A Spirocyclohexyl Nitroxide Amino Acid Spin Label for Pulsed EPR Spectroscopy Distance Measurements

Site‐directed spin labeling and EPR spectroscopy offer accurate, sensitive tools for the characterization of structure and function of macromolecules and their assemblies. A new rigid spin label, spirocyclohexyl nitroxide α‐amino acid and its N‐(9‐fluorenylmethoxycarbonyl) derivative, have been synthesized, which exhibit slow enough spin‐echo dephasing to permit accurate distance measurements by pulsed EPR spectroscopy at temperatures up to 125 K in 1:1 water/glycerol and at higher temperatures in matrices with higher glass transition temperatures. Distance measurements in the liquid nitrogen temperature range are less expensive than those that require liquid helium, which will greatly facilitate applications of pulsed EPR spectroscopy to the study of structure and conformation of peptides and proteins.     

Oxetanes as versatile elements in drug discovery and synthesis

Sizable resources, both financial and human, are invested each year in the development of new pharmaceutical agents. However, despite improved techniques, the new compounds often encounter difficulties in satisfying and overcoming the numerous physicochemical and many pharmacological constraints and hurdles. Oxetanes have been shown to improve key properties when grafted onto molecular scaffolds. Of particular interest are oxetanes that are substituted only in the 3-position, since such units remain achiral and their introduction into a molecular scaffold does not create a new stereocenter. This Minireview gives an overview of the recent advances made in the preparation and use of 3-substituted oxetanes. It also includes a discussion of the site-dependent modifications of various physicochemical and biochemical properties that result from the incorporation of the oxetane unit in molecular architectures.     

2-β-二酮-1,3,2-二苯并[d.f]和二萘并(α,β)[d.f]-二氧硼杂环庚二烯的合成与结构

四配位硼化合物化学是硼化学的重要组成部分,许多化学工作者对此进行过大量研究。然而,有关螺型四配位硼化合物的报道却很少。先前,作者曾合成出以硼为螺原子的螺环[4.5]和螺环[5.5]化合物;本文则报道,     

Dynamic nuclear polarization enhancement of protons and vanadium‐51 in the presence of pH‐dependent vanadyl radicals

We report applications of dynamic nuclear polarization to enhance proton and vanadium‐51 polarization of vanadyl sulfate samples doped with TOTAPOL under magic angle spinning conditions. The electron paramagnetic resonance response stemming from the paramagnetic ⁵¹V species was monitored as a function of pH, which can be adjusted to improve the enhancement of the proton polarization. By means of cross‐polarization from the proton bath, ⁵¹V spins could be hyperpolarized. Enhancement factors, build‐up times, and longitudinal relaxation times T₁(¹H) and T₁(⁵¹V) were investigated as a function of pH. Copyright © 2014 John Wiley & Sons, Ltd.     

19F Dynamic Nuclear Polarization and SEM in Suspensions Consisting of Fluorobenzene Derivatives and Asphaltene Extracted from MC-800 Liquid Asphalt

A variety of analytical techniques, such as scanning electron microscopy and ¹⁹F dynamic nuclear polarization (DNP) methods, are applied to characterize asphaltene extracted from MC-800 liquid asphalt in fluorobenzene derivatives at 1.53 mT and at room temperature. Different solvents show variable affinities for the asphaltene surface. The low field EPR spectrum of the asphaltene/hexafluorobenzene sample was recorded. The DNP parameters were determined. Additionally, the interactions between the nuclei of the solvent and the electrons delocalized on the asphaltene are interpreted. Not only dipolar but also scalar interactions between the nuclear spin and the electron spin were found.     

A [2+2+2]‐Cyclotrimerization Approach to Selectively Substituted Fluorenes and Fluorenols,and Their Conversion to 9,9′‐Spirobifluorenes

Synthesis of selectively substituted fluorenes and fluorenols was achieved by using catalytic [2+2+2]cyclotrimerization. Various starting diynes were reacted with different alkynes in the presence of a catalytic amount of Wilkinson’s catalyst (RhCl(PPh₃)₃) providing the compounds possessing the fluorene scaffold in good isolated yields. A set of four regioselectively substituted fluorenols was converted to the corresponding 9,9′‐spirobifluorenes and their spectral characteristics were measured.     

New spirocyclic sesquiterpenes from the marine sponge Geodia exigua

Three new spirocyclic sesquiterpenes designated exiguamide (1), exicarbamate (2) and exigurin (3), together with (−)-10-epi-axisonitrile-3 (4), have been isolated from the marine sponge Geodia exigua. All four compounds possess the spiro[4.5]decene skeleton and their structures were determined on the basis of spectroscopic data. The structure of 1 was confirmed by X-ray crystallographic analysis and the absolute configuration was determined by applying the modified Mosher's method on its amine derivative. Exiguamide (1) inhibited cell fate specification during sea urchin embryogenesis at a minimum inhibitory concentration of 0.4 μM.     

Modulation of unconventional fluorescence of novel photochromic perimidine spirodimers

Fluorescence modulation by a class of photochromic perimidine spirodimers, which exhibit a characteristic fluorescence associated with their photochromic reactions, has been described. Upon irradiation using 365 nm light, these non-fluorescent spiro molecules undergo a thermally-reversible ring opening at their spiro junction resulting in the generation of strong fluorescence. The fluorescing species is distinctly different from both the stable ring-closed and the ring-opened compounds, though it appears to have been formed from and remains in equilibrium with the photochemically generated ring-opened form. While the fluorescing species possesses a narrow absorption band with its maximum centered at 500 nm, the ring-opened form exhibits a broad absorption across the visible region with two maxima centered at 410 and 650 nm, respectively. After initiating the photochromic reactions in these molecules using 365 nm light, purely photochemically-controlled fluorescence modulation can be carried out using two wavelengths in the visible region, that is, 500 and 700 nm, while the equilibrium concentration of the ring-opened form and the fluorescing species is controlled. Fluorescence modulation is attained also by controlling the ratio of the ring-closed and ring-opened forms by photochemical ring-opening and thermal ring-closing reactions. The study on the effect of substitution of these molecules suggests that by extending the conjugation of the perimidine core in the ring-opened form the molecule is rendered non-fluorescent and hence it can be assumed that the perimidine core forms the fluorescing entity of the molecule.     

Alumina-catalyzed cyclodimerization of 4-hydroxymethyl derivatives of 1,8-bis(dimethylamino)- and 1,8-dimethoxynaphthalenes to symmetrical spiro compounds

4-Hydroxymethyl derivatives of 1,8-bis(dimethylamino)- and 1,8-diiiiethoxynaphthalenes undergo cyclodirnerization on alumina to form symmetrical spir0, compounds of the head-to-tail type. The reaction is considered to be a two-step electrophilic substitution with the participation of naphthyhiiethyl carbocations.Translated fromIzvestiya Akademii Nauk, Seriya Khitnicheskaya, No. 4, pp, 1016–1018, April, 1996.     

Hydrogen‐bonded bilayers in 7‐benzyl‐3‐tert‐butyl‐1‐phenyl‐4,5,6,7‐tetrahydro‐1H‐spiro[pyrazolo[3,4‐b]pyridine‐5,2′‐indan]‐1′,3′‐dione

In the title compound, C₃₁H₂₉N₃O₂, the reduced pyridine ring adopts a conformation intermediate between the envelope and half‐chair forms. The aryl rings of the benzyl and phenyl substituents are nearly parallel and overlap, indicative of an intramolecular π–π stacking interaction. A combination of two C—H...O hydrogen bonds and one C—H...N hydrogen bond links the molecules into a bilayer having tert‐butyl groups on both faces.<!?tpb=19.5pt>     

A Convenient One‐Pot Preparation of Stable Equivalents of Cyclobutane‐1,2‐dione and Cyclobutanetrione

A very short, high‐yielding, one‐pot procedure has been developed for the preparation of half‐protected cyclobutane‐1,2‐dione. This compound is much more stable than cyclobutane‐1,2‐dione itself and allowed further transformation to give diprotected cyclobutanetrione equivalents.