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141.
用同步法合成了端羟丁腈聚氨酯/聚甲基丙烯酸甲酯互穿网络高聚物[PU(HTBN)/PMMA-IPN]。用动态力学方法和透射电镜研究了它们的T_(?)转变行为和形态。理论计算和实验结果表明,样品具有两个明显相互分离但又各自连续的相结构,呈现出分属于组分聚合物的两个Tg转变(Tg_1,Tg_2)。在全IPN中,PMMA相区的尺寸(1000—2000?),比在接枝共聚物(3000—6000?)和半IPN(—3000?)中的明显变小。适当的交联程度可使相区进一步变小,变均匀,相连续性增加。这是网络互穿造成的“强迫互容”所致。部分丁腈羟(HTBN)分子同PMMA的反应,使一些样品出现了Tg_2升高的现象。 相似文献
142.
Erin J. Peterson Wei Qi Ian N. Stanton Peng Zhang Michael J. Therien 《Chemical science》2020,11(31):8095
High quantum yield NIR fluorophores are rare. Factors that drive low emission quantum yields at long wavelength include the facts that radiative rate constants increase proportional to the cube of the emission energy, while nonradiative rate constants increase in an approximately exponentially with decreasing S0–S1 energy gaps (in accordance with the energy gap law). This work demonstrates how the proquinoidal BTD building blocks can be utilized to minimize the extent of excited-state structural relaxation relative to the ground-state conformation in highly conjugated porphyrin oligomers, and shows that 4-ethynylbenzo[c][1,2,5]thiadiazole (E-BTD) units that terminate meso-to-meso ethyne-bridged (porphinato)zinc (PZnn) arrays, and 4,7-diethynylbenzo[c][1,2,5]thiadiazole (E-BTD-E) spacers that are integrated into the backbone of these compositions, elucidate new classes of impressive NIR fluorophores. We report the syntheses, electronic structural properties, and emissive characteristics of neoteric PZn-(BTD-PZn)n, PZn2-(BTD-PZn2)n, and BTD-PZnn-BTD fluorophores. Absolute fluorescence quantum yield (ϕf) measurements, acquired using a calibrated integrating-sphere-based measurement system, demonstrate that these supermolecules display extraordinary ϕf values that range from 10–25% in THF solvent, and between 28–36% in toluene solvent over the 700–900 nm window of the NIR. These studies underscore how the regulation of proquinoidal conjugation motifs can be exploited to drive excited-state dynamical properties important for high quantum yield long-wavelength fluorescence emission.Incorporation of proquinoidal BTD building blocks into conjugated porphyrin oligomers minimizes the extent of excited-state structural relaxation relative to the ground-state conformation, elucidating new classes of impressive NIR fluorophores. 相似文献
143.
Analysis of scopolamine and its eighteen metabolites in rat urine by liquid chromatography-tandem mass spectrometry 总被引:1,自引:0,他引:1
A rapid and sensitive method is described for the determination of scopolamine and its metabolites in rat urine by combining liquid chromatography and tandem mass spectrometry (LC–MS/MS). Various extraction techniques (free fraction, acid hydrolyses and enzyme hydrolyses) and their comparison were carried out for investigation of the metabolism of scopolamine. After extraction procedure, the pretreated samples were injected into a reversed-phase C18 column with mobile phase of methanol/ ammonium acetate (2 mM, adjusted to pH 3.5 with formic acid) (70:30, v/v) and detected by an on-line MS/MS system. Identification and structural elucidation of the metabolites were performed by comparing their changes in molecular masses (ΔM), retention-times and full scan MSn spectra with those of the parent drug. The results revealed that at least 18 metabolites (norscopine, scopine, tropic acid, aponorscopolamine, aposcopolamine, norscopolamine, hydroxyscopolamine, hydroxyscopolamine N-oxide, p-hydroxy-m-methoxyscopolamine, trihydroxyscopolamine, dihydroxy-methoxyscopolamine, hydroxyl-dimethoxyscopolamine, glucuronide conjugates and sulfate conjugates of norscopolamine, hydroxyscopolamine and the parent drug) and the parent drug existed in urine after ingesting 55 mg/kg scopolamine to healthy rats. Hydroxyscopolamine, p-hydroxy-m-methoxyscopolamine and the parent drug were detected in rat urine for up 106 h after ingestion of scopolamine. 相似文献
144.
Biosorption of metal ions with Penicillium chrysogenum 总被引:1,自引:0,他引:1
Biosorption of metal ions with Penicillium chrysogenum mycelium is described in this article. Alkaline pretreatment was used to remove proteins and nucleic acids from cells, and
this treatment increased the adsorption capacities, for Cr3+ from 18.6 mg g−1 to 27.2 mg g−1, for Ni2+ from 13.2 mg g−1 to 19.2 mg g−1, for Zn2+ from 6.8 mg g−1 to 24.5 mg g−1. The adsorption of metal ions was strongly pH dependent. The mycelium could beused for large-scale removal of Cr3+ from tannery wastewater. The results show that this inexpensive mycelium adsorbent has potential in industry because of its
high adsorption capacity. The main chelating sites are amino groups (−NH2) of chitosan in the mycelium. A new model is established, which describes the relation of adsorption of metal ions on pH
according to amino group chelating with metal ions and H+. The relative errors of simulation for Cu2+, Ni2+, Zn2+, and Cr3+ are 4.66%, 5.45%, 11.55%, and 1.69%, respectively. 相似文献
145.
Mixed-mode hydrophilic interaction/cation-exchange chromatography (HILIC/CEX) is a novel high-performance technique which has excellent potential for peptide separations. Separations by HILIX/CEX are carried out by subjecting peptides to linear increasing salt gradients in the presence of high levels of acetonitrile, which promotes hydrophilic interactions overlaid on ionic interactions with the cation-exchange matrix. In the present study, HILIC/CEX has been compared to reversed-phase liquid chromatography (RP-HPLC) for separation of mixtures of diastereomeric amphipathic alpha-helical peptide analogues, where L- and D-amino acid substitutions were made in the centre of the hydrophilic face of the amphipathic alpha-helix. Unlike RP-HPLC, temperature had a substantial effect on HILIC/CEX of the peptides, with a rise in temperature from 25 to 65 degrees C increasing the retention times of the peptides as well as improving resolution. Our results again highlight the potential of HILIC/CEX as a peptide separation mode in its own right as well as an excellent complement to RP-HPLC. 相似文献
146.
In order to characterize the effect of temperature on the retention behaviour and selectivity of separation of polypeptides and proteins in reversed-phase high-performance liquid chromatography (RP-HPLC), the chromatographic properties of four series of peptides, with different peptide conformations, have been studied as a function of temperature (5-80 degrees C). The secondary structure of model peptides was based on either the amphipathic alpha-helical peptide sequence Ac-EAEKAAKEX(D/L)EKAAKEAEK-amide, (position X being in the centre of the hydrophobic face of the alpha-helix), or the random coil peptide sequence Ac-X(D/L)LGAKGAGVG-amide, where position X is substituted by the 19 L- or D-amino acids and glycine. We have shown that the helical peptide analogues exhibited a greater effect of varying temperature on elution behaviour compared to the random coil peptide analogues, due to the unfolding of alpha-helical structure with the increase of temperature during RP-HPLC. In addition, temperature generally produced different effects on the separations of peptides with different L- or D-amino acid substitutions within the groups of helical or non-helical peptides. The results demonstrate that variations in temperature can be used to effect significant changes in selectivity among the peptide analogues despite their very high degree of sequence homology. Our results also suggest that a temperature-based approach to RP-HPLC can be used to distinguish varying amino acid substitutions at the same site of the peptide sequence. We believe that the peptide mixtures presented here provide a good model for studying temperature effects on selectivity due to conformational differences of peptides, both for the rational development of peptide separation optimization protocols and a probe to distinguish between peptide conformations. 相似文献
147.
Acetylation of alcohols with an equivalent amount of acetic anhydride is feasible in the presence of fluorous distannoxane catalyst in heterogeneous single fluorous system. The fluorous layer containing catalyst can be recycled and reused at least 10 times. 相似文献
148.
149.
基质辅助激光解吸附飞行时间质谱分析缩合单宁的阳离子化问题 总被引:6,自引:0,他引:6
以单价金属离子Cs 和Na 作为离子化试剂,对3种缩合单宁进行基质辅助激光解吸附飞行时间(MALD I-TOF)质谱分析。加入Na 作为阳离子化试剂,能得到较高质量的质谱图。但由于实验通道中几乎不可能完全去除的K 的干扰而会高估棓儿茶酚/表棓儿茶酚单元的组成比例,从而影响对棓儿茶酚/表棓儿茶酚单元存在与否的判断;选择Cs 作为阳离子化试剂可以避免此问题,但在复杂的缩合单宁分析中,同样因为杂质离子Na 和K 的干扰而使得质谱图变得更复杂;未去离子处理直接对缩合单宁进行MALD I-TOF质谱分析与去离子并加入Cs 的处理比去离子并加入Na 能检测到更高聚合度的高聚物,检测到离子峰强度最高的聚合物随离子不同而不同。 相似文献
150.
Man WL Lam WW Yiu SM Lau TC Peng SM 《Journal of the American Chemical Society》2004,126(47):15336-15337
[RuVI(N)(salchda)(CH3OH)]PF6 (1) (salchda = N,N'-bis(salicylidene)o-cyclohexyldiamine dianion) reacts readily with 2,3-dimethyl-2-butene at room temperature in the presence of pyridine or 1-methylimidazole to give initially [RuIV(Az1(-H))(salchda)(py)]PF6 (2, Az1 = 2,2,3,3-tetramethylaziridine), which is then slowly reduced to [RuIII(Az1)(salchda)(py)]PF6 (3). 1 also reacts with a variety of aryl-substituted alkenes such as styrene and trans-beta-methylstyrene in the presence of py or 1-MeIm to give the corresponding ruthenium(III) aziridine complexes. The structures of 3 and [RuIII(Az2)(salchda)(1-MeIm)]PF6 (4, Az2 = trans-2-methyl-3-phenylaziridine) have been determined by X-ray crystallography. The Ru-N(aziridine) distances (2.1049, 2.097 A) are consistent with a neutral aziridine ligand. The C-C and C-N distances in the aziridine ligands are all indicative of single bonds. 相似文献