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91.
    
Biocatalytic alkylation reactions can be performed with high chemo-, regio- and stereoselectivity using S-adenosyl-l -methionine (SAM)-dependent methyltransferases (MTs) and SAM analogs. Currently, however, this methodology is limited in application due to the rather laborious protocols to access SAM analogs. It has recently been shown that halide methyltransferases (HMTs) enable synthesis and recycling of SAM analogs with readily available haloalkanes as starting material. Here we expand this work by using substrate profiling of the anion MT enzyme family to explore promiscuous SAM analog synthesis. Our study shows that anion MTs are in general very promiscuous with respect to the alkyl chain as well as the halide leaving group. Substrate profiling further suggests that promiscuous anion MTs cluster in sequence space. Next to iodoalkanes, cheaper, less toxic, and more available bromoalkanes have been converted and several haloalkanes bearing short alkyl groups, alkyl rings, and functional groups such as alkene, alkyne and aromatic moieties are accepted as substrates. Further, we applied the SAM analogs as electrophiles in enzyme-catalyzed regioselective pyrazole allylation with 3-bromopropene as starting material.  相似文献   
92.
    
This work aims to assess the influence of the chemical composition of the binder resulting from the reaction of phosphoric acid and volcanic ash on its final characteristics. Six initial compositions of volcanic ash phosphate geopolymer with molar ratios Fe/P of 0.27, 0.5, 0.54, 0.81, 1, and 1.5 were designed by adding various dosages of phosphoric acid to volcanic ash. The results show that the hardening time increases with the decrease of molar ratios Fe/P. An excess of phosphoric acid leads to an unstable binder that is partially destroyed with the aging of the binder. The volcanic ash phosphate geopolymer with molar ratios of Fe/P = 0.5–0.54 has the optimum compressive strength (49–53 MPa at 90 days), the lowest water absorption (8.8-9.5 wt.%) as well as porosity (18–19.6 vol.%). The main binder is a porous phase of ferro-silico-aluminophosphate. Secondary phases were also identified in some mixes including ferro-aluminophosphate and magnesium phosphate.  相似文献   
93.
94.
    
The introduction of metallic fillers to polymers via the photopolymerization approach can endow the composite materials with some unique properties, but the relevant research is still scarce due to the issue of light penetration and inner filter effect. Herein, for the first time the fabrication of photocomposites based on fine iron powder (i.e., a typical kind of metallic filler) is reported in this work. The free radical polymerization of two different acrylate monomers, poly(ethylene glycol) diacrylate and trimethylolpropane triacrylate, is performed in the presence of iron filler under mild conditions (i.e., light emitting diode (LED)@405 nm irradiation at room temperature under air). And the real-time Fourier transform infrared spectroscopy reveals remarkable photopolymerization kinetics of acrylates with high final conversions and fast polymerization rates despite the increasing contents of iron filler in the composites. Interestingly, the 3D printing technique is applied to the iron filler-based composites to produce tridimensional patterns with excellent spatial resolution. This work not only paves the way for the investigation of photocomposites based on metallic fillers through photochemical methods, but also broadens the potential application prospects.  相似文献   
95.
    
This study aimed to characterize different natural killer (NK) cell phenotypes on bone marrow and peripheral blood cells from acute myeloid leukemia (AML) patients and healthy donors (HDs). Our data show that CD56dimCD16 and CD56brightCD16 NK cells represent the predominant NK cell subpopulations in AML, while the CD56dimCD16+ NK cells are significantly reduced compared to HDs. Moreover, TIGIT+ and PVRIG+ cells cluster on the CD56dimCD16+ subset whereas CD39+ and CD38+ cells do so on CD56brightCD16 NK cells in AML. Furthermore, functional effects of (co-)blockade of TIGIT and CD39 or A2AR on NK cell functionality were analyzed. These experiments revealed that the single blockade of the TIGIT receptor results in an increased NK-92 cell-mediated killing of AML cells in vitro. Combined targeting of CD39 or A2AR significantly augments the anti-TIGIT-mediated lysis of AML cells. Our data indicate that distinct NK cell subsets in AML exhibit different immunosuppressive patterns (via the TIGIT/PVRIG receptors and the purinergic pathway). In summary, we conclude that TIGIT, CD39, and A2AR constitute relevant inhibitory checkpoints of NK cells in AML patients. A combinatorial blockade synergistically strengthens NK-92 cell-mediated cytotoxicity. As inhibitors of TIGIT, CD39, and A2AR are clinically available, studies on their combined use could be conducted in the near future.  相似文献   
96.
The use of slow (~1 Hz) flow oscillation imposed on a stationary flow of liquid has been shown to enhance shear stresses imposed on a surface and to mitigate fouling or enhance cleaning. Examples of the application of pulsed flow are presented in this paper. A new measuring technique in combination with tailored CFD simulations was developed for monitoring the cleaning of complex piping equipment with pulsed flow. A time-independent and isotropic approach to model the wall shear stress is introduced. The optical monitoring procedure uses a model food soil consisting of starch as matrix material and phosphorescent zinc sulfide crystals as optical tracer. Investigations of pulsed flow cleaning published prior to this work focused on tests with straight pipes, whereas difficulties in industrial cleaning operations more often arise while operating piping systems and plant components with complex geometries. Therefore cleaning experiments were performed in a CIP test rig simulating industrial cleaning processes. The results with pulsed flow show an enhancement of cleaning efficiency at locations difficult to access using stationary flow.  相似文献   
97.
Structure oriented screening techniques are discussed with regard to their usefulness and applicability in catalyst screening in research projects with different degrees of exploratory character. Structure oriented screening approaches were applied to build libraries for two target reactions in two case studies presented in this paper one challenging exploratory ammon-oxidation reaction for the conversion of C6-feedstocks to adipodinitrile precursors with currently no relevant useful materials and no technical solution known. In this study the structure driven approach helped to identify lead structures for the conversion. The second case study focuses on the oxidation of acrolein and methacrolein to the corresponding unsaturated acids. Here technical catalyst candidate materials are known and are applied in the actual industrial applications. Therefore, the focus of the second case study is to find a superior material or alternative candidate materials with improved properties with this research strategy. For both case studies the effectiveness of the structure based approach is evaluated and put into perspective with state of the art library design and research strategies in high throughput experimentation and combinatorial catalysis.  相似文献   
98.
Periodic mesoporous silica was modified with metal organic reagents via direct surface substitution reactions, thus introducing functional groups into the channels of the structure. Using materials functionalised with basic aromatic molecules as catalysts, the efficient Michael addition of diethyl malonate to trans-β-nitrostyrene was achieved. The catalysts anchored to the silica surface show high activity in the catalytic process even at low concentrations and low temperatures. The catalysts also prove to be stable during many recycling procedures. In combination with the remarkably reduced cost for the synthesis of these solid bases, the new hybrid systems are promising candidates for a new generation of catalysts.  相似文献   
99.
Emissions of nitrous oxide (N2O) from agricultural soils contribute significantly to the anthropogenic greenhouse effect. Numerous studies have been conducted during the last three decades to improve the understanding of the processes involved in the release of N2O from agricultural soils. This enabled the creation of process based models on site and field scale. In addition, a growing number of N2O emission data are available for different soil-land-use-systems from various climates. The integration of these data in global and national N2O budgets leads to more improved estimations. Surprisingly, N2O-emission calculations are rare on regional meso and macro scales. The spatial identification of areas with a high efflux of N2O on regional meso and macro scales is essential for the implementation of N2O emission mitigation strategies, thus leading to an increased sustainability of land use. On the basis of the ecosystem approach of Matson and Vitousek (1990), we introduce a new method to estimate regional N2O emissions from agricultural soils on meso and macro scales. This method considers spatial environmental information from available spatial and statistical data as well as quantitative and qualitative expertise by using the tools of a geographic information system (GIS). An environmental information system (EIS) was built up for a dairy farm region in Southern Germany which includes soil, land use, topography, N2O emission and farm management data. Using all information in the EIS, it was possible (i) to identify different spatial soil-land-use-systems, (ii) to link emission data and process knowledge to these soil-land-use-systems and (iii) to visualize spatial emission potentials. On this basis, N2O emission potentials for each of the communities in the study region and the whole region were estimated. The estimated annual N2O emission potential from agricultural soils for the examined dairy farm region in Southern Germany covering around 775 km2 is about 3.0 kg N2O-N ha−1. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   
100.
Cone-beam type X-ray computed tomography (CBCT) is a potential method to measure three-dimensional phase distributions in vessels. An example for that is the measurement of gas profiles in stirred chemical reactors. Such data are highly valuable for the assessment and evaluation of chemical processes, for optimisation of the reactor and stirrer design, and for evaluation of computational fluid dynamics codes used to model the fluid flow and heat transfer in reactive systems. However, there are considerable difficulties for accurate quantitative measurements due to beam hardening and radiation scattering effects. In a theoretical and experimental work we have investigated the non-linear effects of both physical phenomena and developed a suitable measurement setup as well as calibration and software correction methods to achieve a highly accurate measurement of void fraction profiles with CBCT.  相似文献   
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