scholarly journals Direct and indirect single electron transfer (SET)-photochemical approaches for the preparation of novel phthalimide and naphthalimide-based lariat-type crown ethers

2014 ◽  
Vol 10 ◽  
pp. 514-527 ◽  
Author(s):  
Dae Won Cho ◽  
Patrick S Mariano ◽  
Ung Chan Yoon

In this review, we describe direct and indirect photochemical approaches that have been developed for the preparation of phthalimide- and naphthalimide-based, lariat-type crown ethers. The direct route utilizes a strategy in which nitrogen-linked side chains containing polyethoxy-tethered phthalimides and naphthalimides, possessing terminal α-trialkylsilyl groups, are synthesized utilizing concise routes and UV-irradiation to form macrocyclic ring systems. In contrast, the indirect route developed for the synthesis of lariat-type crown ethers employs sequences in which SET-promoted macrocyclization reactions of α-trialkylsilyl-terminated, polyethoxy-tethered phthalimides and naphthalimides are followed by a side chain introduction through substitution reactions at the amidol centers in the macrocyclic ethers. The combined observations made in these investigations demonstrate the unique features of SET-promoted photocyclization reactions that make them well-suited for the use in the synthesis of functionalized crown ethers. In addition, while some limitations exist for the general use of SET-photochemical reactions in large-scale organic synthesis, important characteristics of the photoinduced macrocyclization reactions make them applicable to unique situations in which high temporal and spatial control is required.

2021 ◽  
Vol 13 (6) ◽  
pp. 1180
Author(s):  
Da Guo ◽  
Xiaoning Song ◽  
Ronghai Hu ◽  
Xinming Zhu ◽  
Yazhen Jiang ◽  
...  

The Hindu Kush Himalayan (HKH) region is one of the most ecologically vulnerable regions in the world. Several studies have been conducted on the dynamic changes of grassland in the HKH region, but few have considered grassland net ecosystem productivity (NEP). In this study, we quantitatively analyzed the temporal and spatial changes of NEP magnitude and the influence of climate factors on the HKH region from 2001 to 2018. The NEP magnitude was obtained by calculating the difference between the net primary production (NPP) estimated by the Carnegie–Ames Stanford Approach (CASA) model and the heterotrophic respiration (Rh) estimated by the geostatistical model. The results showed that the grassland ecosystem in the HKH region exhibited weak net carbon uptake with NEP values of 42.03 gC∙m−2∙yr−1, and the total net carbon sequestration was 0.077 Pg C. The distribution of NEP gradually increased from west to east, and in the Qinghai–Tibet Plateau, it gradually increased from northwest to southeast. The grassland carbon sources and sinks differed at different altitudes. The grassland was a carbon sink at 3000–5000 m, while grasslands below 3000 m and above 5000 m were carbon sources. Grassland NEP exhibited the strongest correlation with precipitation, and it had a lagging effect on precipitation. The correlation between NEP and the precipitation of the previous year was stronger than that of the current year. NEP was negatively correlated with temperature but not with solar radiation. The study of the temporal and spatial dynamics of NEP in the HKH region can provide a theoretical basis to help herders balance grazing and forage.


Crystals ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 15
Author(s):  
Cheng-An Tao ◽  
Jian-Fang Wang

Metal-organic frameworks (MOFs) have been used in adsorption, separation, catalysis, sensing, photo/electro/magnetics, and biomedical fields because of their unique periodic pore structure and excellent properties and have become a hot research topic in recent years. Ball milling is a method of small pollution, short time-consumption, and large-scale synthesis of MOFs. In recent years, many important advances have been made. In this paper, the influencing factors of MOFs synthesized by grinding were reviewed systematically from four aspects: auxiliary additives, metal sources, organic linkers, and reaction specific conditions (such as frequency, reaction time, and mass ratio of ball and raw materials). The prospect for the future development of the synthesis of MOFs by grinding was proposed.


2018 ◽  
Vol 5 (2) ◽  
Author(s):  
Matthieu J. S. Brinkhuis ◽  
Alexander O. Savi ◽  
Abe D. Hofman ◽  
Frederik Coomans ◽  
Han L. J. Van der Maas ◽  
...  

With the advent of computers in education, and the ample availability of online learning and practice environments, enormous amounts of data on learning become available. The purpose of this paper is to present a decade of experience with analyzing and improving an online practice environment for math, which has thus far recorded over a billion responses. We present the methods we use to both steer and analyze this system in real-time, using scoring rules on accuracy and response times, a tailored rating system to provide both learners and items with current ability and difficulty ratings, and an adaptive engine that matches learners to items. Moreover, we explore the quality of fit by means of prediction accuracy and parallel item reliability. Limitations and pitfalls are discussed by diagnosing sources of misfit, like violations of unidimensionality and unforeseen dynamics. Finally, directions for development are discussed, including embedded learning analytics and a focus on online experimentation to evaluate both the system itself and the users’ learning gains. Though many challenges remain open, we believe that large steps have been made in providing methods to efficiently manage and research educational big data from a massive online learning system.


2006 ◽  
Vol 44 (1) ◽  
pp. 96-105 ◽  
Author(s):  
William Easterly

Jeffrey Sachs's new book (The End of Poverty: Economic Possibilities for Our Time, Penguin Press: New York, 2005) advocates a “Big Push” featuring large increases in aid to finance a package of complementary investments in order to end world poverty. These recommendations are remarkably similar to those first made in the 1950s and 1960s in development economics. Today, as then, the Big Push recommendation overlooks the unsolvable information and incentive problems facing any large-scale planning exercise. A more promising approach would be to design incentives for aid agents to implement interventions piecemeal whenever they deliver large benefits for the poor relative to costs.


Author(s):  
Fabian Guba ◽  
Florian Gaulhofer ◽  
Dirk Ziegenbalg

AbstractDynamic irradiation is a potent option to influence the interaction between photochemical reactions and mass transport to design high performant and efficient photochemical processes. To systematically investigate the impact of this parameter, the photocatalytic reduction of nitrobenzene was conducted as a test reaction. Dynamic irradiation was realized through provoked secondary flow patterns, multiple spatially distributed light emitting diodes (LEDs) and electrical pulsation of LEDs. A combined experimental and theoretical approach revealed significant potential to enhance photochemical processes. The reaction rate was accelerated by more than 70% and even more important the photonic efficiency was increased by more than a factor of 4. This renders imposed dynamic irradiation an innovative and powerful tool to intensify photoreactions on the avenue to large scale sustainable photochemical processes.


2021 ◽  
Author(s):  
Luc Hellemans

<p>For the coming ten years, the heart of Europe will turn into a gigantic construction site for works on one of the largest hubs of the continent: Antwerp. The Oosterweel Link is the project whereby the motorway ring around Antwerp is undergoing a metamorphosis to reinvigorate traffic flow and add living space to the City. The project had come to a standstill for several years as a result of protests by assertive citizens, but was given a second lease of life following a large-scale participation project.</p><p>To ensure its successful completion, unparalleled efforts are being made in the field and in the area of digitization. It is therefore with good reason that in Belgium the project is referred to as “the construction site of the century”.</p>


2011 ◽  
Vol 2011 ◽  
pp. 1-15 ◽  
Author(s):  
Andrius Serva ◽  
Christoph Claas ◽  
Vytaute Starkuviene

In the last years miRNAs have increasingly been recognised as potent posttranscriptional regulators of gene expression. Possibly, miRNAs exert their action on virtually any biological process by simultaneous regulation of numerous genes. The importance of miRNA-based regulation in health and disease has inspired research to investigate diverse aspects of miRNA origin, biogenesis, and function. Despite the recent rapid accumulation of experimental data, and the emergence of functional models, the complexity of miRNA-based regulation is still far from being well understood. In particular, we lack comprehensive knowledge as to which cellular processes are regulated by which miRNAs, and, furthermore, how temporal and spatial interactions of miRNAs to their targets occur. Results from large-scale functional analyses have immense potential to address these questions. In this review, we discuss the latest progress in application of high-content and high-throughput functional analysis for the systematic elucidation of the biological roles of miRNAs.


1969 ◽  
Vol 6 (1) ◽  
pp. 25-37 ◽  
Author(s):  
J. Boissonnas ◽  
S. Borsi ◽  
G. Ferrara ◽  
J. Fabre ◽  
J. Fabries ◽  
...  

The Pharusian belt of west-central Ahaggar belongs to the 'basement complex' underlying the Paleozoic and later sediments of the Sahara. This paper reports and discusses the Rb–Sr ages obtained on total rocks and minerals from two granitic stocks of the belt: the Tioueiine and Iskel intrusions.Both plutons gave good whole-rock isochrons, which show that the systems were closed 560 ± 40 m.y. ago with respect to Rb and Sr. This is, most probably, the age of crystallization. Three of the four values obtained on biotites are somewhat lower and scattered in the range 502–526 m.y. The discrepancies are probably due to deuteric reactions or incipient weathering. They can be ascribed neither to the loss of 87Sr during the cooling down of the granites, nor to rejuvenation by some later thermal or tectonic event.These studies confirm previous results of random sampling in Ahaggar and prove that large-scale igneous activity took place during the Early Cambrian Epoch. Knowing from field data that the Tioueiine and Iskel are late orogenic granites, it must be concluded that the Pharusian orogeny came to an end at that time.Such a result contradicts early assumptions, made in the field, of a middle Precambrian age for the Pharusian orogeny. It gives further weight to modern ideas concerning the 700–500 m.y. events in Africa, and it leaves time for erosion to create the Saharian platform before the deposition of the first Paleozoic sandstones.


2013 ◽  
Vol 70 (8) ◽  
pp. 2566-2573 ◽  
Author(s):  
Xun Jiang ◽  
Jingqian Wang ◽  
Edward T. Olsen ◽  
Thomas Pagano ◽  
Luke L. Chen ◽  
...  

Abstract Midtropospheric CO2 retrievals from the Atmospheric Infrared Sounder (AIRS) were used to explore the influence of stratospheric sudden warming (SSW) on CO2 in the middle to upper troposphere. To choose the SSW events that had strong coupling between the stratosphere and troposphere, the authors applied a principal component analysis to the NCEP/Department of Energy Global Reanalysis 2 (NCEP-2) geopotential height data at 17 pressure levels. Two events (April 2003 and March 2005) that have strong couplings between the stratosphere and troposphere were chosen to investigate the influence of SSW on AIRS midtropospheric CO2. The authors investigated the temporal and spatial variations of AIRS midtropospheric CO2 before and after the SSW events and found that the midtropospheric CO2 concentrations increased by 2–3 ppm within a few days after the SSW events. These results can be used to better understand how the chemical tracers respond to the large-scale dynamics in the high latitudes.


Sign in / Sign up

Export Citation Format

Share Document