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The fluorescence kinetics in intact photosystem II (PS II) core particles from the cyanobacterium Thermosynechococcus elongatus is measured with picosecond resolution at room temperature in open reaction centers. The analysis of the overall trapping kinetics based on the theory of energy migration and trapping on lattices has shown that the charge separation kinetics in photosystem II is extremely trap-limited and not diffusion-to-the-trap limited.

A study was conducted to examine the effect of the single-residue mutation of leucine 42 to arginine (L42R) centrally positioned in the polypeptide binding pocket of SecB on its chaperonin function in Escherichia coli. The study results indicated that a reduced polypeptide binding affinity exhibited by SecB(L42R) mutant facilitated the partial folding of the bound polypeptide chain rendering it translocation-incompetent.

A general route is described for the template-directed preparation of self-assembled heteromultimetallic salen structures by using noncovalent coordinative metal-ligand interactions. Many higher order assemblies are studied by using a combination of NMR spectroscopy and X-ray crystallography.

The interfacial structure of muscovite in contact with aqueous CsI solutions was measured using surface X-ray diffraction for several CsI concentrations (2-1000 mM). At CsI concentrations up to 200 mM, Cs+ adsorption is likely hindered by H3O+, as both cations compete for the adsorption site above the muscovite hexagonal cavity. Above this concentration, more Cs+ adsorbs than is required to compensate the negatively charged muscovite surface, which means that coadsorption of an anion takes place. The I- anion does not coadsorb in an ordered manner. Moreover, the hydration ring and water layers do not change significantly as a function of the CsI concentration. [ABSTRACT FROM AUTHOR]

Toward the development of photoresponsive anion receptors, a stiff-stilbene photoswitch has been equipped with two urea anion-binding motifs. Photoinduced E/Z isomerization has been studied in detail by UV-vis and NMR spectroscopy. Titration experiments (¹H NMR) reveal strong binding of acetate and phosphate to the (Z)-isomer, in which the urea groups are closely together. Isomerization to the (E)-form separates the urea motifs, resulting in much weaker binding. Additionally, geometry optimizations by density functional theory (DFT) illustrate that oxo-anion binding to the (Z)-form involves four hydrogen bonds. [ABSTRACT FROM AUTHOR]

Molecular photoswitches have opened up a myriad of opportunities in applications ranging from responsive materials and control of biological function to molecular logics. Here, we show that the photoswitching mechanism of donor--acceptor Stenhouse adducts (DASA), a recently reported class of photoswitches, proceeds by photoinduced Z--E isomerization, followed by a thermal, conrotatory 4;r-electrocyclization. The photogenerated intermediate is manifested by a bathochromically shifted band in the visible absorption spectrum of the DASA. The identification of the role of this intermediate reveals a key step in the photoswitching mechanism that is essential to the rational design of switching properties via structural modification. [ABSTRACT FROM AUTHOR]

A responsive bis-urea receptor can be switched between three isomers using light and heat as evidenced by ¹H NMR and UV-vis spectroscopy. Anion binding experiments (¹H NMR titrations, ESI-MS) reveal a high selectivity for dihydrogen phosphate. Importantly, a large difference in binding affinity to the interchangeable isomers is observed, which is further rationalized by DFT calculations. As a consequence, the amount of bound substrate can be controlled via photo- and thermal isomerization in a three-step process. [ABSTRACT FROM AUTHOR]

The design, synthesis, and dynamic behavior of a series of novel tetrapodal molecular switches and motors containing common functional groups for attachment to various inorganic and organic surfaces are presented. Using a Diels--Alder reaction, an anthracene unit with four functionalized alkyl substituents ("legs") was coupled to maleimide-functionalized molecular switches or motors under ambient conditions. Terminal functional groups at the "legs" include thioacetates and azides, making these switches and motors ideal candidates for attachment to metallic or alkyne-functionalized surfaces. UV/vis absorption spectroscopy shows that the molecular switches and motors retain their ability to undergo reversible photoinduced and/or thermally induced structural changes after attachment to the tetrapodal anthracene. [ABSTRACT FROM AUTHOR]

A new colorimetric method is presented that allows for simple and effective discrimination between (iso)quinoline nuclei pertinent to many alkaloid species. The method is based on the reversible incorporation of Zn 2+ions into a bis-salphen chromophore under aqueous conditions. The metalation process is a function of the stability of the Zn−N (acceptor−donor) interaction and is accompanied by a clear colorimetric response. [ABSTRACT FROM AUTHOR]

A general route is presented toward the template-directed preparation of self-assembled heteromultimetallic salen structures using noncovalent coordinative metal-ligand interactions. Various higher order assemblies have been studied in detail using a combination of NMR spectroscopy and X-ray crystallography. [ABSTRACT FROM AUTHOR]

Controlling and understanding reaction temperature variations in catalytic processes are crucial for assessing the performance of a catalyst material. Local temperature measurements are challenging, however. Luminescence thermometry is a promising remote-sensing tool, but it is cross-sensitive to the optical properties of a sample and other external parameters. In this work, we measure spatial variations in the local temperature on the micrometer length scale during carbon dioxide (CO 2 ) methanation over a TiO 2 -supported Ni catalyst and link them to variations in catalytic performance. We extract local temperatures from the temperature-dependent emission of Y 2 O 3 :Nd 3+ particles, which are mixed with the CO 2 methanation catalyst. Scanning, where a near-infrared laser locally excites the emitting Nd 3+ ions, produces a temperature map with a micrometer pixel size. We first designed the Y 2 O 3 :Nd 3+ particles for optimal temperature precision and characterized cross-sensitivity of the measured signal to parameters other than temperature, such as light absorption by the blackened sample due to coke deposition at elevated temperatures. Introducing reaction gases causes a local temperature increase of the catalyst of on average 6-25 K, increasing with the reactor set temperature in the range of 550-640 K. Pixel-to-pixel variations in the temperature increase show a standard deviation of up to 1.5 K, which are attributed to local variations in the catalytic reaction rate. Mapping and understanding such temperature variations are crucial for the optimization of overall catalyst performance on the nano- and macroscopic scale.

Photoisomerization of retinal is pivotal to ion translocation across the bacterial membrane and has served as an inspiration for the development of artificial molecular switches and machines. Light-driven synthetic systems in which a macrocyclic component transits along a nonsymmetric axle in a specific direction have been reported; however, unidirectional and repetitive translocation of protons has not been achieved. Herein, we describe a unique protonation-controlled isomerization behavior for hemi-indigo dyes bearing N-heterocycles, featuring intramolecular hydrogen bonds. Light-induced isomerization from the Z to E isomer is unlocked when protonated, while reverse E → Z photoisomerization occurs in the neutral state. As a consequence, associated protons are displaced in a preferred direction with respect to the photoswitchable scaffold. These results will prove to be critical in developing artificial systems in which concentration gradients can be effectively generated using (solar) light energy.

The crucial role of healthy soil in achieving sustainable food production and environment is increasingly recognized, as is the importance of proper assessment of soil quality. We introduce a new framework, open soil index (OSI), which integrally evaluates soil health of agricultural fields and provides recommendation for farming practices. The OSI is an open-source modular framework in which soil properties, functions, indicators and scores, and management advice are linked hierarchically. Soil health is evaluated with respect to sustainable crop production but can be extended to other ecosystem functions. The OSI leverages the existing knowledge base of agronomic research and routine laboratory data, enabling its application with limited cost. The OSI is a generic framework that can be adopted for specific regions with specific objectives. As a proof of concept, the OSI is implemented for all (>700,000) Dutch agricultural fields and illustrated with 11 pairs ("good" and "poor") of local fields and 32 fields where soil quality and crop yield have been monitored. The OSI produced reasonable evaluation for most pairs when soil physical functions were refined with on-site soil visual assessment. The soil functions are sufficiently independent and yet together reflect complex multidimensionality of soil quality. The framework can facilitate designing sustainable soil management programs by bridging regional targets to field-level actions.

Membrane transport proteins fulfill important regulatory functions in biology with a common trait being their ability to respond to stimuli in the environment. Various small-molecule receptors, capable of mediating transmembrane transport, have been successfully developed. However, to confer stimuli-responsiveness on them poses a fundamental challenge. Here we demonstrate photocontrol of transmembrane transport and electric potential using bis(thio)ureas derived from stiff-stilbene. UV-vis and 1 H NMR spectroscopy are used to monitor E - Z photoisomerization of these bis(thio)ureas and 1 H NMR titrations reveal stronger binding of chloride to the ( Z )-form than to the ( E )-form. Additional insight into the binding properties is provided by single crystal X-ray crystallographic analysis and DFT geometry optimization. Importantly, the ( Z )-isomers are much more active in transmembrane transport than the respective ( E )-isomers as shown through various assays. As a result, both membrane transport and depolarization can be modulated upon irradiation, opening up new prospects toward light-based therapeutics as well as physiological and optopharmacological tools for studying anion transport-associated diseases and to stimulate neuronal activity, respectively.

Broadening of multiexciton emission from colloidal quantum dots (QDs) at room temperature is important for their use in high-power applications, but an in-depth characterization has not been possible until now. We present and apply a novel spectroscopic method to quantify the biexciton line width and biexciton binding energy of single CdSe/CdS/ZnS colloidal QDs at room temperature. In our method, which we term "cascade spectroscopy", we select emission events from the biexciton cascade and reconstruct their spectrum. The biexciton has an average emission line width of 86 meV on the single-QD scale, similar to that of the exciton. Variations in the biexciton repulsion ( E b = 4.0 ± 3.1 meV; mean ± standard deviation of 15 QDs) are correlated with but are more narrowly distributed than variations in the exciton energy (10.0 meV standard deviation). Using a simple quantum-mechanical model, we conclude that inhomogeneous broadening in our sample is primarily due to variations in the CdS shell thickness.

Plasmonic modes in optical cavities can be amplified through stimulated emission. Using this effect, plasmonic lasers can potentially provide chip-integrated sources of coherent surface plasmon polaritons (SPPs). However, while plasmonic lasers have been experimentally demonstrated, they have not generated propagating plasmons as their primary output signal. Instead, plasmonic lasers typically involve significant emission of free-space photons that are intentionally outcoupled from the cavity by Bragg diffraction or that leak from reflector edges due to uncontrolled scattering. Here, we report a simple cavity design that allows for straightforward extraction of the lasing mode as SPPs while minimizing photon leakage. We achieve plasmonic lasing in 10-μm-long distributed-feedback cavities consisting of a Ag surface periodically patterned with ridges coated by a thin layer of colloidal semiconductor nanoplatelets as the gain material. The diffraction to free-space photons from cavities designed with second-order feedback allows a direct experimental examination of the lasing-mode profile in real- and momentum-space, in good agreement with coupled-wave theory. In contrast, we demonstrate that first-order-feedback cavities remain "dark" above the lasing threshold and the output signal leaves the cavity as propagating SPPs, highlighting the potential of such lasers as on-chip sources of plasmons.

The temperature-sensitive luminescence of nanoparticles enables their application as remote thermometers. The size of these nanothermometers makes them ideal to map temperatures with a high spatial resolution. However, high spatial resolution mapping of temperatures >373 K has remained challenging. Here, we realize nanothermometry with high spatial resolutions at elevated temperatures using chemically stable upconversion nanoparticles and confocal microscopy. We test this method on a microelectromechanical heater and study the temperature homogeneity. Our experiments reveal distortions in the luminescence spectra that are intrinsic to high-resolution measurements of samples with nanoscale photonic inhomogeneities. In particular, the spectra are affected by the high-power excitation as well as by scattering and reflection of the emitted light. The latter effect has an increasing impact at elevated temperatures. We present a procedure to correct these distortions. As a result, we extend the range of high-resolution nanothermometry beyond 500 K with a precision of 1-4 K. This work will improve the accuracy of nanothermometry not only in micro- and nanoelectronics but also in other fields with photonically inhomogeneous substrates., Competing Interests: The authors declare the following competing financial interest(s): T.v.O., R.G.S., and H.H.P.G. work for DENSsolutions B.V., a company manufacturing and marketing in situ TEM systems. The remaining authors declare no competing interests., (© 2021 The Authors. Published by American Chemical Society.)

Controlling supramolecular polymerization by external stimuli holds great potential toward the development of responsive soft materials and manipulating self-assembly at the nanoscale. Photochemical switching offers the prospect of regulating the structure and properties of systems in a noninvasive and reversible manner with spatial and temporal control. In addition, this approach will enhance our understanding of supramolecular polymerization mechanisms; however, the control of molecular assembly by light remains challenging. Here we present photoresponsive stiff-stilbene-based bis-urea monomers whose trans isomers readily form supramolecular polymers in a wide range of organic solvents, enabling fast light-triggered depolymerization-polymerization and reversible gel formation. Due to the stability of the cis isomers and the high photostationary states (PSS) of the cis - trans isomerization, precise control over supramolecular polymerization and in situ gelation could be achieved with short response times. A detailed study on the temperature-dependent and photoinduced supramolecular polymerization in organic solvents revealed a kinetically controlled nucleation-elongation mechanism. By application of a Volta phase plate to enhance the phase-contrast method in cryo-EM, unprecedented for nonaqueous solutions, uniform nanofibers were observed in organic solvents.

Ackee fruits ( Blighia sapida ), an important food source in some tropical countries, can be the cause of serious poisoning. Ackees contain hypoglycin A and methylenecyclopropylglycine. Experiments were undertaken by a volunteer to elucidate the metabolic details of poisoning. Rapid intestinal absorption of the toxins was followed by their slow degradation to methylenecyclopropylacetyl and methylenecyclopropylformyl conjugates. Impairment of the metabolism of branched chain amino acids and ß-oxidation of fatty acids was found. Reduced enzyme activities were observed for several days after ingestion. A defined dose of fruit material caused significantly higher concentrations of metabolites when consumed 24 h after a previous ingestion than when consumed only once. The accumulation of toxins, toxin metabolites, and products of the intermediate metabolism after repeated consumption may, at least partly, explain the high frequency of fatal cases observed during harvesting. No inhibition of enzymes that degrade long-chain acyl compounds was observed in the experiments.

The flatness of muscovite mica makes it a convenient substrate to study epitaxy. We have analyzed the growth of rhodochrosite (MnCO 3 ) crystals in solution and on muscovite mica. Growth at high supersaturations occurs via the formation of amorphous MnCO 3 , which over time transforms into the crystalline form. In the presence of muscovite mica, epitaxial rhodochrosite crystals with a size of approximately 1 μm form. These crystals are kinetically roughened, because of the high supersaturation. The lattice match between MnCO 3 and muscovite was found not to be the main reason for epitaxy. If the growth experiment is performed twice, the original epitaxial MnCO 3 crystals are overgrown by many small crystallites. Similarly, spherical MnCO 3 crystals with many overgrown facets can be formed on a muscovite surface that is exposed to humidity or by using a higher MnCO 3 supersaturation. A comparison with calcite shows that epitaxy strongly depends on initial supersaturation for both carbonates. In contrast to previous studies, we find that at the right supersaturation, epitaxial calcite crystal growth is possible on freshly cleaved muscovite., Competing Interests: The authors declare no competing financial interest.

Bright and fast fluorescence makes semiconductor nanocrystals, or quantum dots (QDs), appealing for applications ranging from biomedical research to display screens. However, a few percent of their fluorescence intensity is surprisingly slow. Research into this "delayed emission" has been scarce, despite undesired consequences for some applications and potential opportunities for others. Here, we characterize the dynamics of delayed emission exhibited by individual CdSe/CdS core/shell QDs and correlate these with changes in the emission spectrum. The delayed-emission intensity from a single QD fluctuates strongly during an experiment of several minutes and is thus not always "on", implying that control over delayed emission may be possible. Periods of bright delayed emission correlate with red-shifted emission spectra. This behavior is consistent with exciton polarization by fluctuating electric fields due to diffusing surface charges, which have been known to cause spectral diffusion in QDs. Our findings thus provide a stepping stone for future efforts to control delayed emission.

Metal-halide perovskite nanocrystals show promise as the future active material in photovoltaics, lighting, and other optoelectronic applications. The appeal of these materials is largely due to the robustness of the optoelectronic properties to structural defects. The photoluminescence quantum yield (PLQY) of most types of perovskite nanocrystals is nevertheless below unity, evidencing the existence of nonradiative charge-carrier decay channels. In this work, we experimentally elucidate the nonradiative pathways in CsPbBr 3 nanoplatelets, before and after chemical treatment with PbBr 2 that improves the PLQY. A combination of picosecond streak camera and nanosecond time-correlated single-photon counting measurements is used to probe the excited-state dynamics over 6 orders of magnitude in time. We find that up to 40% of the nanoplatelets from a synthesis batch are entirely nonfluorescent and cannot be turned fluorescent through chemical treatment. The other nanoplatelets show fluorescence, but charge-carrier trapping leads to losses that are prevented by chemical treatment. Interestingly, even without chemical treatment, some losses due to trapping are mitigated because trapped carriers spontaneously detrap on nanosecond-to-microsecond timescales. Our analysis shows that multiple nonradiative pathways are active in perovskite nanoplatelets, which are affected differently by chemical treatment with PbBr 2 . More generally, our work highlights that in-depth studies using a combination of techniques are necessary to understand nonradiative pathways in fluorescent nanocrystals. Such understanding is essential to optimize synthesis and treatment procedures., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH 2 -MIL-53(Al) were dispersed in a Matrimid polymer matrix with different weight ratios (0-100 wt %) and drop-casted on planar capacitive transducer devices. These coated devices were electrically analyzed using impedance spectroscopy and investigated for their sensing properties toward the detection of a series of alcohols and water in the gas phase. The measurements indicated a reversible and reproducible response in all devices. Sensor devices containing 40 wt % NH 2 -MIL-53(Al) in Matrimid showed a maximum response for methanol and water. The sensor response time slowed down with increasing MOF concentration until 40 wt %. The half time of saturation response (τ 0.5 ) increased by ∼1.75 times for the 40 wt % composition compared to devices coated with Matrimid only. This is attributed to polymer rigidification near the MOF/polymer interface. Higher MOF loadings (≥50 wt %) resulted in brittle coatings with a response similar to the 100 wt % MOF coating. Cross-sensitivity studies showed the ability to kinetically distinguish between the different alcohols with a faster response for methanol and water compared to ethanol and 2-propanol. The observed higher affinity of the pure Matrimid polymer toward methanol compared to water allows also for a higher uptake of methanol in the composite matrices. Also, as indicated by the sensing studies with a mixture of water and methanol, the methanol uptake is independent of the presence of water up to 6000 ppm of water. The NH 2 -MIL-53(Al) MOFs dispersed in the Matrimid matrix show a sensitive and reversible capacitive response, even in the presence of water. By tuning the precise compositions, the affinity kinetics and overall affinity can be tuned, showing the promise of this type of chemical sensors.

Consumption of ackee (Blighia sapida) and lychee (Litchi chinensis) fruit has led to severe poisoning. Considering their expanded agricultural production, toxicological evaluation has become important. Therefore, the biochemical effects of eating 1 g/kg canned ackee, containing 99.2 μmol/kg hypoglycin A, and 5 g/kg canned lychee, containing 1.3 μmol/kg hypoglycin A, were quantified in a self-experiment. Using ultra-high-performance liquid chromatography/mass spectrometry, hypoglycin A, methylenecyclopropylacetyl-glycine, and methylenecyclopropylformyl-glycine, as well as the respective carnitine conjugates, were found in urine after ingesting ackee. Hypoglycin A and its glycine derivative were also present in urine after eating lychee. Excretion of physiological acyl conjugates was significantly increased in the ackee experiment. Ingestion of ackee led to up to 15.1 nmol/L methylenecyclopropylacetyl-glycine and traces of methylenecyclopropylformyl-carnitine in the serum. These compounds were not found in the serum after eating lychee. Hypoglycin A accumulated in the serum in both experiments.

Ordered two-dimensional (2D) superstructures of colloidal nanocrystals (NCs) can be tailored by the size, shape, composition, and surface chemistry of the NC building blocks, which can give directionality to the resulting superstructure geometry. The exact formation mechanism of 2D NC superstructures is however not yet fully understood. Here, we show that oleic acid (OA) ligands induce atomic alignment of wurtzite ZnS bifrustum-shaped NCs. We find that in the presence of OA ligands the {002} facets of the ZnS bifrustums preferentially adhere to the liquid-air interface. Furthermore, OA ligands induce inter-NC interactions that also orient the NCs in the plane of the liquid-air interface, resulting in atomically aligned 2D superstructures. We follow the self-assembly process in real-time with in situ grazing incidence small-angle X-ray scattering and find that the NCs form a hexagonal superstructure at early stages after which they come closer over time, resulting in a close-packed NC superstructure. Our results demonstrate the profound influence that surface ligands have on the directionality of 2D NC superstructures and highlight the importance of detailed in situ studies in order to understand the self-assembly of NCs into 2D superstructures.