During the past three decades, the most rapid warming at the surface has occurred during the Arctic winter. By analyzing daily ERA-Interim data, it is found that the majority of the winter warming trend north of 70°N can be explained by the trend in the downward infrared radiation (IR). This downward IR trend can be attributed to an enhanced poleward flux of moisture and sensible heat into the Arctic by poleward-propagating Rossby waves, which increases the total column water and temperature within this region. This enhanced moisture flux is mostly due to changes in the planetary-scale atmospheric circulation rather than an increase in moisture in lower latitudes. The results of this study lead to the question of whether Arctic amplification has mostly arisen through changes in the Rossby wave response to greenhouse gas forcing and its impact on moisture transport into the Arctic.
This study presents mechanisms for the polar amplification of surface air temperature that occurred in the Northern Hemisphere (NH) between the periods of 1958-77 (P1) and 1982-2001 (P2). Using European Centre for Medium-Range Weather Forecasts Re-Analysis (ERA-40) reanalysis data, it is found that over the ice-covered Arctic Ocean, the winter surface warming arises from dynamic warming (stationary eddy heat flux and adiabatic warming). Over the ice-free Arctic Ocean between the Greenland and the Barents Seas, downward infrared radiative (IR) flux is found to dominate the warming.To investigate whether the difference in the flow between P1 and P2 is due to changes in the frequency of occurrence of a small number of teleconnection patterns, a coupled self-organizing map (SOM) analysis of the 250-hPa streamfunction and tropical convective precipitation is performed. The latter field was specified to lead the former by 5 days. The results of the analysis showed that the P2 2 P1 trend arises from a decrease in the frequency of negative phase PNA-like and circumglobal streamfunction patterns and a corresponding increase in the frequency of positive PNA-like and circumglobal streamfunction patterns. The occurrence of the two strong 1982-83 and 1997-98 El Niñ o events also contributes toward this trend. The corresponding trend in the convective precipitation is from below average to above average values in the tropical Indo-western Pacific region. Each of the above patterns was found to have an e-folding time scale from 6 to 8 days, which implies that the P2 2 P1 trend can be understood as arising from the change in the frequency of occurrence of teleconnection patterns that fluctuate on intraseasonal time scales.The link between intraseasonal and interannual variability was further examined by linearly regressing various quantities against trend patterns with interannual variability subtracted. It was found that enhanced convective precipitation is followed 3-6 days later by the occurrence of the P2 2 P1 circulation trend pattern, and then 1-2 days later by the corresponding trend pattern in the downward IR flux. This finding suggests that an increased frequency of the above sequence of events, which occurs on intraseasonal time scales, can account for the NH winter polar amplification of the surface air temperature via increased dynamic warming and downward IR flux.
The Arctic has been warming faster than elsewhere, especially during the cold season. According to the leading theory, ice‐albedo feedback warms the Arctic Ocean during the summer, and the heat gained by the ocean is released during the winter, causing the cold‐season warming. Screen and Simmonds (2010; SS10) concluded that the theory is correct by comparing trend patterns in surface air temperature (SAT), surface turbulence heat flux (HF), and net surface infrared radiation (IR). However, in this comparison, downward IR is more appropriate to use. By analyzing the same data used in SS10 using the surface energy budget, it is shown here that over most of the Arctic the skin temperature trend, which closely resembles the SAT trend, is largely accounted for by the downward IR, not the HF, trend.
In this paper, the lead–lag relationship between the Arctic sea ice variability over the Barents–Kara Sea (BKS) and Ural blocking (UB) in winter (DJF) ranging from 1979/80 to 2011/12 is examined. It is found that in a regressed DJF-mean field an increased UB frequency (days) corresponds to an enhanced sea ice decline over the BKS, while the high sea surface temperature over the BKS is accompanied by a significant Arctic sea ice reduction. Lagged daily regression and correlation reveal that the growth and maintenance of the UB that is related to the positive North Atlantic Oscillation (NAO+) through the negative east Atlantic/west Russia (EA/WR−) wave train is accompanied by an intensified negative BKS sea ice anomaly, and the BKS sea ice reduction lags the UB pattern by about four days. Because the intensified UB pattern occurs together with enhanced downward infrared radiation (IR) associated with the intensified moisture flux convergence and total column water over the BKS, the UB pattern contributes significantly to the BKS sea ice decrease on a time scale of weeks through intensified positive surface air temperature (SAT) anomalies resulting from enhanced downward IR. It is also found that the BKS sea ice decline can persistently maintain even when the UB has disappeared, thus indicating that the UB pattern is an important amplifier of the BKS sea ice reduction. Moreover, it is demonstrated that the EA/WR− wave train formed by the combined NAO+ and UB patterns is closely related to the amplified warming over the BKS through the strengthening (weakening) of mid-to-high-latitude westerly wind in the North Atlantic (Eurasia).
Chemodynamic therapy (CDT) by introducing the Fenton-/Fenton-like reaction in an acidic and H 2 O 2 environment for toxic hydroxyl radical (•OH) generation, is a newly developed tumor-selective therapeutic. However, tumor acidosis, characterized by extracellular acidity (pH e ≈ 6.5) and intracellular alkalinity (pH i ≈ 7.2), undoubtedly confers a large chemical barrier for effective implementation of intracellular CDT and thus limits its functional activity and therapeutic efficacy. Here, the unique amorphous iron nanoparticles (AFeNPs) loaded with carbonic anhydrase IX inhibitor (CAI) are constructed to re-establish tumor acidosis with decreased pH i and increased pH e via inhibiting the over-expressed CA IX in cancer cells by CAI for self-enhanced CDT. The suppression of CA IX leads to H + accumulation in cells that could accelerate the AFeNPs-based Fenton reaction to drastically exacerbate oxidative stress in cells and subsequently induce cell death; meanwhile, the inhibition of H + formation outside cells efficiently represses the potential of tumor invasion and metastasis owing to the insufficient acidic ions for degradation of tumor extracellular matrix. Re-establishedtumor acidosis not only assists in the optimization of CDT, but also presents an opportunity for the development of new antitumor methods that are more tumor-acidity specific.
A pyridinium-carboxylate compound undergoes reversible color change under pressure owing to the formation of radicals via electron transfer; dehydration and hydration can also trigger electron transfer.
An electron-deficient and potentially chromic ligand has been utilized to impart redox activity, photo- and hydrochromism, and solvotomagnetism to metal-organic frameworks (MOFs). A pair of MOFs were constructed from the flexible zwitterionic viologen-tethered tetracarboxylate linker N,N'-bis(3,5-dicarboxylatobenzyl)-4,4'-bipyridinium (L): [Co(L)(N)] (1) and [Mn(L)(N)(HO)]·3HO (2). Both compounds show three-dimensional frameworks in which mixed azido- and carboxylato-bridged chains are connected through the electron-deficient viologen moieties. The chain in 1 is built from alternating bis(azide) and (azide)bis(carboxylate) bridges, while that in 2 contains uniform (azide) (carboxylate) bridges. The MOFs shows the characteristic redox properties of the viologen moieties. The redox activity affords the MOFs with different chromic properties, owing to subtle differences in chemical environments. 1 shows reversible photochromism, which is related to the radical formation through photoinduced electron transfer from azide-carboxylate to viologen according to UV-vis, X-ray photoelectron, and electron spin resonance spectroscopy and DFT calculations. 2 is nonphotochromic for lack of appropriate pathways for electron transfer. Unexpectedly, 2 shows a novel type of solid-state hydrochromism. Upon the removal and reabsorption of water, the compound shows remarkable color change because of reversible electron transfer accompanying a reversible structural transformation. The radical mechanism is distinct from those for traditional hydrochromic inorganic and organic materials. Magnetic studies indicate ferro- and antiferromagnetic coupling in 1 and 2, respectively. What's more, 2 shows marked magnetic response to the removal of water molecules owing to the formation of radicals. The compound illustrates a unique material exhibiting dual responses (color and magnetism) to water.
Redox homeostasis is one of the main reasons for reactive oxygen species (ROS) tolerance in hypoxic tumors, limiting ROS‐mediated tumor therapy. Proposed herein is a redox dyshomeostasis (RDH) strategy based on a nanoplatform, FeCysPW@ZIF‐82@CAT Dz, to disrupt redox homeostasis, and its application to improve ROS‐mediated hypoxic tumor therapy. Once endocytosed by tumor cells, the catalase DNAzyme (CAT Dz) loaded zeolitic imidazole framework‐82 (ZIF‐82@CAT Dz) shell can be degraded into Zn2+ as cofactors for CAT Dz mediated CAT silencing and electrophilic ligands for glutathione (GSH) depletion under hypoxia, both of which lead to intracellular RDH and H2O2 accumulation. These “disordered” cells show reduced resistance to ROS and are effectively killed by ferrous cysteine‐phosphotungstate (FeCysPW) induced chemodynamic therapy (CDT). In vitro and in vivo data demonstrate that the pH/hypoxia/H2O2 triple stimuli responsive nanocomposite can efficiently kill hypoxic tumors. Overall, the RDH strategy provides a new way of thinking about ROS‐mediated treatment of hypoxic tumors.
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