Conformational ordering of apolar, chiral m-phenylene ethynylene oligomers

A series of m-phenylene ethynylene oligomers containing nonpolar, (S)-3,7-dimethyl-1-octanoxy side chains have been synthesized and studied. In apolar alkane solvents, oligomers of sufficient length (n > 10) were found to adopt a helical conformation with a large twist sense bias. In contrast, in chloroform the oligomers adopt a random coil conformation. Surprisingly, the strong twist sense bias was determined to be highly time dependent and is partially attributed to intermolecular aggregation.     

Side chain effect on the double helix formation of ethynylhelicene oligomers

Three series of ethynylhelicene oligomers with different side chains were synthesized: (P)-bD-n (n = 2-6) with branched alkyloxycarbonyl side chains; (P)-S-n (n = 2-7) with decylsulfanyl side chains; and (P)-DF-n (n = 4, 6, 8, 10) with alternating decyloxycarbonyl and perfluorooctyl side chains. The double helix formation of these side chain derivatives was compared to that of (P)-D-n with decyloxycarbonyl side chains. CD, UV-vis, and vapor pressure osmometry (VPO) studies showed that (P)-bD-n formed double helices as well as (P)-D-n. CD studies in trifluoromethylbenzene at different temperatures and concentrations indicated that the stability of the aggregate of (P)-bD-6 was similar to that of (P)-D-6. Bulkiness of side chains had little effect on aggregation, which indicated that π-π interactions of the aromatic moiety were essential for double helix formation. (P)-S-n were random coils in all solvents examined except in trifluoromethylbenzene. Whereas (P)-D-7 formed a double helix at 1 × 10(-3) M in toluene, (P)-S-7 was a random coil. This result indicated that the double helix forming ability of (P)-S-n was substantially lower than that of (P)-D-n. Based on the previous observation that (P)-F-n formed a more stable double helix than (P)-D-n, the order of stability may be summarized as follows: (P)-F-n > (P)-D-n and (P)-bD-n >(P)-S-n. The lower stability of (P)-S-n compared to that of (P)-F-n was ascribed to the softness and/or the electron-rich nature at the m-phenylene moiety. (P)-DF-n did not form a stable double helix. It was speculated that a regular alternating arrangement of soft/hard or electron-rich/deficient moieties is important for stable double helix formation. Side chains of ethynylhelicene oligomers can play significant roles in determining the stability of double helices.     

Why a hexabromodiquinoline host preferentially includes small aromatic hydrocarbon guests

The preparation and properties of the new hexabromodiquinoline derivative 4 are described. This lattice inclusion host shows a strong preference for trapping small aromatic hydrocarbons. The X-ray crystal structures of the benzene, toluene, o-xylene, and p-xylene compounds are reported, and are analysed from a crystal engineering perspective. Crystallisation of 4 from the dual-nature solvent trifluoromethylbenzene yields the solvent-free material. Comparison of the parent crystal structure with those of its inclusion compounds reveals why inclusion of aromatic hydrocarbon guests is such a favoured process. The high concentration of Br...Br interactions in the structure of pure 4 is diluted and increasingly replaced by aromatic offset face-face (OFF) and aromatic edge-face (EF) interactions in the inclusion compounds, and this results in better lattice packing energies. For toluene, o-xylene, and p-xylene the host-guest ratio is 1:1. Inclusion of the smaller benzene molecule results in a change to 2:3 stoichiometry. This increase in guest content is assisted by replacement of host-host OFF and EF motifs with host-host pi-halogen dimer (PHD) interactions, which provide space for inclusion of the additional guest molecules. These changes result in the most efficient lattice packing of the series for compound (4)2.(benzene)3.     

Guest-enhanced kinetic stability of hydrogen-bonded dimeric capsules of tetraurea Calix

Inclusion complexes of self-assembled molecular dimers composed of two tetratolylurea calix[4]arenes show strongly different kinetic stability for different guests. In cyclohexane-d(12), half-life times for the exchange of a guest against the solvent vary from 2.9 h (chloroform) through 20 h (benzene) and 74 h (fluorobenzene) to 78 days for cyclohexane. This demonstrates that the kinetic stability of such a dimer can be strongly increased by the choice of a suitable guest.     

Synthesis of fluorine-containing dibenzenechromium nitriles using chromium vapor

Conclusions The cocondensation of chromium and two aromatic compounds gives mixed bisarenchromium complexes, namely, fluorobenzene(benzonitrile)chromium and trifluoromethylbenzene(benzo-nitrile)chromium.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 237–239, January, 1986.The authors thank N. I. Basyukova for carrying out the mass spectral measurements.     

Structural Evolution Process in Solvent-Induced Crystallization Phenomenon of Syndiotactic Polystyrene

Structural change has been traced in the solvent-induced crystallization phenomenon of syndiotactic polystyrene through the time-resolved measurements of infrared and Raman spectra and X-ray diffraction. Immediately after the solvent is supplied to the glassy sample, the random coils start a micro-Brownian motion and locally change to short regular helical segments after some induction time. These segments grow longer and gather together to form the crystal lattice. This crystallization occurs even at room temperature far below the original glass transition temperature (Tg = ca. 100°C), because Tg is shifted to ca. −90°C (in the case of chloroform) due to the plasticizing effect, as revealed by the temperature-dependent infrared spectral measurement and the molecular dynamics calculation. The thus-created sPS-solvent complex was found to show a fast and reversible solvent exchange phenomenon between the originally-existing solvent (toluene, for example) and the newly-supplied different type of solvent (chloroform, for example). The time-dependent measurement of wide-angle and small-angle X-ray scatterings using a synchrotron radiation source revealed that the solvent exchange occurs with keeping both the columnar structure of the crystal and the stacked lamellar structure, and that the solvent exchange rate is in the order of chloroform > benzene > toluene, reflecting the difference in diffusion rate of solvent molecules and polymer-solvent interaction.     

Equilibrium Shift in Solution: Molecular Shape Recognition and Precipitation of a Synthetic Double Helix Using Helicene‐Grafted Silica Nanoparticles

Chiral silica nanoparticles (70 nm) grafted with (P)‐helicene recognized the molecular shape of double helix and random coil (P)‐ethynylhelicene oligomers in solution. A mixture of the (P)‐nanoparticles and double helix precipitated much faster than a mixture of the (P)‐nanoparticles and random coil, and the precipitate contained only the double helix. The mixture of the (P)‐nanoparticles and (P)‐ethynylhelicene pentamer reversibly dispersed in trifluoromethylbenzene upon heating at 70 °C and precipitated upon cooling at 25 °C. When a 10:90 equilibrium mixture of the double helix and random coil in solution was treated with the (P)‐nanoparticles, the double helix was precipitated in 53 % yield and was accompanied by equilibrium shift.     

1,3,5-三[(4’-乙炔基苯基)乙炔基]苯的合成

设计了多种合成路线制备芳香炔基树枝状化合物中间体1,3,5-三[(4’-乙炔基苯基)乙炔基]苯,通过一系列的合成路线和反应条件的对比,发现多官能团的端基炔化合物与芳基溴化合物之间发生多重Sonogashira反应时,常会生成不同取代程度的极性相似化合物,因而难以分离.采用多官能团的端基炔化合物与芳基碘化合物反应可以避免这种情况.最终确定以1,3,5-三溴苯和2-甲基-3-丁炔-2-醇为原料,制得中间产物1,3,5-三乙炔基苯;再以对碘苯胺和三甲基硅乙炔为原料,经重氮化化、卤代反应制得4-三甲基硅乙炔基碘苯;后者与1,3,5-三乙炔苯经Sonogashira反应、裂解去保护反应,制得化合物1,3,5-三[(4’-乙炔基苯基)乙炔基]苯.用1H NMR,13C NMR,元素分析等表征手段确认了中间体及最终产物的结构.     

Polymerization of aromatic nuclei. XII. Oligomerization of halobenzenes by aluminum chloride-cupric chloride

Polymerization of chloro- and fluorobenzene by aluminum chloride-cupric chloride produced highly colored oligomers. Chlorobenzene reacted under the standard conditions, i.e., 6/1/0.5 (molar ratio) of aromatic/catalyst/oxidant at 60°C. for 1 hr., to give a red solid in 14% yield. Evidence concerning the structure was obtained from elemental analyses, infrared and ultraviolet spectra, dechlorination, oxidation, solubility, molecular weight, and color. The data indicate that the backbone chain consists of an o-polyphenyl structure with chlorine atoms situated at the 4-positions. Polynuclear regions presumably comprise part of the structure. Molecular weight data pointed to an average of 10–12 units per chain. The coupled product from fluorobenzene was very similar to the chlorobenzene oligomer in most respects. In contrast to the chlorobenzene case, there was evidence of propagation occurring to some extent by attack ortho to the fluorine. Bromobenzene produced brominated p-polyphenyl apparently by disproportionation to benzene which then functioned as the monomer. An oxidative cationic mechanism (σ polymerization) is proposed for the nuclear coupling.     

Poly(γ-alkyl L-glutamates). II. Optical rotatory dispersion studies in organic solvents

Conformations of a series of poly(γ-alkyl L -glutamates) (ethyl, n-propyl, n-butyl, isobutyl, and isoamyl) were studied by ORD and infrared absorption methods. All except the n-propyl ester were found to be in helical form in nonpolar non-aromatic solvents such as ethyl acetate, chloroform, ethylene dichloride, methylene chloride, carbon tetrachloride, 2-chloroethanol, dimethylformamide, and dioxane. In such cases, the Cotton effects due to the n–π* transition of peptide bonds occurred near 234 mμ and were of a magnitude similar to those found for poly(γ-benzyl L -glutamate) and poly-L -methionine in nonpolar non-aromatic organic solvents. These four polypeptides in aromatic nonpolar solvents, such as benzene, benzyl alcohol, pyridine, and m-cresol, were also found to be in helical form, although the ORD parameters differed considerably from the values in non-aromatic solvents. An essential cause seems to be the interaction of π electrons on peptide bonds with π electrons in the solvents. Helix-coil transitions of these esters in chloroform-dichloroacetic acid mixtures (dichloroacetic acid seems to be a random coil-forming solvent) were expressed by the Shechter-Blout formulation. This was not true, however, for helix–coil transitions in benzyl alcohol–dichloroacetic acid mixtures. The dependence of the helical stability of these polypeptides in chloroform solution upon the side-chain length and upon temperature is discussed.     

单取代芳烃的硝化

以甲苯、乙苯、异丙苯、叔丁基苯、氟苯等为硝化底物,通过混酸硝化得到这些单取代芳烃转化率最大时的混酸硝化强度φ。 运用密度泛涵理论,在B3LYP/6-311G**水平上优化了9种单元芳烃的几何构型,计算苯环上C原子电荷分布。 讨论了9种取代基的定位效应,以苯环取代基以外环上C原子总净电荷QRΣC(2~6)表示单取代苯的硝化反应活性与硝化强度φ之间的关系。 实验结果表明,烷基苯、卤苯、硝基苯的硝化反应活性与其混酸硝化转化率达最大时的混酸硝化强度φ呈良好的线性关系。     

Phenanthroline dicarboxamide-based helical foldamers: stable helical structures in methanol

A series of new aromatic oligoamides 2-5 based on 1,10-phenanthroline diacid and o-phenylenediamine have been synthesized through a convergent segment coupling strategy. These oligomers can fold into well-defined helical structures in solution through intramolecular hydrogen bonds and aromatic stacking interactions, which has been established by 1H NMR, fluorescence, and UV/vis spectra. In particular, it was found that the oligomers were more favorable to fold into stable helical structures in methanol than in chloroform and dichloromethane. The helical foldamers formed in the solid state have been characterized by single-crystal X-ray diffraction analysis. The results showed that the high curvature of the strands led to one and a half turns for both 2 and 21, three turns for 4, and nearly four turns for 5.     

New Activated Difluoroaromatic Compounds Containing Internal Acetylenic Moieties

New activated difluoroaromatic compounds having an internal acetylenic moiety were synthesized by reaction of trichloroacetaldehyde with fluorobenzene, followed by reaction with iodobenzene and cross coupling with acetylene in the presence of palladium complexes. According to the results of quantum-chemical calculations and ¹⁹F NMR data, the products are highly reactive compounds which can be used for the preparation of high-molecular-weight aromatic polyethers.     

Crystal structures of monohalogenated benzoic acids

Crystal structures resulting from a combination of different types of specific intermolecular interactions have been analysed using examples of 12 monohalogenated benzoic acids (HBA). These have been compared with structures known for corresponding monofunctional compounds, namely benzoic acid, fluorobenzene, chlorobenzene and iodobenzene. It is found that common for carboxylic acids centrosymmetric hydrogen-bonded dimers exist in all HBA, and at the same time a degree of halogen atoms aggregation is rather high in the most part of HBA, similarly to chlorobenzene and iodobenzene crystals. Previously reported tendency to increasing degree of Hal-aggregation in the sequence F < Cl ≤ Br ≤ I is confirmed. It is remarkable that a stacking motif of benzene rings is realised in all HBA crystals though it is absent in all considered monofunctional substances.     

Simultaneous determination of benzene and toluene in the blood using head-space gas chromatography

A head-space method for the simultaneous determination of benzene and toluene in blood using a gas chromatograph equipped with a photoionization detector was developed. Internal standards for benzene and toluene were fluorobenzene and o-xylene, respectively, and the detection limit was 5 nmol/l for both solvents. This method is sensitive enough for needs of biological monitoring of benzene and toluene in exposed workers. With automation it offers a possibility for routine measurements. An application of the method in monitoring exposed workers in the industry is presented.     

Monitoring folding transitions of synthetic,branched-chain polypeptides by capillary zone electrophoresis

The coil/helix transition of a synthetic, branched-chain polymeric polypeptide (poly (Lys(Glu(1)-DL-Ala(3))EAK), 50-Lys residues long in the backbone, as a function of increasing molarities of methanol in solution, is here studied by both, circular dichroism (CD) and capillary zone electrophoresis. CD spectra showed that, at 75% v/v methanol, the transition from random coil to fully helical structure was obtained, in a pH 1.1 HCI solution in the presence of 20 mM NaCI. CZE studies, run in parallel, exhibited the classical unfolding to folding sigmoidal transition, with mid-point at 60% v/v methanol concentration, plateauing at ca. 80% v/v organic solvent. Surprisingly, though, such unfolding to folding transition was accompanied by an expansion, rather than a contraction, of the resulting ordered polypeptide. As the charge of the polypeptide (a pure polycation at a pH of 2.1 in CZE) was kept rigorously constant, a plot of the radius of the polymer along the sigmoidal transition clearly showed that the radius of gyration of the helical, structured polypeptide was in fact larger than that of the random coil. Such results were confirmed by molecular dynamics simulations, which indicated that the dimensions of such polypeptide, in alpha-helix configuration, were 8.5 nm (in length) and 3.2 nm (in diameter), whereas those of the corresponding random coil were 7.2 nm (in length) and 5.1 nm (length of shorter axis). It would thus appear that the randomized structure assumes the shape of a more compact object, roughly resembling a "rugby ball".     

Consistent assignment of the vibrations of monosubstituted benzenes

We investigate the consistency of the labeling and assignments of the vibrations of the monosubstituted benzenes in the electronic ground state. In doing so, we also identify some inconsistencies in the labeling of the benzene modes. We commence by investigating the behavior of the benzene vibrations as one hydrogen is replaced by an artificial atomic substituent of increasing mass via quantum chemical calculations; the wavenumber variations with mass give insight into the assignments. We also examine how well the monohalobenzene vibrations can be described in terms of the benzene ones: consistent with some recent studies, we conclude that this is futile in a significant number of cases. We then show that "isotopic wavenumbers" obtained by artificially changing the mass of the fluorine atom in fluorobenzene are in very good agreement with the wavenumbers obtained via explicit calculation for the relevant monohalobenzene (chlorobenzene, bromobenzene, and iodobenzene) vibrations. As a consequence, we propose that the vibrations of monofluorobenzene be used as the basis for labelling the vibrational assignments of monosubstituted benzenes. As well as the four monohalobenzenes, we also apply this approach to the vibrations of aniline, toluene, benzonitrile, phenylacetylene, phenylphosphine, and nitrobenzene. This has allowed a much more consistent picture of the vibrational assignments to be obtained across ten monosubstituted benzenes.     

Adsorption of radioisotopes from their organic solutions on filter papers the Sb(III)-nonpolar solvents-system

The extraction of Sb(III) chloride by nonpolar solvents from 0.15M HCl was studied as a function of sulphuric acid concentrations in the aqueous phase. The distribution of Sb(III) chloride between the nonpolar solvents benzene, toluene, xylene, nitrobenzene, cyclohexane, chloroform and carbon tetrachloride and filter paper is reported. In case of benzene the Sb(III) activity (given in counts·s^–1·ml^–1) decreases from 1500 to 200 after 24 hours. The corresponding values are about 1200 and 540 for toluene, 1330 and 50 for xylene, 1050 and 700 for nitrobezene, 1080 and 22 for cyclohexane, 330 and 30 for chloroform and 130 and 40 for carbon tetrachloride. More than 95% of the adsorbed Sb(III) is desorbed by 1M HNO₃, 1M HCl or 0.5M H₂SO₄ by contacting the loaded filter paper with any of these acids for 27 hours.     

Kinetics of Helix‐Handedness Inversion: Folding and Unfolding in Aromatic Amide Oligomers

A series of helically folded oligoamides of 8‐amino‐2‐quinoline carboxylic acid possessing 6, 7, 8, 9, 10 or 16 units are prepared following convergent synthetic schemes. The right‐handed (P) and the left‐handed (M) helical conformers of these oligomers undergo an exchange slow enough to allow their chromatographic separation on a chiral stationary phase. Thus, the M conformer is isolated for each of these oligomers and its slow racemization in hexane/CHCl₃ solutions is monitored at various temperatures using chiral HPLC. The kinetics of racemization at different temperatures in hexane/CHCl₃ (75:25 vol/vol) are fitted to a first order kinetic model to yield the kinetic constant and the Gibbs energy of activation for oligomers having 6, 7, 8, 9, 10 or 16 quinoline units. This energy gives the first quantitative measure of the exceptional stability of the helical conformers of an aromatic amide foldamer with respect to its partly unfolded conformations that occur between an M helix and a P helix. The trend of the Gibbs energy as a function of oligomer length suggests that helix‐handedness inversion does not require a complete unfolding of a helical strand and may instead occur through the propagation of a local unfolding separating two segments of opposite handedness.     

Preresonance Raman intensity studies in electron donor/acceptor complexes of tetracyanoethylene

The preresonance Raman intensity enhancement for the ν_C=C and ν_CN vibrations of TCNE complexed with toluene, benzene and fluorobenzene is established. Conclusions regarding the electronic states responsible for the effect are presented.