have extensively studied these interactions using powerful experimental techniques. Herein, we demonstrate that, depending on the electron-donating abilities (Lewis basicity) of anions and electron-accepting abilities (π-acidity) of NDIs, modes of anion-NDI interactions vary from extremely weak non-chromogenic anion-π interactions to chromogenic anion-induced charge-transfer (CT) and electron-transfer (ET) phenomena. In aprotic solvents, electron-donating abilities of anions generally follow their Lewis basicity order, whereas π-acidity of NDIs can be fine-tuned by installing different electron-rich and electron-deficient substituents. While strongly Lewis basic anions (OH(-) and F(-)) undergo thermal ET with most NDIs, generating NDI(?-) radical anions and NDI(2-) dianions in aprotic solvents, weaker Lewis bases (AcO(-), H(2)PO(4)(-), Cl(-), etc.) often require the photoexcitation of moderately π-acidic NDIs to generate the corresponding NDI(?-) radical anions via photoinduced ET (PET). Poorly Lewis basic I(-) does not participate in thermal ET or PET with most NDIs (except with strongly π-acidic core-substituted dicyano-NDI) but forms anion/NDI CT or anion-π complexes. We have looked for experimental evidence that could indicate alternative mechanisms, such as a Meisenheimer complex or CH···anion hydrogen-bond formation, but none was found to support these possibilities.     

Delivery of 9-Cis retinal to photoreceptors from bovine serum albumin

Retinoids are labile compounds with less than micromolar solubility in aqueous solutions. They are normally associated with a carrier protein, interphotoreceptor retinoid binding protein, in the interstitial spaces of the retina. In the past, experimental retinoids have been delivered to isolated retinas and photoreceptors using either unprotected ethanolic suspensions or phospholipid vesicles that protect but require burdensome preparation. The objective of these experiments was to characterize the protection of retinoids and their delivery to isolated photoreceptor cells at high concentrations using fatty-acid-free bovine serum albumin (BSA) as a convenient vehicle and protectant. Our results confirm that BSA is a useful protectant and vehicle for delivery of retinoids to isolated retinas and photoreceptors.     

The 6-property for simplicial complexes and a combinatorial Cartan-Hadamard theorem for manifolds

The 6-property for 2-dimensional simplicial complexes is the condition that every nontrivial circuit in the link of a vertex has length greater than or equal to six. If a compact -manifold has a 2-dimensional spine with the 6-property, then we show that the interior of is covered by euclidean -space. In dimension , we show further that such a 3-manifold is Haken.

     

Nodal quasiparticle lifetime in the superconducting state of Bi(2)Sr(2)CaCu(2)O(8+delta)

We have measured the complex conductivity sigma of a Bi(2)Sr(2)CaCu(2)O(8+delta) thin film between 0.2 and 0.8 THz. We find sigma in the superconducting state to be well described as the sum of contributions from quasiparticles, condensate, and order parameter fluctuations which draw 30% of the spectral weight from the condensate. An analysis based on this decomposition yields a quasiparticle scattering rate on the order of k(B)T/Planck's over 2pi for temperatures below T(c).     

INTERPHOTORECEPTOR RETINOID-BINDING PROTEIN AND α-TOCOPHEROL PRESERVE THE ISOMERIC AND OXIDATION STATE OF RETINOL

Retinol decomposes rapidly into a number of products, including its aldehyde form, retinal, when introduced into buffer in phospholipid vesicles or ethanol. Interphotoreceptor retinoid-binding protein at low concentrations is found to protect retinol from isomerization and oxidation. The addition of alpha-tocopherol to either liposomes or an ethanolic-buffer solution also prevents decomposition. Neither of these agents interferes with the successful regeneration of pigment with 9-cis retinal in rod outer segment preparations or the restoration of sensitivity by retinoids in isolated rod photoreceptors.