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C19H14FN5O, monoclinic, P21/c(no. 14), a= 7.2944(3) Å, b= 12.2032(5) Å, c= 18.1070(7) Å, β= 95.807(4)°, V= 1603.52(11) Å3, Z= 4, Rgt(F) = 0.0451, wRref= 0.1217, T = 100(2) K.

Colloidal semiconductor nanocrystals have long been considered a promising source of time-correlated and entangled photons via the cascaded emission of multiexcitonic states. The spectroscopy of such cascaded emission, however, is hindered by efficient nonradiative Auger-Meitner decay, rendering multiexcitonic states nonemissive. Here we present room-temperature heralded spectroscopy of three-photon cascades from triexcitons in giant CsPbBr3nanocrystals. We show that this system exhibits second- and third-order correlation function values, g(2)(0) and g(3)(0,0), close to unity, identifying very weak binding of both biexcitons and triexcitons. Combining fluorescence lifetime analysis, photon statistics, and spectroscopy, we can readily identify emission from higher multiexcitonic states. We use this to verify emission from a single emitter despite high emission quantum yields of multiply excited states and comparable emission lifetimes of singly and multiply excited states. Finally, we present potential pathways toward control of the photon number statistics of multiexcitonic emission cascades.

A new asymmetric synthetic route to (+)- and (−)-limaspermidine was devised, starting with chirally resolved enantiomerically pure 2-pyrone Diels–Alder cycloadducts. This route utilizes intramolecular Pd-catalyzed aromatic C–H amidation and imino-Diels–Alder reactions to construct the key indoline and indolizidine subunits onto the central cyclohexane core, allowing the straightforward formal total syntheses of both (+)- and (−)-limaspermidine.

Colloidal quantum dots (cQDs), semiconductor materials with widely tunable properties, can be printed in submicrometer patterns through electrohydrodynamic printing, avoiding aggressive photolithography steps. Postprinting ligand exchange determines the final optoelectronic properties of the cQD structures. However, achieving a complete bulk exchange is challenging, and the conventional vibrational analysis lacks the required spatial resolution. Infrared nanospectroscopy enables quantitative analysis of vibrational signals and structural topography on the nanometer scale upon ligand substitution on lead sulfide cQDs. A solution of ethanedithiol led to rapid (∼60 s) exchange of ≤90% of the ligands, in structures up to ∼750 nm thick. Prolonged exposures (>1 h) caused the degradation of the microstructures, with a systematic removal of cQDs regulated by surface:bulk ratios and solvent interactions. This study establishes a method for the development of devices through a combination of tunable photoactive materials, additive manufacturing of microstructures, and their quantitative nanometer-scale analysis.

Successful reproduction in mammals requires gamete development, fertilization, and early embryonic development. Defects in any of these processes can lead to infertility, recurrent miscarriages, and congenital defects. The clinical recognition of the genetic causes of female reproductive insufficiency using increasingly advanced genetic technologies poses a serious challenge for reproductive medicine in the 21st century. Herein, the current literature on genetic factors involved in reproductive losses was summarized. A literature search was conducted using Web of Science, MEDLINE, and PubMed databases for articles written in English on the genetic causes of women’s reproductive health disorders. Future implementation of whole-exome and whole-genome sequencing is expected to identify numerous genetic factors responsible for oocyte quality. Which will aid in increasing the likelihood of successful female reproductive function, improve the outcomes of assisted reproductive technologies, optimize treatment, and facilitate genetic diagnosis of patients.

Abstract: Mineral exchange is a crucial factor for all functions within the organisms of living beings. Chemical elements are integral components of cellular structures, organs, and tissues, as well as the blood and lymph. Together with water, they maintain osmotic pressure, support acid–base balance, and participate in various metabolic reactions within the body. Calcium and magnesium ions are also involved in metabolic interactions. The absorption of calcium by the organism requires magnesium, with magnesium reserves being drawn from various organs and tissues. Therefore, the ratio of calcium-to-magnesium ion concentrations in water is of significant importance. In this study, the results of a chronic experiment demonstrated that desalinated water, devoid of macroelements, affected the vitality of the organisms, even when the test crustaceans were fed. According to experimental data, the maximum survival duration of the experimental group of crustaceans was observed in a water environment with a calcium-to-magnesium ion ratio of 4 : 1. Given the nontoxicity of the water environment, it can be concluded that at such a ratio of these elements, metabolic processes within the organism operate optimally, thereby prolonging the lifespan of the test organisms.

Lead halide perovskite quantum dots (QDs), the latest generation of the colloidal QD family, exhibit outstanding optical properties, which are now exploited as both classical and quantum light sources. Most of their rather exceptional properties are related to the peculiar exciton fine-structure of band-edge states, which can support unique bright triplet excitons. The degeneracy of the bright triplet excitons is lifted with energetic splitting in the order of millielectronvolts, which can be resolved by the photoluminescence (PL) measurements of single QDs at cryogenic temperatures. Each bright exciton fine-structure-state (FSS) exhibits a dominantly linear polarization, in line with several theoretical models based on the sole crystal field, exchange interaction, and shape anisotropy. Here, we show that in addition to a high degree of linear polarization, the individual exciton FSS can exhibit a non-negligible degree of circular polarization even without external magnetic fields by investigating the four Stokes parameters of the exciton fine-structure in individual CsPbBr3QDs through Stokes polarimetric measurements. We observe a degree of circular polarization up to ∼38%, which could not be detected by using the conventional polarimetric technique. In addition, we found a consistent transition from left- to right-hand circular polarization within the fine-structure triplet manifold, which was observed in magnetic-field-dependent experiments. Our optical investigation provides deeper insights into the nature of the exciton fine structures and thereby drives the yet-incomplete understanding of the unique photophysical properties of this class of QDs for the benefit of future applications in chiral quantum optics.

Near-infrared (NIR) luminescence and photoacoustic (PA) imaging have attracted increasing attention for the real-time monitoring of biological samples due to high sensitivity, resolution, and pronounced signal detection depth, respectively. For improved contrast, both techniques require imaging agents possessing high absorption in the red-NIR range. Herein, we took advantage of a ternary complex formed with the anionic ytterbium(III) tetrakis(2-thenoyltrifluoroacetonate) ([Yb(tta)4]−) and the cationic NIR-absorbing chromophore, 1,1′-diethyl-2,2′-dicarbocyanine (Cy+), to evaluate its potential to act as a dual-mode NIR luminescence and PA imaging agent. We demonstrated that, upon excitation with red-NIR light, Cy[Yb(tta)4] encapsulated into polystyrene nanoparticles is able to generate both NIR Yb3+emission and a PA signal in an imaging experiment performed in a tissue-mimicking phantom.

One step method of iron oxides nanoparticles synthesis using novel type of microreactors was reported. All the data received from analysis of physical and chemical properties demonstrated that the nanoparticles obtained by means of the new method are similar to the nanopowders synthesized by wet precipitation. They are magnetite-maghemite solid solutions with unit cell parameter between 8.362 and 8.374 Å, with coherent scattering range values about 9 nm. In comparison with precipitated nanopowders they have lesser degree of agglomeration. Samples obtained in microreactor have smaller value and smaller spread in regard of the specific surface (76–86 m2/g) in comparison with precipitated ones (75–125 m2/g). All the samples from microreactor consist of spherical inhomogeneities with a diffuse surface, while sample of iron oxide nanopowder synthesized by the co-precipitation method consists of scattering cylindrical inhomogeneities with nearly smooth phase boundary. It was shown that microreactor with intensively swirling flows has demonstrated several advantages: (i) possibility to control the degree of oxidation of the product which depends on the flow rates of reagents solutions to the reactor; (ii) high productivity (up to 7 L/min for the suspension with particles, approx. 200 kg/day for the dried particles) that eases the scaling-up of the proposed synthesis method.

Although the construction of peptides with well-defined three-dimensional structures and predictable functions, including biological activity, using conformationally constrained β-amino acids has been shown to be a very successful strategy, their broad application is limited by access to the appropriate building blocks. In particular, trans- and cis-stereoisomers of 2-aminocyclopentanecarboxylic acid (ACPC) are of high interest. The scalable synthesis of all four stereoisomers of Fmoc derivatives of ACPC is presented with NMR-based analysis methods for their enantiomeric purity.

Abstract: The discharge of synthetic surfactants into the environment poses a serious threat to natural water bodies, as even at relatively low concentrations, they harm the biological processes of aquatic organisms. The molecules of dissolved detergents, by wedging themselves between water molecules, weaken the surface film. The hydrophilic part promotes the dissolution of the substance in water, while the hydrophobic part repels it. As a result, the entire water surface is covered with a peculiar film, which leads to the accumulation of toxic substances and a decrease in the oxygen concentration in the aquatic environment. To study the impact of surfactants on living organisms, we assess the ecological impact of synthetic surfactants on the biota of natural water bodies. We performed toxicological bioassays of aqueous solutions with low concentrations of sodium dodecylbenzenesulfonate on the crustacean Daphnia magna, which serves as a standard test organism both in Ukraine and abroad. The concentration of sodium dodecylbenzenesulfonate that caused the mortality of 50% of test organisms (LC50) was determined, and the degree of toxicity of sodium dodecylbenzenesulfonate to aquatic ecosystems was found according to the EU Directive 93/67/EEC.

Nanocrystal superlattices (NC SLs) have long been sought as promising metamaterials, with nanoscale-engineered properties arising from collective and synergistic effects among the constituent building blocks. Lead halide perovskite (LHP) NCs come across as outstanding candidates for SL design, as they demonstrate collective light emission, known as superfluorescence, in single- and multicomponent SLs. Thus far, LHP NCs have only been assembled in single-component SLs or coassembled with dielectric NC building blocks acting solely as spacers between luminescent NCs. Here, we report the formation of multicomponent LHP NC-only SLs, i.e., using only CsPbBr3NCs of different sizes as building blocks. The structural diversity of the obtained SLs encompasses the ABO6, ABO3, and NaCl structure types, all of which contain orientationally and positionally locked NCs. For the selected model system, the ABO6-type SL, we observed efficient NC coupling and Förster-like energy transfer from strongly confined 5.3 nm CsPbBr3NCs to weakly confined 17.6 nm CsPbBr3NCs, along with characteristic superfluorescence features at cryogenic temperatures. Spatiotemporal exciton dynamics measurements reveal that binary SLs exhibit enhanced exciton diffusivity compared to single-component NC assemblies across the entire temperature range (from 5 to 298 K). The observed coherent and incoherent NC coupling and controllable excitonic transport within the solid NC SLs hold promise for applications in quantum optoelectronic devices.

Rechargeable garnet-based solid-state Li batteries hold immense promise as nonflammable, nontoxic, and high energy density energy storage systems, employing Li7La3Zr2O12(LLZO) with a garnet-type structure as the solid-state electrolyte. Despite substantial progress in this field, the advancement and eventual commercialization of garnet-based solid-state Li batteries are impeded by void formation at the LLZO/Li interface at practical current densities and areal capacities beyond 1 mA cm–2and 1 mAh cm–2, respectively, resulting in limited cycling stability and the emergence of Li dendrites. Additionally, developing a fabrication approach for thin LLZO electrolytes to achieve high energy density remains paramount. To address these critical challenges, herein, we present a facile methodology for fabricating self-standing, 50 μm thick, porous LLZO membranes with a small pore size of ca. 2.3 μm and an average porosity of 51%, resulting in a specific surface area of 1.3 μm–1, the highest reported to date. The use of such LLZO membranes significantly increases the Li/LLZO contact area, effectively mitigating void formation. This methodology combines two key elements: (i) the use of small pore formers of ca. 1.5 μm and (ii) the use of ultrafast sintering, which circumvents ceramics overdensification using rapid heating/cooling rates of ca. 50 °C per second. The fabricated porous LLZO membranes demonstrate exceptional cycling stability in a symmetrical Li/LLZO/Li cell configuration, exceeding 600 h of continuous operation at a current density of 0.1 mA cm–2.

The brightness of an emitter is ultimately described by Fermi’s golden rule, with a radiative rate proportional to its oscillator strength times the local density of photonic states. As the oscillator strength is an intrinsic material property, the quest for ever brighter emission has relied on the local density of photonic states engineering, using dielectric or plasmonic resonators1,2. By contrast, a much less explored avenue is to boost the oscillator strength, and hence the emission rate, using a collective behaviour termed superradiance. Recently, it was proposed3that the latter can be realized using the giant oscillator-strength transitions of a weakly confined exciton in a quantum well when its coherent motion extends over many unit cells. Here we demonstrate single-photon superradiance in perovskite quantum dots with a sub-100 picosecond radiative decay time, almost as short as the reported exciton coherence time4. The characteristic dependence of radiative rates on the size, composition and temperature of the quantum dot suggests the formation of giant transition dipoles, as confirmed by effective-mass calculations. The results aid in the development of ultrabright, coherent quantum light sources and attest that quantum effects, for example, single-photon emission, persist in nanoparticles ten times larger than the exciton Bohr radius.

The success of colloidal semiconductor nanocrystals (NCs) in science and optoelectronics is inextricable from their surfaces. The functionalization of lead halide perovskite NCs1–5poses a formidable challenge because of their structural lability, unlike the well-established covalent ligand capping of conventional semiconductor NCs6,7. We posited that the vast and facile molecular engineering of phospholipids as zwitterionic surfactants can deliver highly customized surface chemistries for metal halide NCs. Molecular dynamics simulations implied that ligand–NC surface affinity is primarily governed by the structure of the zwitterionic head group, particularly by the geometric fitness of the anionic and cationic moieties into the surface lattice sites, as corroborated by the nuclear magnetic resonance and Fourier-transform infrared spectroscopy data. Lattice-matched primary-ammonium phospholipids enhance the structural and colloidal integrity of hybrid organic–inorganic lead halide perovskites (FAPbBr3and MAPbBr3(FA, formamidinium; MA, methylammonium)) and lead-free metal halide NCs. The molecular structure of the organic ligand tail governs the long-term colloidal stability and compatibility with solvents of diverse polarity, from hydrocarbons to acetone and alcohols. These NCs exhibit photoluminescence quantum yield of more than 96% in solution and solids and minimal photoluminescence intermittency at the single particle level with an average ON fraction as high as 94%, as well as bright and high-purity (about 95%) single-photon emission.

Strong coupling between lead halide perovskite materials and optical resonators enables both polaritonic control of the photophysical properties of these emerging semiconductors and the observation of fundamental physical phenomena. However, the difficulty in achieving optical-quality perovskite quantum dot (PQD) films showing well-defined excitonic transitions has prevented the study of strong light–matter coupling in these materials, central to the field of optoelectronics. Herein we demonstrate the formation at room temperature of multiple cavity exciton-polaritons in metallic resonators embedding highly transparent Cesium Lead Bromide quantum dot (CsPbBr3-QD) solids, revealed by a significant reconfiguration of the absorption and emission properties of the system. Our results indicate that the effects of biexciton interaction or large polaron formation, frequently invoked to explain the properties of PQDs, are seemingly absent or compensated by other more conspicuous effects in the CsPbBr3-QD optical cavity. We observe that strong coupling enables a significant reduction of the photoemission line width, as well as the ultrafast modulation of the optical absorption, controllable by means of the excitation fluence. We find that the interplay of the polariton states with the large dark state reservoir plays a decisive role in determining the dynamics of the emission and transient absorption properties of the hybridized light-quantum dot solid system. Our results should serve as the basis for future investigations of PQD solids as polaritonic materials.

The number of hip revisions makes up over 12 % of all hip arthroplasty cases. For large acetabular defects custom-made acetabular component (CMAC) are required. Rates of malposition of CMACs are highly variable. Our study aims to develop a readily available, reliable and easily reproducible method for positioning of the CMAC. We tried to answer the following questions: 1) how often does the postoperative position of the implant corresponds to the planned one; 2) is the use of intrawound navigation improve the precision of acetabular implant position.

AbstractAminoacyl-tRNA synthetases are crucial enzymes involved in protein synthesis and various cellular physiological reactions. Aside from their standard role in linking amino acids to the corresponding tRNAs, they also impact protein homeostasis by controlling the level of soluble amino acids within the cell. For instance, leucyl-tRNA synthetase (LARS1) acts as a leucine sensor for the mammalian target of rapamycin complex 1 (mTORC1), and may also function as a probable GTPase-activating protein (GAP) for the RagD subunit of the heteromeric activator of mTORC1. In turn, mTORC1 regulates cellular processes, such as protein synthesis, autophagy, and cell growth, and is implicated in various human diseases including cancer, obesity, diabetes, and neurodegeneration. Hence, inhibitors of mTORC1 or a deregulated mTORC1 pathway may offer potential cancer therapies. In this study, we investigated the structural requirements for preventing the sensing and signal transmission from LARS to mTORC1. Building upon recent studies on mTORC1 regulation activation by leucine, we lay the foundation for the development of chemotherapeutic agents against mTORC1 that can overcome resistance to rapamycin. Using a combination of in-silico approaches to develop and validate an alternative interaction model, discussing its benefits and advancements. Finally, we identified a set of compounds ready for testing to prevent LARS1/RagD protein-protein interactions. We establish a basis for creating chemotherapeutic drugs targeting mTORC1, which can conquer resistance to rapamycin. We utilize in-silico methods to generate and confirm an alternative interaction model, outlining its advantages and improvements, and pinpoint a group of novel substances that can prevent LARS1/RagD interactions.Communicated by Ramaswamy H. Sarma

Coupled discrete event system have subsystems that share a common transition are subject to model deviation due to wear and tear of subsystem physical components. A fault due to model deviation can result in a fault in a corresponding physical system. Silent faults are faults that can propagate from one subsystem to another due to faults that are modeled as unobservable events. In this work, we investigate the problem of modeling silent faults in coupled discrete event systems with model deviations. Our goal is to introduce properties for subsystem to prevent the propagation of a silent fault. First, we provide a formal definition of deviation for coupled discrete event systems. Then, we provide the sufficient properties for deviation safety of the coupled discrete event system. Finally, using a case study, we show how using these properties can help a designer mitigate the occurrence of silent faults in cyber physical systems.

Understanding the origin of electron–phonon coupling in lead halide perovskites is key to interpreting and leveraging their optical and electronic properties. Here we show that photoexcitation drives a reduction of the lead–halide–lead bond angles, a result of deformation potential coupling to low-energy optical phonons. We accomplish this by performing femtosecond-resolved, optical-pump–electron-diffraction-probe measurements to quantify the lattice reorganization occurring as a result of photoexcitation in nanocrystals of FAPbBr3. Our results indicate a stronger coupling in FAPbBr3than CsPbBr3. We attribute the enhanced coupling in FAPbBr3to its disordered crystal structure, which persists down to cryogenic temperatures. We find the reorganizations induced by each exciton in a multi-excitonic state constructively interfere, giving rise to a coupling strength that scales quadratically with the exciton number. This superlinear scaling induces phonon-mediated attractive interactions between excitations in lead halide perovskites.

Vibrational control (VC) of photochemistry through the optical stimulation of structural dynamics is a nascent concept only recently demonstrated for model molecules in solution. Extending VC to state-of-the-art materials may lead to new applications and improved performance for optoelectronic devices. Metal halide perovskites are promising targets for VC due to their mechanical softness and the rich array of vibrational motions of both their inorganic and organic sublattices. Here, we demonstrate the ultrafast VC of FAPbBr3perovskite solar cells via intramolecular vibrations of the formamidinium cation using spectroscopic techniques based on vibrationally promoted electronic resonance. The observed short (~300 fs) time window of VC highlights the fast dynamics of coupling between the cation and inorganic sublattice. First-principles modelling reveals that this coupling is mediated by hydrogen bonds that modulate both lead halide lattice and electronic states. Cation dynamics modulating this coupling may suppress non-radiative recombination in perovskites, leading to photovoltaics with reduced voltage losses.