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71.
Joanna Witos Erno Karjalainen Heikki Tenhu Susanne K. Wiedmer 《Journal of separation science》2020,43(12):2495-2505
Amphiphilic diblock copolymers consisting of a hydrophobic core containing a polymerized ionic liquid and an outer shell composed of poly(N‐isoprolylacrylamide) were investigated by capillary electrophoresis and asymmetrical flow‐field flow fractionation. The polymerized ionic liquid comprised poly(2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate) with a constant block length (n = 24), while the length of the poly(N‐isoprolylacrylamide) block varied (n = 14; 26; 59; 88). Possible adsorption of the block copolymer on the fused silica capillary, due to alterations in the polymeric conformation upon a change in the temperature (25 and 45 °C), was initially studied. For comparison, the effect of temperature on the copolymer conformation/hydrodynamic size was determined with the aid of asymmetrical flow‐field flow fractionation and light scattering. To get more information about the hydrophilic/hydrophobic properties of the synthesized block copolymers, they were used as a pseudostationary phase in electrokinetic chromatography for the separation of some model compounds, that is, benzoates and steroids. Of particular interest was to find out whether a change in the length or concentration of the poly(N‐isoprolylacrylamide) block would affect the separation of the model compounds. Overall, our results show that capillary electrophoresis and asymmetrical flow‐field flow fractionation are suitable methods for characterizing conformational changes of such diblock copolymers. 相似文献
72.
Joanna Bojarska Milan Remko Izabela D. Madura Krzysztof Kaczmarek Janusz Zabrocki Wojciech M. Wolf 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(4):328-345
Recently, fluorenylmethoxycarbonyl (Fmoc) amino acids (e.g. Fmoc–tyrosine or Fmoc–phenylalanine) have attracted growing interest in biomedical research and industry, with special emphasis directed towards the design and development of novel effective hydrogelators, biomaterials or therapeutics. With this in mind, a systematic knowledge of the structural and supramolecular features in recognition of those properties is essential. This work is the first comprehensive summary of noncovalent interactions combined with a library of supramolecular synthon patterns in all crystal structures of amino acids with the Fmoc moiety reported so far. Moreover, a new Fmoc‐protected amino acid, namely, 2‐{[(9H‐fluoren‐9‐ylmethoxy)carbonyl](methyl)amino}‐3‐{4‐[(2‐hydroxypropan‐2‐yl)oxy]phenyl}propanoic acid or N‐fluorenylmethoxycarbonyl‐O‐tert‐butyl‐N‐methyltyrosine, Fmoc‐N‐Me‐Tyr(t‐Bu)‐OH, C29H31NO5, was successfully synthesized and the structure of its unsolvated form was determined by single‐crystal X‐ray diffraction. The structural, conformational and energy landscape was investigated in detail by combined experimental and in silico approaches, and further compared to N‐Fmoc‐phenylalanine [Draper et al. (2015). CrystEngComm, 42 , 8047–8057]. Geometries were optimized by the density functional theory (DFT) method either in vacuo or in solutio. The polarizable conductor calculation model was exploited for the evaluation of the hydration effect. Hirshfeld surface analysis revealed that H…H, C…H/H…C and O…H/H…O interactions constitute the major contributions to the total Hirshfeld surface area in all the investigated systems. The molecular electrostatic potentials mapped over the surfaces identified the electrostatic complementarities in the crystal packing. The prediction of weak hydrogen‐bonded patterns via Full Interaction Maps was computed. Supramolecular motifs formed via C—H…O, C—H…π, (fluorenyl)C—H…Cl(I), C—Br…π(fluorenyl) and C—I…π(fluorenyl) interactions are observed. Basic synthons, in combination with the Long‐Range Synthon Aufbau Modules, further supported by energy‐framework calculations, are discussed. Furthermore, the relevance of Fmoc‐based supramolecular hydrogen‐bonding patterns in biocomplexes are emphasized, for the first time. 相似文献
73.
Tomasz ?ojewski Jacek Bagniuk Andrzej Ko?odziej Joanna ?ojewska 《Applied Physics A: Materials Science & Processing》2011,105(3):753-761
This study proposes a method to estimate the lipid content in binding media in paintings that can be used at any laboratory
equipped with an infrared spectrometer. The lipid content estimator, termed greasiness index (GI), is defined as a ratio of
lipid ν(C=O) and protein amide I bands at 1743 and 1635 cm−1, respectively. Three Fourier transform infrared (FTIR) sampling techniques were evaluated for GI determination: reflective
attenuated total reflection—ATR, specular reflection microscopy—μSR and photoacoustic—PAS. A set of model painting samples containing three tempera binding media (casein, egg, egg + oil),
seven pigments and one varnish type were used in the study. Multivariate analysis was used to evaluate the resulting data.
A good reproducibility of GI was obtained by ATR and PAS but not with μSR. The discriminative power of the technique is higher for unvarnished samples, but, generally, the GI estimator can be used
for the categorisation of binding media in large populations of painting samples analysed with the same FTIR technique (sampling
technique, detection, etc.). 相似文献
74.
A new concept of using acrylated epoxidized soybean oil (AESO) in the production of 3D cellulose biocomposites was evaluated. Cellulose-AESO composites were prepared by dissolving pulp in N,N-dimethylacetamide/lithium chloride and adding AESO and an initiator to the solutions followed by thermal curing and compression moulding at room temperature. The resulting biocomposites were characterized by FE-SEM, FT-IR, XRD, GC, TGA and nano- and microindentation. SEM images indicated the presence of spherical morphology and FT-IR together with TGA results showed no hydrogen or covalent bonding between the two components. The existence of hydrophobic interactions between AESO molecules and cellulose hydrophobic domains was proposed. AESO aggregates captured and covered by cellulose chains increase the flexibility of the composites acting as specific plasticizer and after polymerization introduce strength to the material. It was found that the optimal amount of AESO for achieving both desired hardness and good mouldability should be below 20 %. 相似文献
75.
Mesoporous carbons containing silver nanoparticles have been successfully synthesized under acidic conditions by employing
resorcinol and formaldehyde as carbon precursors and triblock copolymer EO101PO56EO101 (Lutrol F127) as a soft template. Silver nanoparticles of ∼90 nm were added to the synthesis mixture to achieve 10 wt% and
20 wt% of Ag loading in the carbon. Also, tetraethyl orthosilicate (TEOS) was introduced to the system in order to improve
adsorption properties of the silver-carbon composites and to reinforce its structure. The resulting carbons with incorporated
silver nanoparticles featured high surface areas, large total pore volumes and primary mesopores in the range between ∼6–7 nm. 相似文献
76.
Manganese(III) sulfato complexes cause the oxidative degradation of methylene blue and its partially and fully N-demethylated derivatives, azure B and thionine dyes, respectively, in sulfuric acid media. The reaction proceeds through
a colored reactive organic radical generated in the first stage via one-electron oxidation of the starting material, leading
to a mixture of N-demethylated and/or deaminated species. The rates of formation of the methylene blue and azure B radicals are much higher
than those of their further decomposition, whereas the generation of the thionine radical is much slower than its immeasurably
fast decay. The kinetics of decomposition of all three dyes and the methylene blue and azure B radicals were studied spectrophotometrically
under isolation conditions at 298 K. The first stage of each reaction proceeds according to a second-order rate expression,
being first order in the dyes and in the manganese(III) concentrations. Dependence of the pseudo-first-order rate constants
on the oxidant concentration for the second stage exhibits a saturation effect under the applied conditions. It is postulated
that electron transfer takes place between the [Mn(SO4)3]3− complex and the protonated form of the dye. The reactivity order of the dyes as determined from the second-order rate constants
for the first reaction stage corresponds to the order of their HOMO energies. 相似文献
77.
Microgel applications and commercial considerations 总被引:3,自引:0,他引:3
Joanna B. Thorne George J. Vine Martin J. Snowden 《Colloid and polymer science》2011,289(5-6):625-646
78.
The oxidative degradation of phenothiazine derivatives (PTZ) by manganese(III) was studied in the presence of a large excess
of manganese(III)-pyrophosphate (P2O7
2−), phosphate (PO4
3−), and H+ ions using UV–vis. spectroscopy. The first irreversible step is a fast reaction between phenothiazine and manganese pyrophosphate
leading to the complete conversion to a stable phenothiazine radical. In the second step, the cation radical is oxidized by
manganese to a dication, which subsequently hydrolyzes to phenothiazine 5-oxide. The reaction rate is controlled by the coordination
and stability of manganese(III) ion influenced by the reduction potential of these ions and their strong ability to oxidize
many reducing agents. The cation radical might also be transformed to the final product in another competing reaction. The
final product, phenothiazine 5-oxide, is also formed via a disproportionation reaction. The kinetics of the second step of
the oxidative degradation could be studied in acidic phosphate media due to the large difference in the rates of the first
and further processes. Linear dependences of the pseudo-first-order rate constants (k
obs) on [MnIII] with a significant non-zero intercept were established for the degradation of phenothiazine radicals. The rate is dependent
on [H+] and independent of [PTZ] within the excess concentration range of the manganese(III) complexes used in the isolation method.
The kinetics of the disproportionation of the phenothiazine radical have been studied independently from the further oxidative
degradation process in acidic sulphate media. The rate is inversely dependent on [PTZ+.], dependent on [H+], and increases slightly with decreasing H+ concentration. Mechanistic consequences of all these results are discussed. 相似文献
79.
A sensitive and specific liquid chromatography electrospray ionisation-tandem mass spectrometry method for determination of new non-imidazole histamine H(3) receptor antagonist 1-[3-(4-tert-butylphenoxy)propyl]piperidine (DL76) in rat serum has been developed and validated. Chromatography was performed on a XBridge? C18 analytical column (2.1?×?30?mm, 3.5?μm, Waters, Ireland) with gradient elution using a mobile phase containing acetonitrile and water with an addition of 0.1% of formic acid. Detection was achieved by an Applied Biosystems MDS Sciex (Concord, Ontario, Canada) API 2000 triple quadrupole mass spectrometer. Electrospray ionization (ESI) was used for ion production. The limit of detection in the SRM mode was found to be 0.5?ng?mL(-1). The limit of quantification was 1?ng?mL(-1). The precision and accuracy for both intra- and inter-day determination of DL76 ranged from 1.65 to 15.09% and from 88.74 to 113.43%. The results of this analytical method validation allow to carry out pharmacokinetic studies in rats. The method was used for the pilot study of the pharmacokinetic behavior of DL76 in rats after intravenous administration. 相似文献
80.
Information switching and swapping seem to be fundamental elements of quantum communication protocols. Another crucial issue is the presence of entanglement and its level in inspected quantum systems. In this article, a formal definition of the operation of the swapping local quantum information and its existence proof, together with some elementary properties analysed through the prism of the concept of the entropy, are presented. As an example of the local information swapping usage, we demonstrate a certain realisation of the quantum switch. Entanglement levels, during the work of the switch, are calculated with the Negativity measure and a separability criterion based on the von Neumann entropy, spectral decomposition and Schmidt decomposition. Results of numerical experiments, during which the entanglement levels are estimated for systems under consideration with and without distortions, are presented. The noise is generated by the Dzyaloshinskii-Moriya interaction and the intrinsic decoherence is modelled by the Milburn equation. This work contains a switch realisation in a circuit form—built out of elementary quantum gates, and a scheme of the circuit which estimates levels of entanglement during the switch’s operating. 相似文献