An efficient Ir(III)-catalyzed C–H activation and annulations of aryloxime with α-diazocarbonyl compounds has been developed for the synthesis of substituted isoquinoline N-oxides. The reaction ...proceeds under mild atmospheric conditions, without any external oxidants and releases N2 and H2O as the byproducts. In addition, synthetic applications of the N-oxide products have been established by performing further functionalization. An interesting dimeric iridacyclic complex allied through a bis-silver carboxylate bridge has been isolated that efficiently catalyzed the reaction.
Tropical cyclones play an important role in modifying the tropopause structure and dynamics as well as stratosphere–troposphere exchange (STE) processes in the upper troposphere and lower ...stratosphere (UTLS) region. In the present study, the impact of cyclones that occurred over the north Indian Ocean during 2007–2013 on the STE processes is quantified using satellite observations. Tropopause characteristics during cyclones are obtained from the Global Positioning System (GPS) radio occultation (RO) measurements, and ozone and water vapour concentrations in the UTLS region are obtained from Aura Microwave Limb Sounder (MLS) satellite observations. The effect of cyclones on the tropopause parameters is observed to be more prominent within 500 km of the centre of the tropical cyclone. In our earlier study, we observed a decrease (increase) in the tropopause altitude (temperature) up to 0.6 km (3 K), and the convective outflow level increased up to 2 km. This change leads to a total increase in the tropical tropopause layer (TTL) thickness of 3 km within 500 km of the centre of cyclone. Interestingly, an enhancement in the ozone mixing ratio in the upper troposphere is clearly noticed within 500 km from the cyclone centre, whereas the enhancement in the water vapour in the lower stratosphere is more significant on the south-east side, extending from 500 to 1000 km away from the cyclone centre. The cross-tropopause mass flux for different intensities of cyclones is estimated and it is found that the mean flux from the stratosphere to the troposphere for cyclonic storms is 0.05 ± 0.29 × 10−3 kg m−2, and for very severe cyclonic storms it is 0.5 ± 1.07 × 10−3 kg m−2. More downward flux is noticed on the north-west and south-west side of the cyclone centre. These results indicate that the cyclones have significant impact in effecting the tropopause structure, ozone and water vapour budget, and consequentially the STE in the UTLS region.
During early embryogenesis, the ectoderm is rapidly subdivided into neural, neural crest and sensory progenitors. How the onset of lineage determinants and the loss of pluripotency markers are ...temporally and spatially coordinated
is still debated. Here, we identify a crucial role for the transcription factor PRDM1 in the orderly transition from epiblast to defined neural lineages in chick.
is initially expressed broadly in the entire epiblast, but becomes gradually restricted as cell fates are specified. We find that PRDM1 is required for the loss of some pluripotency markers and the onset of neural, neural crest and sensory progenitor specifier genes. PRDM1 directly activates their expression by binding to their promoter regions and recruiting the histone demethylase Kdm4a to remove repressive histone marks. However, once neural lineage determinants become expressed, they in turn repress
, whereas prolonged PRDM1 expression inhibits neural, neural crest and sensory progenitor genes, suggesting that its downregulation is necessary for cells to maintain their identity. Therefore, PRDM1 plays multiple roles during ectodermal cell fate allocation.
The most important means for tuning and improving a catalyst's properties is the delicate exchange of the ligand shell around the central metal atom. Perhaps for no other organometallic-catalyzed ...reaction is this statement more valid than for ruthenium-based olefin metathesis. Indeed, even the simple exchange of an oxygen atom for a sulfur atom in a chelated ruthenium benzylidene about a decade ago resulted in the development of extremely stable, photoactive catalysts. This Account presents our perspective on the development of dormant olefin metathesis catalysts that can be activated by external stimuli and, more specifically, the use of light as an attractive inducing agent.The insight gained from a deeper understanding of the properties of
-dichlororuthenium benzylidenes opened the doorway for the systematic development of new and efficient light-activated olefin metathesis catalysts and catalytic chromatic-orthogonal synthetic schemes. Following this, ways to disrupt the ligand-to-metal bond to accelerate the isomerization process that produced the active precatalyst were actively pursued. Thus, we summarize herein the original thermal activation experiments and how they brought about the discoveries of photoactivation in the sulfur-chelated benzylidene family of catalysts. The specific wavelengths of light that were used to dissociate the sulfur-ruthenium bond allowed us to develop noncommutative catalytic chromatic-orthogonal processes and to combine other photochemical reactions with photoinduced olefin metathesis, including using external light-absorbing molecules as "sunscreens" to achieve novel selectivities. Alteration of the ligand sphere, including modifications of the N-heterocyclic carbene (NHC) ligand and the introduction of cyclic alkyl amino carbene (CAAC) ligands, produced more efficient light-induced activity and special chemical selectivity. The use of electron-rich sulfoxides and, more prominently, phosphites as the agents that induce latency widened the spectrum of light-induced olefin metathesis reactions even further by expanding the colors of light that may now be used to activate the catalysts, which can be used in applications such as stereolithography and 3D printing of tough metathesis-derived polymers.
We report the synthesis, characterization, and enhanced propane dehydrogenation properties of hierarchical Ga-MFI zeolite catalysts synthesized by two different methods: (i) repetitive branching and ...(ii) utilization of a long chain alkyl SDA. Structural, compositional, and morphological characterizations confirm that the Ga-MFI catalyst materials have hierarchical structures including micropores and mesopores in a single particle and show that Si/Ga ratios comparable to bulk Ga-MFI catalysts can be obtained. Acid site analysis using NH3-TPD and pyridine adsorption followed by in situ IR spectroscopy allowed quantification of the number and types of acid sites present and show that the hierarchical catalysts have considerably higher Lewis acid site concentrations than the bulk catalysts. The hierarchical Ga-MFI catalysts show superior PDH performance (at 600 °C) compared to bulk Ga-MFI catalysts. Propane conversion rates are increased 2–6-fold and propylene selectivities are 10–100% higher. We also examine the effects of synthesis variationssuch as addition of 3-mercaptopropyltrimethoxysilane during synthesis and H+ ion-exchangeand find that both these steps have a beneficial effect on PDH properties. Calculations suggest that PDH in both the bulk and the hierarchical Ga-MFI is not diffusion-limited. Therefore, the superior performance of hierarchical Ga-MFI is due to intrinsically higher activity and selectivity. Potential reasons for this behavior are outlined. The present findings showing enhancement of PDH in hierarchical Ga-MFI catalysts suggests that the utility of the hierarchical zeolites is not limited to diffusion-limited reactions involving large, bulky molecules and that they may be useful in more diverse applications involving gas-phase reactions with small molecules.
Numerous studies have been conducted to prove the calming and stress-reducing effects on humans of visiting aquatic environments. As a result, many institutions have utilized fish to provide ...entertainment and treat patients. The most common issue in this approach is controlling the movement of fish to facilitate human interaction. This study proposed an interactive robot, a robotic fish, to alter fish swarm behaviors by performing an effective, unobstructed, yet necessary, defined set of actions to enhance human interaction. The approach incorporated a minimalistic but futuristic physical design of the robotic fish with cameras and infrared (IR) sensors, and developed a fish-detecting and swarm pattern-recognizing algorithm. The fish-detecting algorithm was implemented using background subtraction and moving average algorithms with an accuracy of 78%, while the swarm pattern detection implemented with a Convolutional Neural Network (CNN) resulted in a 77.32% accuracy rate. By effectively controlling the behavior and swimming patterns of fish through the smooth movements of the robotic fish, we evaluated the success through repeated trials. Feedback from a randomly selected unbiased group of subjects revealed that the robotic fish improved human interaction with fish by using the proposed set of maneuvers and behavior.
Accurate estimation of the planetary boundary layer (PBL) top is essential for air quality prediction, weather forecast, and assessment of regional and global climate models. In this article, the ...long-term climatology of seasonal, global distribution of PBL is presented by using global positioning system radio occultation (GPSRO) based payloads such as Constellation Observing System for Meteorology, Ionosphere, and Climate (COSMIC), Communication/Navigation Outage Forecast System (C/NOFS), TerraSAR-X, and The Gravity Recovery and Climate Experiment (GRACE) from the year 2006–2015. We used Wavelet Covariance Transform (WCT) technique for precise PBL top identification. The derived PBL top from GPSRO data is rigorously evaluated with GPS radiosonde data over Gadanki. Significant seasonal variation is noticed in both radiosonde and GPSRO observations. Further, we compared the PBL obtained GPS RO with global radiosonde network and observed very good correlation. The number of occultations reaching down to 500 m and retrieval rate of PBL top from WCT method is very high in mid-latitudes compared to tropical latitudes. The global distribution of PBL top shows significant seasonal variation with higher during summer followed by spring, fall, and minimum in winter. In the vicinity of Inter Tropical Convergence Zone (ITCZ), the PBL top is high over eastern Pacific compared to other regions. The ERA-Interim reanalysis data underestimate the PBL top compared to GPS RO observations due to different measurement techniques. The seasonal variation of global averaged PBL top over land and ocean shows contrasting features at different latitude bands.
A mild and efficient Ir(III)-catalyzed C-H carbenoid functionalization strategy has been developed to access N-methoxyisoquinolinediones and N-methoxyisoquinolinones. The reaction proceeds ...efficiently in high yield at room temperature over a broad range of substrates without requirement of any additional oxidants or a base.
A straightforward technique is presented for correcting the position of an inaccurately oriented implant analog in a digitally printed definitive cast. The technique enables the operator to ...reposition the analog accurately in the definitive cast and obviates the need of an additional scanning procedure or printing a new cast. The technique also permits accurate reproduction of the soft tissue contours around the implant.
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