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51.
Gordon D. Airey Jasmin Wilmot James R.A. Grenfell Derek J. Irvine Ian A. Barker Jaouad El Harfi 《European Polymer Journal》2011,47(6):1300-1314
Catalytic chain transfer polymerization has been successfully used to produce a range of methyl acrylate (MA) and butyl acrylate (BA) synthetic polymers of specific, targeted molecular weights, with polydispersity index values in the range of 2–4.5. The rheological properties of a subgroup of these synthetic binders consisting of four MA homo-polymers and one MA–BA co-polymer were then determined by means of oscillatory testing using a dynamic shear rheometer (DSR). The rheological tests consisted of a combination of stress/strain amplitude and frequency sweeps using a standard 8 mm diameter parallel plate testing geometry. The rheological parameters of phase angle and complex, storage and loss moduli were then shifted to form master curves at a reference temperature of 25 °C and isochronal plots at 0.1, 1 and 10 Hz. The rheological properties of the synthetic polymers were also compared to those of standard road pavement bitumens. The results show that it is possible to produce a range of synthetic polyacrylates with different rheological responses by altering the reactant type, reactant concentration and polymerization conditions to match the rheological properties of road bitumens. All the polyacrylate binders showed a similar rheological profile with a unique viscoelastic response as represented by the phase angle master curves together with an upper limiting stiffness and intermediate temperature/frequency ‘plateau’ region as shown in the complex modulus master curves. The results of the rheological examination of the binders showed that the key material property that influenced the performance of the polyacrylates in these specific application tests was glass transition temperature rather than molecular weight. Over this range of investigated molecular weights, it is the ratio between the two polymers which determines the glass transition and as such determines the material properties. These findings suggest that such sustainably sourced polyacrylate binders may allow for a move from petrochemical feed stocks to be made and allow for targeted road pavement design based on local climates, offering improved mechanical robustness. 相似文献
52.
Thalhammer A Mecinović J Loenarz C Tumber A Rose NR Heightman TD Schofield CJ 《Organic & biomolecular chemistry》2011,9(1):127-135
Based on structural analysis of the human 2-oxoglutarate (2OG) dependent JMJD2 histone N(ε)-methyl lysyl demethylase family, 3-substituted pyridine 2,4-dicarboxylic acids were identified as potential inhibitors with possible selectivity over other human 2OG oxygenases. Microwave-assisted palladium-catalysed cross coupling methodology was developed to install a diverse set of substituents on the sterically demanding C-3 position of a pyridine 2,4-dicarboxylate scaffold. The subsequently prepared di-acids were tested for in vitro inhibition of the histone demethylase JMJD2E and another human 2OG oxygenase, prolyl-hydroxylase domain isoform 2 (PHD2, EGLN1). A subset of substitution patterns yielded inhibitors with selectivity for JMJD2E over PHD2, demonstrating that structure-based inhibitor design can enable selective inhibition of histone demethylases over related human 2OG oxygenases. 相似文献
53.
Molecular approaches towards mixed metal oxides and their behaviour in mixed oxide support Au catalysts for CO oxidation 总被引:1,自引:0,他引:1
Geserick J Fröschl T Hüsing N Kucerova G Makosch M Diemant T Eckle S Behm RJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(13):3269-3286
We herein report a water-based sol-gel approach towards porous mixed Si/Ti oxides using co-precipitated glycol-modified precursors. By adjusting synthesis parameters such as the pH value and the Si/Ti ratio of the precursor, the morphology as well as the Si/Ti-composition of the resulting mixed oxide particles can be varied in a wide range. The behaviour of the mixed oxides as substrates for Au catalysts and the performance of the resulting catalysts in the CO oxidation reaction was investigated and compared to catalysts supported on mesoporous anatase and rutile synthesized analogously. For comparable Au particle sizes and Au loadings, the composition of the mixed oxide support was found to significantly affect the reactivity and reaction behaviour, with mixed oxide supported Au catalysts synthesized at pH=5 or 10 and with a Si/Ti-ratio of 1:19 and 1:34 exhibiting the maximum activity. In contrast to the enhanced activity, the mixed oxide supports do not lead to a significant improvement in deactivation behaviour and catalyst stability. 相似文献
54.
Hamed RB Henry L Gomez-Castellanos JR Mecinović J Ducho C Sorensen JL Claridge TD Schofield CJ 《Journal of the American Chemical Society》2012,134(1):471-479
The biocatalytic versatility of wildtype and engineered carboxymethylproline synthases (CMPSs) is demonstrated by the preparation of functionalized 5-carboxymethylproline derivatives methylated at C-2, C-3, C-4, or C-5 of the proline ring from appropriately substituted amino acid aldehydes and malonyl-coenzyme A. Notably, compounds with a quaternary center (at C-2 or C-5) were prepared in a stereoselective fashion by engineered CMPSs. The substituted-5-carboxymethyl-prolines were converted into the corresponding bicyclic β-lactams using a carbapenam synthetase. The results demonstrate the utility of the crotonase superfamily enzymes for stereoselective biocatalysis, the amenability of carbapenem biosynthesis pathways to engineering for the production of new bicyclic β-lactam derivatives, and the potential of engineered biocatalysts for the production of quaternary centers. 相似文献
55.
56.
Christoph Schoo Sebastian Bestgen Alexander Egeberg Jasmin Seibert Sergey N. Konchenko Claus Feldmann Peter W. Roesky 《Angewandte Chemie (International ed. in English)》2019,58(13):4386-4389
Zintl phases of arsenic and molecular compounds containing Zintl‐type polyarsenide ions are of fundamental interest in basic and applied sciences. Unfortunately, the most obvious and reactive arsenic source for the preparation of defined molecular polyarsenide compounds, yellow arsenic As4, is very inconvenient to prepare and neither storable in pure form nor easy to handle. Herein, we present the synthesis and reactivity of elemental As0 nanoparticles (As0Nano, d=7.2±1.8 nm), which were successfully utilized as a reactive arsenic source in reductive f‐element chemistry. Starting from [Cp*2Sm] (Cp*=η5‐C5Me5), the samarium polyarsenide complexes [(Cp*2Sm)2(μ‐η2:η2‐As2)] and [(Cp*2Sm)4As8] were obtained from As0nano, thereby generating the largest molecular polyarsenide of the f‐elements and circumventing the use of As4 in preparative chemistry. 相似文献
57.
The catalytic hydrogenation of CO2 includes the dissociation of hydrogen and further reaction with CO2 and intermediates. We investigate how the amount of hydrogen in the bulk of the catalyst affects the hydrogenation reaction taking place at the surface. For this, we developed an experimental setup described herein, based on a magnetic suspension balance and an infrared spectrometer, and measured pressure-composition isotherms of the Pd−H system under conditions relevant for CO2 reduction. The addition of CO2 has no influence on the measured hydrogen absorption isotherms. The pressure dependence of the CO formation rate changes suddenly upon formation of the β-PdH phase. This effect is attributed to a smaller surface coverage of hydrogen due to repulsive electronic interactions affecting both bulk and surface hydrogen. 相似文献
58.
Kalpani K. Somarathne Jordan A. J. McCone Amira Brackovic Jos Luis Pinedo Rivera J. Robin Fulton Euan Russell Jessica J. Field Christopher L. Orme Hedley L. Stirrat Jasmin Riesterer Paul H. Teesdale‐Spittle John H. Miller Joanne E. Harvey 《化学:亚洲杂志》2019,14(8):1230-1237
The fungal metabolite TAN‐2483B has a 2,6‐trans‐relationship across the pyran ring of its furo[3,4‐b]pyran‐5‐one core, which has thwarted previous attempts at its synthesis. We have now developed a chiral pool approach to this core and prepared side‐chain analogues of TAN‐2483B. The synthesis relies on ring expansion of a reactive furan ring‐fused dibromocyclopropane and alkynylation of the resulting pyran. The furan ring is constructed by palladium‐catalysed carbonylative lactonisation. Various side‐chains are appended through Wittig‐type chemistry. The prepared analogues showed micromolar activity towards cancer cell lines HL‐60, 1A9 and MCF‐7 and certain human disease‐relevant kinases, including Bruton's tyrosine kinase (Btk). 相似文献
59.
David Schmidt Matthias Stolte Jasmin Süß Andreas Liess Vladimir Stepanenko Frank Würthner 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(38):13519-13523
Strongly emissive solid‐state materials are mandatory components for many emerging optoelectronic technologies, but fluorescence is often quenched in the solid state owing to strong intermolecular interactions. The design of new organic pigments, which retain their optical properties despite their high tendency to crystallize, could overcome such limitations. Herein, we show a new material with monomer‐like absorption and emission profiles as well as fluorescence quantum yields over 90 % in its crystalline solid state. The material was synthesized by attaching two bulky tris(4‐tert‐butylphenyl)phenoxy substituents at the perylene bisimide bay positions. These substituents direct a packing arrangement with full enwrapping of the chromophore and unidirectional chromophore alignment within the crystal lattice to afford optical properties that resemble those of their natural pigment counterparts, in which chromophores are rigidly embedded in protein environments. 相似文献