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921.
Owing to their favorable porous structure with pore size distribution shifted towards large flow-through pores, organic polymer monoliths have been mainly employed for the separation of macromolecules in gradient elution liquid chromatography. The absence of significant amounts of small pores with a stagnant mobile phase and the resulting low surface area were considered as the main reason for their poor behavior in the isocratic separation of small molecules. Several recent efforts have improved the separation power of organic polymer monoliths for small molecules offering column efficiency up to tens of thousands of plates per meter. These attempts include optimization of the composition of polymerization mixture, including the variation of functional monomer, the cross-linking monomer, and the porogen solvents mixture, adjustment of polymerization temperature, and time. Additionally, post-polymerization modifications including hypercross-linking and the use of carbon nanostructures showed significant improvement in the column properties. This review describes recent developments in the preparation of organic polymer monoliths suitable for the separation of small molecules in the isocratic mode as well as the main factors affecting the column efficiency. 相似文献
922.
Jií Urban 《Journal of separation science》2020,43(9-10):1628-1633
Thirty years after their introduction, monolithic stationary phases are an important member of chromatographic phases. When compared to conventional particulate materials, the continuous internal structure of both inorganic silica and organic polymer monoliths allows some hydrodynamic and analytical possibilities that are not provided by conventional particulate stationary phases. Polymer‐based monolithic stationary phases offer simple preparation and straightforward surface modification, which makes them very versatile materials that are applicable, for example, as chromatographic stationary phases, sample enrichment units, enzymatic reactors, and external trigger‐responding materials. On the other hand, current polymer monoliths cannot compete with efficiency provided by superficially porous and sub 2 µm particles. In this highlight article, I take advantage of the 30th anniversary of their introduction to discuss several concerns related to polymer‐based monolithic stationary phases. Particularly, I focus on preparation repeatability, porous properties, swelling of the polymers in organic solvents, column efficiency for small molecules, and heterogeneity of dominant flow‐through pores. In the end, I offer three possible approaches on how to overcome drawbacks related to stationary phases heterogeneity to further increase the applicability of polymer‐based monolithic stationary phases. 相似文献
923.
Paulina X. Medina Rangel Elena Moroni Franck Merlier Levi A. Gheber Razi Vago Bernadette Tse Sum Bui Karsten Haupt 《Angewandte Chemie (International ed. in English)》2020,59(7):2816-2822
One of the most promising strategies to treat cancer is the use of therapeutic antibodies that disrupt cell–cell adhesion mediated by dysregulated cadherins. The principal site where cell–cell adhesion occurs encompasses Trp2 found at the N‐terminal region of the protein. Herein, we employed the naturally exposed highly conserved peptide Asp1‐Trp2‐Val3‐Ile4‐Pro5‐Pro6‐Ile7, as epitope to prepare molecularly imprinted polymer nanoparticles (MIP‐NPs) to recognize cadherins. Since MIP‐NPs target the site responsible for adhesion, they were more potent than commercially available therapeutic antibodies for inhibiting cell–cell adhesion in cell aggregation assays, and for completely disrupting three‐dimensional tumor spheroids as well as inhibiting invasion of HeLa cells. These biocompatible supramolecular anti‐adhesives may potentially be used as immunotherapeutic or sensitizing agents to enhance antitumor effects of chemotherapy. 相似文献
924.
Przemysław Kula Albert Aptacy Jakub Herman Wioleta Wójciak Stanisław Urban 《Liquid crystals》2013,40(4):482-491
The synthesis of 4-butyl-4′-[(4-butyl-2,6-difluorophenyl)ethynyl]biphenyl and its higher fluorinated analogues is presented and discussed. Correlations between molecular structure and mesomorphic properties for presented compounds as well as other known from the literature analogues have been drawn. The dielectric study of four synthesised compounds and their mixtures are presented and discussed. Trifluoro-substituted analogues are trade off between low dielectric anisotropy of difluorinated compounds and lower clearing points of tetrafluorinated ones. 相似文献
925.
Abstract The results of high pressure dielectric studies of 4-n-pentyl-4′-cyanobiphenyl (5CB) are analysed in terms of theories of the nematic state. The retardation factor g∥ = τ∥/τ0 and the effective, single-particle potential of mean torque were calculated at the nematic–isotropic transition temperature T NI and along the isothermal, isobaric and isochoric paths within the nematic phase of 5CB. The potential of mean torque is compared with the order parameter known for the same conditions. The values of parameter γ relating the potential to the volume is discussed. 相似文献
926.
Abstract Dielectric studies of 4-(trans-4′-n-hexylcyclohexyl) isothiocyanatobenzene (6CHBT) were performed in the pressure range 0·1–150 MPa, the frequency range 1 kHz–13 MHz and the temperature range 295–325 K. The temperature and pressure dependencies of the static permittivity ?0∥ and of the relaxation time τ∥ are analysed and compared with the analogous data obtained recently for 4-n-pentyl-4′-cyanobiphenyl (5CB) (Parts I and II of this series). Marked differences in the dielectric properties of the nematic phases of the two substances are observed. They are interpreted as a result of varying degrees of molecular association in particular compounds. It is concluded that in the nematic phase of 6CHBT dipole–dipole correlations do not exist or are very weak, whereas for 5CB they are easily broken by a relatively low pressure. 相似文献
927.
Stanisław Urban Albert Würflinger Bo Gestblom Roman Dąbrowski Jan Przedmojski 《Liquid crystals》2013,40(3):305-311
The pressure-temperature phase diagram of 4′-tetradecyl-4-cyanobiphenyl (14CB) up to 220 MPa (2.2 kbar) and between 320–400 K was established using DTA. The temperature range of the smectic A (SmA) phase slightly increases with pressure. The layer spacing d at 1 atm was determined as a function of temperature using X-ray diffraction. It was related to the molecular length l by the ratio d/l ? 1.4. The dielectric relaxation measurements in the isotropic and smectic Ad phases of 14CB at 1 atm were performed in the frequency range 10 kHz-3 GHz. Contributions from both principal rotational motions, i.e. around the short and long molecular axes, were separated. The relaxation measurements under high pressure in the SmA phase covered the low frequency process. The longitudinal relaxation time τ1, characterizing the molecular reorientations around the short axis, was analysed with respect to the pressure and temperature dependences, giving activation volumes, Δ# V = RT (? ln τ1 / ?p)T, and activation enthalpies, Δ# H = RT(? ln τ1 / ?T -1)p, respectively. Surprisingly, all the activation quantities characterizing the rotational motions of 14CB molecules under different conditions are nearly the same as those determined recently for the much shorter homologue, 8CB. This indicates that the 14CB molecule is in fact relatively short due to conformational motions of the alkyl tail. 相似文献
928.
The low frequency relaxation process was studied for 6OCB/8OCB mixtures with three concentrations (27.0, 27.3 and 27.5 wt %) exhibiting the isotropic-nematic-smectic A-nematic re-entrant-crystalline phase sequence and four mixtures (28.5, 30.0, 35.0 and 40.0 wt %) with the isotropic-nematic-crystalline phase sequence. In the liquid crystalline phases, all dielectric spectra could be excellently described by the Debye equation. The relaxation time tau passes smoothly through the phase transitions separating the liquid crystalline phases. The activation barriers hindering the molecular rotations around the short axes are practically the same in the nematic and smectic phases and become larger in the re-entrant nematic phase. Smaller values of the barrier in the nematic phase of mixtures in comparison with those obtained recently for pure 6OCB and 8OCB are explained as an effect of weakening of the molecular interactions caused by increased dipole-dipole associations between molecules in mixtures in relation to pure substances. The slightly larger activation barrier in the nematic re-entrant phase indicates stronger molecular associations in this phase. d 相似文献
929.
The formation of four differently protected 4‐deoxy‐D‐lyxo‐hexose derivatives 7, 8, 12, and 14 is described. In the first procedure, a nucleophilic displacement of the allylic mesylate 4 by hydride was combined with a highly stereoselective osmylation of olefin 6 to afford diol 7. In the second radical procedure, tributyl tin hydride was substituted by the cheap and environmentally friendly hypophosphorous acid as a hydrogen donor in the reduction of xanthate 13 to 4‐deoxy lyxo‐hexose 14. 相似文献
930.
Shriwas S. Ashtaputre Aparna Deshpande Sonali Marathe M. E. Wankhede Jayashree Chimanpure Renu Pasricha J. Urban S. K. Haram S. W. Gosavi S. K. Kulkarni 《Pramana》2005,65(4):615-620
Zinc oxide and cadmium selenide particles in the nanometer size regime have been synthesized using chemical routes. The particles
were capped using thioglycerol in case of ZnO and 2-mercaptoethanol in case of CdSe to achieve the stability and avoid the
coalescence. Zinc oxide nanoparticles were doped with europium to study their optical properties. A variety of techniques
like UV-Vis absorption spectroscopy, X-ray diffraction (XRD), photoluminescence (PL), X-ray photoelectron spectroscopy (XPS),
Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) were used to carry out structural
and spectroscopic characterizations of the nanoparticles. 相似文献