Light emission from gamma-irradiated alkane glasses containing olefins

After gamma-radiolysis at 77°K, glassy alkanes emit weakly in the visible on warning. The similar but stronger emission from dilute olefin solutions suggests that the alkane luminescence is due to radiolysis products. The nature of the emitters is discussed: it is concluded tentatively that they are olefins in twisted excited states formed by recombination of olefin cations.     

Kraftfeldrechnungen an Fluorenylidenfluorenen. Vergleich der berechneten Geometrie eines stark tordierten Olefins mit den R?ntgenstrukturdaten

Ohne Zusammenfassung

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Force field calculations with fluorenylidene fluorenes. Comparison of the calculated geometry of a strongly twisted olefin with the X-ray structural data

     

Fibrillisation of ring-closed amyloid peptides

Ring-closing olefin metathesis reactions are used to create intra-molecularly ring closed peptides or inter-molecularly ring-closed peptide dimers based on a designed amyloid peptide sequence. The uncrosslinked peptide self-assembles into high aspect ratio nanotubes, however ring-closing leads to the formation of fibrillar and twisted/helical ribbon structures.     

Activation of Aromatic C−F Bonds by a N-Heterocyclic Olefin (NHO)

A N-heterocyclic olefin (NHO), a terminal alkene selectively activates aromatic C−F bonds without the need of any additional catalyst. As a result, a straightforward methodology was developed for the formation of different fluoroaryl-substituted alkenes in which the central carbon–carbon double bond is in a twisted geometry.     

Olefin-linked covalent organic frameworks with twisted tertiary amine knots for enhanced ultraviolet detection

Though Olefin-linked covalent organic frameworks(oCOFs) possess excellent π-electron delocalization,the barely reversible olefin linkage brings challenges for oCOFs’ synthesis and functionalization. Here, we synthesize new oCOFs with tertiary amine knots which have twisted configuration and electron-donating nature. Investigation into the structural variation and photoelectric performance shows that the twisted configuration of oCOF-TFPA could favor to the intramolecular charge transfer process ...     

On the structure and stability of singlet and triplet disilene and silylsilylene

Ab initio SCΓ calculations on the lowest singlet and triplet states of disilene and silylsilylene with extended basis sets including polarization functions are reported. The twisted orthogonal structure for triplet disilene treated so far in the literature corresponds to a saddle point of second order whereas the true minimum is represented by a twisted bent structure.     

Cubanes: Starting Materials for the Chemistry of the 1990s and the New Century

The study of non-natural products has led to a broad understanding of bonding and reactivity in organic chemistry. Many times, compounds thought impossible have been realized in the course of such studies. Cubane, a landmark in the world of “impossible” compounds, has been found to have a rich chemistry, full of the unexpected. The recent renaissance of cubane chemistry, triggered by potential applications of the system to the production of high-energy fuels and the like, has led to many discoveries including the first methods for systematic substitution on strained, saturated systems and a new process for the metalation of arenes, ortho magnesiation. Reactive intermediates with exceptional bonding parameters have been uncovered and characterized including 1(9)-homocubene, the most twisted olefin; cubene, the most pyramidalized olefin; cubyl cation, once the “least likely” cation; cubylmethyl radical, a saturated radical that rearranges on the picosecond timescale; and many other extraordinary species. There is certainly good reason to believe that future work in the cubane arena will be at least as productive (probably more so), and that it will help develop a deeper understanding of chemistry.     

Radiationless decay of red fluorescent protein chromophore models via twisted intramolecular charge-transfer states

We use CASSCF and MRPT2 calculations to characterize the bridge photoisomerization pathways of a model red fluorescent protein (RFP) chromophore model. RFPs are homologues of the green fluorescent protein (GFP). The RFP chromophore differs from the GFP chromophore via the addition of an N-acylimine substitution to a common hydroxybenzylidene-imidazolinone (HBI) motif. We examine the substituent effects on the manifold of twisted intramolecular charge-transfer (TICT) states which mediates radiationless decay via bridge isomerization in fluorescent protein chromophore anions. We find that the substitution destabilizes states associated with isomerization about the imidazolinone-bridge bond and stabilizes states associated with phenoxy-bridge bond isomerization. We discuss the results in the context of chromophore conformation and quantum yield trends in the RFP subfamily, as well as recent studies on synthetic models where the acylimine has been replaced with an olefin.     

A multifaceted phosphate tether: application to the C1-C14 subunit of dolabelides A-D

A phosphate tether approach to the C1-14 subunit of dolabelide is described. The phosphate tether serves a multifaceted role mediating several processes, including (i) diastereotopic differentiation via RCM, (ii) selective CM by imparting Type III behavior to the exocyclic olefin, (iii) regioselective hydrogenation, and (iv) regioselective Pd(0)-catalyzed reductive opening of the bicyclic phosphate. Overall, this strategy uses orthogonal protecting- and leaving-group properties innate to phosphate esters to rapidly assembly the titled subunit.     

Metal—olefin bonding. X-ray structures of trichloro-1,6-bis(diphenylphosphino)-trans-hex-3-enerhodium(III) and dichlorocarbonyl-1,6-bis(diphenylphosphino)-trans-hex-3-eneruthenium(II)

X-ray structures have been determined for the olefin-containing complexes RuCl₃(BDPH) and RuCl₂(CO)(BDPH); BDPH = 1,6-bis(diphenylphosphino)-trans-hex-3-ene. Both compounds crystallise in space group Pbca with eight molecules in unit cells of dimensions RhCl₃(BDPH) a 16.109(8), b 20.359(12), c 17.194(4) Å; RuCl₂(CO)(BDPH) a 16.279(1), b 20.160(1), c 17.334(1) Å. Least-squares refinement returned residuals, R, of 0.030 and 0.067 respectively. In the ruthenium complex the CO and one Cl ligand are statistically interchanged. Both complexes are characterised by weak metal—olefin bonding and a twisted olefin orientation. The geometries are compared with those in other Ir^I and Ir^III complexes containing the BDPH ligand.     

Isomerizing Olefin Metathesis

Isomerizing olefin metathesis is currently undergoing a transformation from laboratory curiosity to powerful synthetic concept at the heart of orthogonal tandem catalysis. In this process, an isomerization catalyst continuously moves double bonds along carbon chains, while a metathesis catalyst scrambles the residues at the C−C double bonds. This cooperative action of two catalysts can be used to access single, defined products from a complex mixture of compounds. Alternatively, it enables the transformation of uniform starting materials into complex product blends with defined, tunable properties. This concept article highlights recent developments and potential applications of this fascinating reaction concept.     

An efficient and enantioselective total synthesis of naturally occurring L-783277

Naturally occurring L-783277 which belongs to 14-membered resorcylic acid lactones (RALs) turned out to be a potent kinase inhibitor against MEK (MAP kinase kinase). We successfully accomplished efficient and enantioselective total synthesis of L-783277 based on convergent assembly of one aromatic unit and two chiral building blocks with efficient orthogonal protection-deprotection strategy. Three key steps composed of olefin cross metathesis, addition of acetylene derivative to aldehyde, and Yamaguchi macrolactonization were subsequently employed to construct the framework of L-783277. The optical rotation value of L-783277 is for the first time presented in this Letter.     

Twisted aromatics, 9-anthryl and 1-pyrenyl terpyridines organize into novel multi-directional ‘ladder-like’ motifs in the solid state

9-Anthryl and 1-pyrenyl terpyridines (1 and 2, respectively), key precursors for the design of novel fluorescent sensors have been synthesized and characterized by ¹H NMR, mass spectroscopy and X-ray crystallography. Twisted molecular conformations for each 1 and 2 were observed in their single crystal structures. Energy minimization calculations for the 1 and 2 using the semi-empirical AM1 method show that the ‘twisted’ conformation is intrinsic to these systems. We observe interconnected networks of edge-to-face CHπ interactions, which appear to be cooperative in nature, in each of the crystal structures. The two twisted molecules, although having differently shaped polyaromatic hydrocarbon substituents, show similar patterns of edge-to-face CHπ interactions.The presently described systems comprise of two aromatic surfaces that are almost orthogonal to each other. This twisted or orthogonal nature of the molecules leads to the formation of interesting multi-directional ladder like supramolecular organizations. A combination of edge-to-face and face-to-face packing modes helps to stabilize these motifs. The ladder like architecture in 1 is helical in nature.     

Prevention of undesirable isomerization during olefin metathesis

1,4-Benzoquinones have been found to prevent olefin isomerization of a number of allylic ethers and long-chain aliphatic alkenes during ruthenium-catalyzed olefin metathesis reactions. Electron-deficient benzoquinones are the most effective additives for the prevention of olefin migration. This mild, inexpensive, and effective method to block olefin isomerization increases the synthetic utility of olefin metathesis via improvement of overall product yield and purity.     

工业Fe-Mn催化剂上基于详细反应机理的F-T合成动力学模型Ⅱ.不同校正方法的动力学模型分析

 通过平衡闪蒸模拟催化剂孔道液体组成、烯烃物理吸附和虚拟烯烃分压等方法,考察了化学反应以外的非本征因素对F-T合成动力学模型的校正. 平衡闪蒸模拟催化剂孔道中烯烃组成的校正计算结果表明,在烯烃浓度出现峰值前,溶解度效应对烯烃再吸附及参与二次反应起主导作用,而在烯烃浓度出现峰值后,烯烃的扩散和物理吸附等效应可能起主导作用. 分析烯烃添加的反应器模拟结果发现,考虑烯烃物理吸附作用的动力学模型校正方法不能够正确反映烯烃添加实验的定性规律,而虚拟烯烃分压校正方法能够正确反映烃分布规律并可定量预测烯烃添加对产物分布规律的影响,这对需要尾气循环的F-T合成工业操作具有重要意义.     

On the determination of order parameters for homogeneous and twisted nematic liquid crystals from Raman spectroscopy

Traditional approaches to the use of Raman spectroscopy as an aid to the determination of local order parameters in liquid crystalline materials have employed polarizations of the excitation source and/or the analyser which are orthogonal to the liquid crystalline director. The present paper describes a Raman study, which seeks to take advantage of the additional information available from examining the complete range of orientations of the director in relation to these polarization directions. A theory is developed which shows how it is possible to use this additional information to derive more reliable values of the P₂ and P₄ local order parameters in homogeneous and twisted nematic liquid crystal cells.     

π Groups in ion pair bonding: the structural effects of reduction on the olefinic bond as observed in the molecular structure of Δ9,9′-bifluorenyl bis(lithium tetramethylethylenediamine)

The reaction of 9,9′-bifluorene with n-butyllithium in the presence of tetramethylethylenediamine (TMEDA) results in the formation of Δ^9,9′-bifluorenyl bis-(lithium tetramethylethylenediamine). In the molecular structure of this material, which formally can be considered to be the dianion of the olefin Δ^9,9′-bifluorene, two TMEDALi groups are closely associated with the 9,9′ bond. The fluorenyl groups are twisted relative to each other by an angle of 48.0(5)°, as compared to 42° in the parent olefin. The 9,9′ bond length is increased from 1.39(2) Å in Δ^9,9′-bifluorene to 1.487(5)Å in the dianion.Single crystal X-ray diffraction techniques were used and resulted in a final discrepancy factor of R_w = 0.064 for 2426 observations. The crystal system is monoclinic (C2/c) with a = 10.814(3), b = 16.717(6) and c = 19.766(6) Å, β = 102.55(2)°; ?_obs = 1.10(3) g cm^?3; ?_calc = 1.095 g cm^?3 for four molecules per unit cell.     

Olefin Recovery by *BEA-Type Zeolite Membrane: Affinity-Based Separation with Olefin−Ag+ Interaction

Ag⁺ was introduced into *BEA-type zeolite membrane by an ion-exchange method to enhance olefin selectivity. Ag−*BEA membrane exhibited superior olefin separation performance for both ethylene/ethane and propylene/propane mixtures. Particularly, the separation factor for ethylene at 373 K reached 57 with the ethylene permeance of 1.6×10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹. Adsorption properties of olefin and paraffin were evaluated to discuss contribution of Ag⁺ to separation performance enhancement. A strong interaction between olefin and Ag⁺ in the membrane caused preferential adsorption of olefin against paraffin, leading to selective permeation of olefin. Ag−*BEA membrane also exhibited high olefin selectivities from olefin/N₂ mixtures. The affinity-based separation through Ag−*BEA membrane showed a high potential for olefin recovery and purification from various gas mixtures.     

Synthesis of calcineurin-resistant derivatives of FK506 and selection of compensatory receptors

We used olefin metathesis to synthesize C40 derivatives of FK506 and measured their ability, when complexed to FKBP12, to inhibit calcineurin's phosphatase activity. We identified modular dimerization domains (CABs) containing segments of the calcineurin A and B polypeptides. These CABs respond to FK506 both when overexpressed in mammalian cells and in yeast or mammalian three-hybrid assays. Using chemical genetic selection, we identified compensatory mutant CABs that respond to a calcineurin-resistant FK506 derivative at concentrations well below the response threshold for CABs containing only wild-type calcineurin sequence. These reagents provide a small molecule-protein combination orthogonal to existing dimerizer systems and may be used with existing systems to increase the complexity of induced-proximity experiments. This new use of the "bump-hole" strategy protects target cells from complications arising from the inhibition of endogenous calcineurin.     

催化裂化油浆中烯烃分布研究

以某催化裂化油浆为原料,通过二烯值和溴价分析方法测定了其四组分和五个馏分中共轭烯烃(双键)和烯烃(双键)的含量;同时结合紫外光谱法、核磁共振氢谱法(~1H-NMR)对其四组分和五个馏分中的烯烃类型和含量进行了表征和测定。结果表明,催化裂化油浆中的确存在烯烃(双键)和共轭烯烃(双键),其烯烃(双键)和共轭烯烃(双键)的含量高达21%和6%,四组分中的共轭烯烃(双键)含量依次增多,五个馏分中共轭烯烃(双键)的含量在5%左右,且四组分和五个馏分中烯烃(双键)的含量均呈现先减小后增大的趋势。同时,不同组分和不同馏分之间正构α-烯烃和内烯烃的含量也存在差异。