Proteins in the cellular milieu reside in environments crowded by macromolecules and other solutes. Although crowding can significantly impact the protein folded state stability, most experiments are conducted in dilute buffered solutions. To resolve the effect of crowding on protein stability, we use 19F nuclear magnetic resonance spectroscopy to follow the reversible, two-state unfolding thermodynamics of the N-terminal Src homology 3 domain of the Drosophila signal transduction protein drk in the presence of polyethylene glycols (PEGs) of various molecular weights and concentrations. Contrary to most current theories of crowding that emphasize steric protein–crowder interactions as the main driving force for entropically favored stabilization, our experiments show that PEG stabilization is accompanied by significant heat release, and entropy disfavors folding. Using our newly developed model, we find that stabilization by ethylene glycol and small PEGs is driven by favorable binding to the folded state. In contrast, for larger PEGs, chemical or soft PEG–protein interactions do not play a significant role. Instead, folding is favored by excluded volume PEG–protein interactions and an exothermic nonideal mixing contribution from release of confined PEG and water upon folding. Our results indicate that crowding acts through molecular interactions subtler than previously assumed and that interactions between solution components with both the folded and unfolded states must be carefully considered.
Among the varied environmental factors that influence insect life-history, temperature has a relatively profound effect that can be mathematically estimated with non-linear equations. Thus, many models that aim to predict insect-pest population dynamics use meteorological data as input to descriptive functions that predict the development rate, survival and reproduction of pest populations. In a previous study, we developed a temperature-dependent population dynamics model for the global insect-pest Bemisia tabaci, and verified its accuracy under field conditions. In the current work, which focused on Northern Israel, seasonal meteorological forecasts from the ECMWF SEAS5 coupled model were spatially and temporally stochastically downscaled by a weather generator tool using records from ERA5-Land reanalysis and meteorological stations. The local, hourly temperature time series served as input data to a population dynamics model, creating an ensemble of seasonal population forecasts from which probabilistic predictions could be made already at the beginning of the season (which lasts from March to November). Post-hoc evaluation of the seasonal forecast was done using the observed station temperatures as model input. Comparisons to predictions made using climatologic temperatures found the weather generator-based ones much more accurate in predicting the timing of each insect generation, although there was no difference between the two approaches in predicting the population size. Moreover, the weather generator-based predictions highly matched field observations made by pest inspectors during the growing season of 2021. Taken together, our findings indicate that the developed forecasting tool is capable of providing decision makers with the supporting data required for smart seasonal planning and economical- and environmental-driven optimal management of agricultural systems.
Violently contested cities are at the heart of ongoing ethnonational conflicts, and their final status is often a central issue for peace negotiations, without which no final resolution can be reached. These negotiations, typically led by national politicians and diplo- mats, include little, if any, representation of local actors and voices. These voices are often fundamentally different from those of state- centric actors, and they may bring to the table different ideas, values, and perspectives concerning the future of contested cities. This article integrates the seeing like a city theoretical approach with the growing literature on urban peacebuilding and asks: How is seeing peace like a city different from seeing peace like a state? and whether the visions of local pro-peace grassroots leaders are com- plementary or contradictory to the models that national decision- makers propose for cities. We analyse the case study of Jerusalem using historical analysis, public opinion surveys, and in-depth inter- views to illustrate the tension between state-centric and city-centric logics. Our findings show the distinction between the focus of state-centric processes on ‘rigid’ issues (e.g. security and sover- eignty) and the focus of city-centric processes on ‘soft’ issues (e.g. tolerance and daily life). We conclude the paper with an explication of the implications of our framework, seeing peace like a city for research and practice in other violently contested societies.
Photosystem II reaction centers extract electrons from water, providing the basis of oxygenic life on earth. Among the light-sensitive pigments of the reaction center, a central chlorophyll a dimer, known as the special pair, so far has escaped a complete theoretical characterization of its excited state properties. The close proximity of the special pair pigments gives rise to short-range effects that comprise a coupling between local and charge transfer (CT) excited states as well as other intermolecular quantum effects. Using a multiscale simulation and a diabatization technique, we show that the coupling to CT states is responsible for 45% of the excitonic coupling in the special pair. The other short-range effects cause a nonconservative nature of the circular dichroism spectrum of the reaction center by effectively rotating the electric transition dipole moments of the special pair pigments inverting and strongly enhancing their intrinsic rotational strength.Photosystem II reaction centers extract electrons from water, providing the basis of oxygenic life on earth. Among the light-sensitive pigments of the reaction center, a central chlorophyll a dimer, known as the special pair, so far has escaped a complete theoretical characterization of its excited state properties. The close proximity of the special pair pigments gives rise to short-range effects that comprise a coupling between local and charge transfer (CT) excited states as well as other intermolecular quantum effects. Using a multiscale simulation and a diabatization technique, we show that the coupling to CT states is responsible for 45% of the excitonic coupling in the special pair. The other short-range effects cause a nonconservative nature of the circular dichroism spectrum of the reaction center by effectively rotating the electric transition dipole moments of the special pair pigments inverting and strongly enhancing their intrinsic rotational strength.
The problem of tunneling ionization and the associated questions of how long it takes for an electron to tunnel through the barrier, and what the tunneling rate has fascinated scientists for almost a century. In strong field physics, tunnel ionization plays an important role, and accurate knowledge of the time-dependent tunnel rate is of paramount importance. The Keldysh theory and other more advanced related theories are often used, but their accuracy is still controversial. In previous work, we suggested using a curved waveguide as a quantum simulator to simulate the tunnel ionization process. Here we implemented for the first time such a curved waveguide and observed the simulated tunneling ionization process. We compare our results with the theory.
In recent years, there has been a significant increase in the number of East Jerusalem Palestinian students studying at Israeli higher education institutions in Israel and in pre- academic preparatory programs. This study examines how spontaneousencounters with Jewish students while attending an Israeli academic institution are associated with young East Jerusalem Palestinian students’ attitudes toward the integration of East Jerusalem Palestinians into the city of Jerusalem and cooperation with Israeli Jews. We analyze the responses to an online survey of 106 East Jerusalem Palestinian students attending a one-year preparatory program at an Israeli academic institute. We find that Palestinian students who report spontaneous contact with Jewish students on campus during the year express more favorable attitudes toward the integration of East Jerusalem Palestinians into the city of Jerusalem and more positive attitudes toward Jewish Israelis in general.
Binary compositions of surface ligands are known to improve the colloidal stability and fluorescence quantum yield of nanocrystals (NCs), due to ligand–ligand interactions and surface organization. Herein, we follow the thermodynamics of a ligand exchange reaction of CdSe NCs with alkylthiol mixtures. The effects of ligand polarity and length difference on ligand packing were investigated using isothermal titration calorimetry (ITC). The thermodynamic signature of the formation of mixed ligand shells was observed. Correlating the experimental results with thermodynamic mixing models has allowed us to calculate the interchain interactions and to infer the final ligand shell configuration. Our findings demonstrate that, in contrast to macroscopic surfaces, the small dimensions of the NCs and the subsequent increased interfacial region between dissimilar ligands allow the formation of a myriad of clustering patterns, controlled by the interligand interactions. This work provides a fundamental understanding of the parameters determining the ligand shell structure and should help guide smart surface design toward NC-based applications.
Social organization is commonly dynamic, with extreme examples in annual social insects, but little is known about the underlying signals and mechanisms. Bumble bee larvae with close contact to a queen do not differentiate into gynes, pupate at an earlier age, and are commonly smaller than siblings that do not contact a queen. We combined detailed observations, proteomics, microRNA transcriptomics, and gland removal surgery to study the regulation of brood development and division of labor in the annual social bumble bee Bombus terrestris. We found that regurgitates fed to larvae by queens and workers differ in their protein and microRNA composition. The proteome of the regurgitate overlaps significantly with that of the mandibular (MG) and hypopharyngeal glands (HPG), suggesting that these exocrine glands are sources of regurgitate proteins. The proteome of the MG and HPG, but not the salivary glands, differs between queens and workers, with caste-specificity preserved for the MG and regurgitate proteomes. Queens subjected to surgical removal of the MG showed normal behavior, brood care, and weight gain, but failed to shorten larval development. These findings suggest that substances in the queen MG are fed to larvae and influence their developmental program. We suggest that when workers emerge and contribute to larval feeding, they dilute the effects of the queen substances, until she can no longer manipulate the development of all larvae. Longer developmental duration may allow female larvae to differentiate into gynes rather than to workers, mediating the colony transition from the ergonomic to the reproductive phase.
