The preparation and properties of cyanobiphenyl liquid crystal droplets encapsulated by the polymerizable lecithin 1,2-bis(10,12-tricosadiynoyl)-sn-glyero-3-phosphocholine (DC8,9PC) are described. Under a wide variety of preparation conditions the droplets obtain a diameter of approximately 10 mum. These droplets are stable for periods of over one year at room temperature. Furthermore, they are stable upon temperature cycling between the nematic and isotropic phases and between the smectic A to nematic to isotropic phase transitions. 相似文献
In this work we show through an analytic solution of the set of two coupled dynamic equations for the slowly varying amplitudes of the Stokes optical field and material density in stimulated Brillouin scattering (SBS), its analysis and a set of experiments, that the SBS-induced delay of an output Stokes pulse which is amplified by the SBS interaction is due exclusively to the inertia of the acoustic wave excitation. 相似文献
Middle-sized bn (n????5) fragments of protonated peptides undergo selective complex formation with ammonia under experimental conditions typically used to probe hydrogen?Cdeuterium exchange in Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Other usual peptide fragments like y, a, a*, etc., and small bn (n????4) fragments do not form stable ammonia adducts. We propose that complex formation of bn ions with ammonia is characteristic to macrocyclic isomers of these fragments. Experiments on a protonated cyclic peptide and N-terminal acetylated peptides fully support this hypothesis; the protonated cyclic peptide does form ammonia adducts while linear bn ions of acetylated peptides do not undergo complexation. Density functional theory (DFT) calculations on the proton-bound dimers of all-Ala b4, b5, and b7 ions and ammonia indicate that the ionizing proton initially located on the peptide fragment transfers to ammonia upon adduct formation. The ammonium ion is then solvated by N+-H??O H-bonds; this stabilization is much stronger for macrocyclic bn isomers due to the stable cage-like structure formed and entropy effects. The present study demonstrates that gas-phase guest?Chost chemistry can be used to selectively probe structural features (i.e., macrocyclic or linear) of fragments of protonated peptides. Stable ammonia adducts of b9, b9-A, and b9-2A of A8YA, and b13 of A20YVFL are observed indicating that even these large b-type ions form macrocyclic structures. 相似文献
The fragmentation reactions of the MH+ ions as well as the b7, a7, and a7* ions derived therefrom have been studied in detail for the octapeptides MAAAAAAA, AAMAAAAA, AAAAMAAA, and AAAAAAMA. Ionization was by electrospray using a QqToF mass spectrometer, which allowed a study of the evolution of the fragmentation channels as a function of the collision energy. Not surprisingly, the product ion mass spectra for the b7 ions are independent of the original precursor sequence, indicating macrocyclization and reopening to the same mixture of protonated oxazolones prior to fragmentation. The results show that this sequence scrambling results in a distinct preference to place the Met residue in the C-terminal position of the protonated oxazolones. The a7 and a7* ions also produce product ion mass spectra independent of the original peptide sequence. The results for the a7 ions indicate that fragmentation occurs primarily from an amide structure analogous to that observed for a4 ions (Bythell et al. in J Am Chem Soc 132:14766–14779, 2010). Clearly, the rearrangement reaction they have proposed applies equally well to an ions as large as a7. The major fragmentation modes of the MH+ ions at low collision energies produce b7, b6, and b5 ions. As the collision energy is increased further fragmentation of these primary products produces, in part, non-direct sequence ions, which become prominent at lower m/z values, particularly for the peptides with the Met residue near the N-terminus.
The fragmentation reactions of the MH+ ions of Leu-enkephalin amide and a variety of heptapeptide amides have been studied in detail as a function of collision energy using a QqToF beam type mass spectrometer. The initial fragmentation of the protonated amides involves primarily formation of bn ions, including significant loss of NH3 from the MH+ ions. Further fragmentation of these bn ions occurs following macrocyclization/ring opening leading in many cases to bn ions with permuted sequences and, thus, to formation of non-direct sequence ions. The importance of these non-direct sequence ions increases markedly with increasing collision energy, making peptide sequence determination difficult, if not impossible, at higher collision energies.
Electrophilic trisubstituted ethylenes, ring-disubstituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO2CH3, where R is 2,5-dichloro, 3,5-dichloro, 2,3-difluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro, 4-chloro-3-fluoro, 2-chloro-5-nitro, and 2-chloro-6-nitro were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and methyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. The order of relative reactivity (1/r1) for the monomers is 4-Cl-3-F (4.87) > 2,3-F2 (4.49) > 3-Cl-4-F (3.50) > 3-Cl-2-F (2.96) > 2-Cl-5-NO2 (2.02) > 2,5-Cl2 (1.54) > 2-Cl-6-NO2 (1.00) > 3,5-Cl2 (0.41). Relatively high Tg of the copolymers in comparison with that of polystyrene indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500ºC range with residue (1.5–34.5% wt), which then decomposed in the 500-800ºC range. 相似文献
Abstract High molecular weight polyphenyl-as-triazines were prepared at ambient temperature by the cyclopolycondensation of perfluoroglutaramidrazone and perfluoroadipamidrazone with various bis(1,2-dicarbonyl) monomers. The effect which the perfluoroalkylene group had upon certain chemical and physical properties of the polymers was determined. Thermal evaluation involved TGA, DSC, TMA, and isothermal weight loss studies of films at 232 °C in air. The polymers exhibited excellent hydrolytic stability as evidenced by retention of ninh after boiling in water (24 hr) and 10% sodium hydroxide solution (8 hr). A stable uncyclized intermediate was isolated from the reaction of perfluoroadipamidrazone and benzil which was cyclized to the phenyl-as-triazine model compound [3,3′ -perfluorotetramethylenedi (5,6-diphenyl-as-triazine)]. 相似文献
A straightforward synthesis of a novel class of sugar surfactants is described. The key step is the chemoselective condensation of a hydrophobic alkoxyamine with the resident aldehyde/ketone moiety on a hydrophilic sugar. Neither protection/deprotection of the sugars nor extensive product purification is required. The method allows for the facile adjustment of hydrophobic and hydrophilic domains of the sugar oxime ether surfactant and uses inexpensive, readily accessible, and renewable materials. 相似文献
Although cellulose nanomaterials have promising properties and performance in a wide application space, one hinderance to their wide scale industrial application has been associated with their economics of dewatering and drying and the ability to redisperse them back into suspension without introducing agglomerates or lose of yield. The present work investigates the dewatering of aqueous suspensions of cellulose nanofibrils (CNFs) using ultrasound as a potentially low-cost, non-thermal, and scalable alternative to traditional heat-based drying methods such as spray drying. Specifically, we use vibrating mesh transducers to develop a direct-contact mode ultrasonic dewatering platform to remove water from CNF suspensions in a continuous manner. We demonstrate that the degree of dewatering is modulated by the number of transducers, their spatial configuration, and the flow rate of the CNF suspension. Water removal of up to 72 wt.% is achieved, corresponding to a final CNF concentration of 11 wt.% in 30 min using a two-transducer configuration. To evaluate the redispersibility of the dewatered CNF material, we use a microscopic analysis to quantify the morphology of the redispersed CNF suspension. By developing a custom software pipeline to automate image analysis, we compare the histograms of the dimensions of the redispersed dewatered fibrils with the original CNF samples and observe no significant difference, suggesting that no agglomeration is induced due to ultrasonic dewatering. We also perform SEM analysis to evaluate the nanoscale morphology of these fibrils showing a width range of 20 nm–4 um. We estimate that this ultrasound dewatering technique is also energy-efficient, consuming up to 36% less energy than the enthalpy of evaporation per kilogram of water. Together with the inexpensive cost of transducers (<?$1), the potential for scaling up in parallel flow configurations, and excellent redispersion of the dewatered CNFs, our work offers a proof-of-concept of a sustainable CNF dewatering system, that addresses the shortcomings of existing techniques.
We report measurements of the de Haas-van Alphen effect in CeIn(3) in magnetic fields extending to approximately 90 T, well above the Néel critical field of mu(0)H(c) approximately 61 T. The unreconstructed Fermi surface a sheet is observed in the high magnetic field polarized paramagnetic limit, but with its effective mass and Fermi surface volume strongly reduced in size compared to that observed in the low magnetic field paramagnetic regime under pressure. The spheroidal topology of this sheet provides an ideal realization of the transformation from a "large Fermi surface" accommodating f electrons to a "small Fermi surface" when the f-electron moments become polarized. 相似文献