Mechanochemical Synthesis of α-halo Alkylboronic Esters.

α-halo alkylboronic esters, acting as ambiphilic synthons, play a pivotal role as versatile intermediates in fields like pharmaceutical science and organic chemistry. The sequential transformation of carbon-boron and carbon-halogen bonds into a broad range of carbon-X bonds allows for programmable bond formation, facilitating the incorporation of multiple substituents at a single position and streamlining the synthesis of complex molecules. Nevertheless, the synthetic potential of these compounds is constrained by limited reaction patterns. Additionally, the conventional methods often necessitate the use of bulk toxic solvents, exhibit sensitivity to air/moisture, rely on expensive metal catalysts, and involve extended reaction times. In this report, a ball milling technique is introduced that overcomes these limitations, enabling the external catalyst-free multicomponent coupling of aryl diazonium salts, alkenes, and simple metal halides. This approach offers a general and straightforward method for obtaining a diverse array of α-halo alkylboronic esters, thereby paving the way for the extensive utilization of these synthons in the synthesis of fine chemicals.

Expanding the Anti-Stokes Shift of TTA-UC to 1.04 eV by Chemical Tuning of BODIPY-Based Organic Photosensitizers.

A series of BODIPY-derivatives B-1 ∼ B-5 were synthesized as metal-free photosensitizers in triplet-triplet annihilation (TTA) upconversion (UC) with the purpose of finely tuning the excited state properties to reduce the energy loss during intersystem crossing (ISC), and hence to expand the anti-Stokes shift of TTA-UC. It was revealed that B-5 showed a ΔEST of as small as 0.28 eV, thus, providing a large anti-Stokes shift of 1.04 eV in TTA-UC with organic sensitizers. A deep red-blue upconversion emission with UC quantum yields of up to 10.7% (out of a 50% maximum) was observed.

Mechanochemical synthesis of organoselenium compounds.

We disclose herein a strategy for the rapid synthesis of versatile organoselenium compounds under mild conditions. In this work, magnesium-based selenium nucleophiles are formed in situ from easily available organic halides, magnesium metal, and elemental selenium via mechanical stimulation. This process occurs under liquid-assisted grinding (LAG) conditions, requires no complicated pre-activation procedures, and operates broadly across a diverse range of aryl, heteroaryl, and alkyl substrates. In this work, symmetrical diselenides are efficiently obtained after work-up in the air, while one-pot nucleophilic addition reactions with various electrophiles allow the comprehensive synthesis of unsymmetrical monoselenides with high functional group tolerance. Notably, the method is applied to regioselective selenylation reactions of diiodoarenes and polyaromatic aryl halides that are difficult to operate via solution approaches. Besides selenium, elemental sulfur and tellurium are also competent in this process, which showcases the potential of the methodology for the facile synthesis of organochalcogen compounds.

72-hour real-time forecasting of ambient PM2.5 by hybrid graph deep neural network with aggregated neighborhood spatiotemporal information.

The observation-based air pollution forecasting method has high computational efficiency over traditional numerical models, but a poor ability in long-term (after 6 h) forecasting due to a lack of detailed representation of atmospheric processes associated with the pollution transport. To address such limitation, here we propose a novel real-time air pollution forecasting model that applies a hybrid graph deep neural network (GNN_LSTM) to dynamically capture the spatiotemporal correlations among neighborhood monitoring sites to better represent the physical mechanism of pollutant transport across the space with the graph structure which is established with features (angle, wind speed, and wind direction) of neighborhood sites to quantify their interactions. Such design substantially improves the model performance in 72-hour PM2.5 forecasting over the whole Beijing-Tianjin-Hebei region (overall R2 increases from 0.6 to 0.79), particularly for polluted episodes (PM2.5 concentration > 55 µg/m3) with pronounced regional transport to be captured by GNN_LSTM model. The inclusion of the AOD feature further enhances the model performance in predicting PM2.5 over the sites where the AOD can inform additional aloft PM2.5 pollution features related to regional transport. The importance of neighborhood site (particularly for those in the upwind flow pathway of the target area) features for long-term PM2.5 forecast is demonstrated by the increased performance in predicting PM2.5 in the target city (Beijing) with the inclusion of additional 128 neighborhood sites. Moreover, the newly developed GNN_LSTM model also implies the "source"-receptor relationship, as impacts from distanced sites associated with regional transport grow along with the forecasting time (from 0% to 38% in 72 h) following the wind flow. Such results suggest the great potential of GNN_LSTM in long-term air quality forecasting and air pollution prevention.

Triplet-triplet annihilation upconversion in LAPONITE®/PVP nanocomposites: absolute quantum yields of up to 23.8% in the solid state and application to anti-counterfeiting.

The low quantum efficiency in the solid phase and the highly efficient quenching by oxygen are two major weaknesses limiting the practical applications of triplet-triplet annihilation (TTA) upconversion (UC). Herein, we report an organic-inorganic hybrid nanocomposites fabricated by self-assembly of LAPONITE® clay and poly(N-vinyl-2-pyrrolidone) (PVP), which serves as excellent matrix for solid-state TTA-UC even in air. In the hybrid hydrogel doped by TTA-UC components, the anionic acceptors are arranged in an ordered manner at the nano-disk edge through electrostatic attraction, which avoids haphazard accumulation of the acceptors and allows for highly efficient inter-acceptor triplet energy migration. Moreover, the entangled PVP could not only protect the triplet excitons from oxygen quenching but even proactively eliminate oxygen by photoirradiation. Significantly, the dried gel prepared by completely removing water from the hydrogel gave absolute UC quantum efficiencies of up to 23.8% (out of a 50% maximum), which is the highest TTA-UC efficiency obtained in the solid state. The dried gels are readily made into powder by grinding with maintained UC emissions, making them convenient for application to information encryption and anti-counterfeiting security by virtue of the high UC quantum efficiency and insensitivity to oxygen.

Catalytic Chiral Photochemistry Sensitized by Chiral Hosts-Grafted Upconverted Nanoparticles.

Singlet chiral photocatalysis is highly challenging. Herein, we report fluorescence resonance energy transfer (FRET)-based chiral photocatalysis with γ-cyclodextrin (CD)-grafted lanthanide-doped upconverted nanoparticles (UCNP). The CD-modified UCNP strongly emits in the UV wavelength region upon excitation with a 980 nm laser, which selectively sensitizes the photosubstrates complexed by CD on the surface of UCNP through FRET. Therefore, enantiodifferentiating photocyclodimerization of anthracene or naphthalene derivatives sensitized by the CD-modified UCNP gives photoproducts in good enantioselectivity even in the presence of a catalytic amount of CD-modified UCNP. Moreover, the photocatalysts are readily separated and could be reused for at least six cycles without decreasing the enantioselectivity.

The More the Slower: Self-Inhibition in Supramolecular Chirality Induction, Memory, Erasure, and Reversion.

Self-inhibition has been observed widely in hierarchical biochemical processes but has yet to be demonstrated in pure molecular physical rather than chemical or biological processes. Herein, we report an unprecedented example of self-inhibition during the supramolecular chirality induction, memory, erasure, and inversion processes of pillar[5]arene (P[5]) derivatives. The addition of chiral alanine ethyl ester to bulky substituent-modified P[5]s led to time-dependent chirality induction due to the shift in the equilibrium of the SP and RP conformers P[5]. Intriguingly, more chiral inducers led to more intensive final chiroptical properties but lower chiral induction rates. Thus, the chiral inducer plays the role of both activator and inhibitor. Such self-inhibition essentially arises from kinetics manipulation of three tandem equilibria. Moreover, the chiroptical properties could be memorized by replacing the chiral inducer with an achiral competitive binder, and the chiroptical signal could be erased and reversed by an antipodal chiral inducer, which also showed the self-inhibition property.

A Quinoline-Appended Cyclodextrin Derivative as a Highly Selective Receptor and Colorimetric Probe for Nucleotides.

The design and development of specific recognition and sensing systems for biologically important anionic species has received growing attention in recent years, as they play significant roles in biology, pharmacy, and environmental sciences. Herein, a new supramolecular sensing probe L1 was developed for highly selective differentiation of nucleotides. L1 displayed extremely marked absorption and emission differentiation upon binding with nucleotide homologs of AMP, ADP, and ATP, due to the divergent spatial orientations of guests upon binding, which allowed for a naked-eye colorimetric differentiation for nucleotides. A differentiating mechanism was unambiguously rationalized by using various spectroscopic studies and theoretical calculations. Furthermore, we successfully demonstrated that L1 can be applied to the real-time monitoring of the enzyme-catalyzed phosphorylation/dephosphorylation processes and thus demonstrated an unprecedented visualizable strategy for selectively differentiating the structurally similar nucleotides and real-time monitoring of biological processes via fluorescent and colorimetric changes.

Trace mild acid-catalysed Z → E isomerization of norbornene-fused stilbene derivatives: intelligent chiral molecular photoswitches with controllable self-recovery.

Stilbene derivatives have long been known to undergo "acid-catalyzed" Z → E isomerization, where a strong mineral acid at high concentration is practically necessary. Such severe reaction conditions often cause undesired by-reactions and limit their potential application. Herein, we present a trace mild acid-catalyzed Z → E isomerization found with stilbene derivatives fused with a norbornene moiety. By-reactions, such as the migration of the C[double bond, length as m-dash]C double bond and electrophilic addition reactions, were completely inhibited because of the ring strain caused by the fused norbornene component. Direct photolysis of the E isomers at selected wavelengths led to the E → Z photoisomerization of these stilbene derivatives and thus constituted a unique class of molecular switches orthogonally controllable by light and acid. The catalytic amount of acid could be readily removed, and the Z → E isomerization could be controlled by turning on/off the irradiation of a photoacid, which allowed repeated isomerization in a non-invasive manner. Moreover, the Z isomer produced by photoisomerization could spontaneously self-recover to the E isomer in the presence of a catalytic amount of acid. The kinetics of Z → E isomerization were adjustable by manipulating catalytic factors and, therefore, unprecedented molecular photoswitches with adjustable self-recovery were realized.

Synthesis, enantioseparation and photophysical properties of planar-chiral pillar[5]arene derivatives bearing fluorophore fragments.

Planar chiral pillar[5]arene derivatives (P5A-DPA and P5A-Py) bearing bulky fluorophores were obtained in high yield by click reaction. The photophysical properties of both compounds were investigated in detail. P5A-DPA with two 9,10-diphenylanthracene (DPA) pigments grafted on the pillar[5]arene showed a high fluorescence quantum yield of 89.5%. This is comparable to the monomer DPA-6, while P5A-Py with two perylene (Py) pigments grafted on the pillar[5]arene showed a significantly reduced quantum yield of 46.4% vs 78.2% for the monomer Py-6. The oxygen-through-annulus rotation of the phenolic units was inhibited for both compounds due to the bulky chromophore introduced, and the resolution of the enantiomers was achieved due to the bulky size of the fluorophores. The absolute configuration of the enantiomers was determined by circular dichroism (CD) spectra. The solvent-induced aggregation behavior was investigated with the enantiopure P5A-DPA and P5A-Py. It was found that the CD signals were enhanced by aggregation. P5A-DPA showed aggregation-induced emission enhancement, while P5A-Py showed aggregation-induced emission quenching, accompanied by excimer emission when aggregating in water and THF mixed solution.

Efficient Triplet-Triplet Annihilation Upconversion with an Anti-Stokes Shift of 1.08 eV Achieved by Chemically Tuning Sensitizers.

A series of Pt(II)-Schiff base complexes were synthesized as triplet sensitizers for the purpose of tuning the singlet and triplet energy levels so as to minimize energy loss during triplet-triplet annihilation (TTA) upconversion (UC). A deep-red to blue TTA-UC was achieved with an unprecedentedly large anti-Stokes shift of 1.08 eV. UC quantum yields of up to 21% (with a theoretical maximum efficiency of 50%) were observed in solution. The complexes also showed efficient UC emission in air-saturated hydrogels with a UC quantum yield up to 14.8%, which is much higher than the highest previously reported value. The low threshold excitation intensity provided by the present system offers promising potential for application in terrestrial solar energy conversion.

Precise Manipulation of Temperature-Driven Chirality Switching of Molecular Universal Joints through Solvent Mixing.

Three chiral bicyclic pillar[5]arene derivatives termed as molecular universal joints (MUJs), were synthesized and separated enantiomerically. These MUJs showed temperature-driven chirality switching in certain solvents. Herein, it is demonstrated that temperature-driven chirality switching could also be realized by mixing two miscible organic solvents, in each of which chirality inversion is not accomplishable. Additionally, solvent mixing drastically varied the inversion temperature of the MUJs, for example, from far below zero to room temperature. Moreover, the temperature-driven Sp /Rp to Rp /Sp chirality switching direction could be reversed by the solvent mixing and it was critically controlled by the mixing ratios of the two solvents. These observations allowed precise manipulation of the chirality switching behavior of the MUJs. Such a chirality switching was ascribed to the influences of solvent and temperature on the in-out equilibrium of the side rings, which is delicately controlled by several processes, including the solvation/desolvation and the inclusion/exclusion of the side rings and solvent molecules. Crucially, the solvent mixing introduced new supramolecular processes, in particular the desolvation of solvent molecules from the mixed solvent system and the solvation of the side ring by the mixed solvent, which significantly disturbed the original in-out equilibrium of MUJs and drastically switched the entropy and enthalpy changes of conformational interconversion.

Induced chirality sensing through formation and aggregation of the chiral imines double winged with pyrenes or perylenes.

Reaction of chiral amines with benzaldehydes 3,5-disubstituted by two pyrenes or perylenes afforded corresponding double winged chiral imines, which aggregated to show significantly enhanced circular dichroism spectra at the transition bands of the chromophores in the mixture solutions of DMF and H2O.

Supramolecular Assembly-Improved Triplet-Triplet Annihilation Upconversion in Aqueous Solution.

Water-soluble 9,10-diphenylanthracene-modified γ-cyclodextrin derivatives A1 and A2, in which the γ-cyclodextrin unit serves as a molecular host for a binding sensitizer, and the 9,10-diphenylanthracene moiety plays a role as an emitter/annihilator, were synthesized to investigate the supramolecular triplet-triplet annihilation (TTA) upconversion in aqueous solution. Both A1 and A2 readily aggregate and form nanoscale assemblies in water as a combined result of host-guest complexation and π-π stacking among the 9,10-diphenylanthracenes. The aggregation behavior of the supramolecular emitters was fully characterized by using a diversity of methods, including dynamic light scattering (DLS), SEM, NMR, fluorescence, and circular dichroism studies. Fluorescence spectroscopic analysis reveals that the emitters have high fluorescence quantum yields in water (82 and 90 % for A1 and A2, respectively), thus demonstrating that aggregation does not quench the fluorescence. By using a coordinated ruthenium sensitizer, a high TTA upconversion quantum yield of up to 6.9 % was observed for this supramolecular TTA system, which is significantly higher than the value (<0.5 %) obtained with nonassembled emitters in organic solvent and in contrast to the fact that TTA upconversion emission in aqueous solution is usually low or negligible. We ascribe the strong TTA upconversion emission in the present supramolecular assembly system to an efficient TTA process, which is facilitated along the stacked emitters by triplet energy migration and improved triplet-triplet energy transfer through host-guest complexation.

Photocatalytic Supramolecular Enantiodifferentiating Dimerization of 2-Anthracenecarboxylic Acid through Triplet-Triplet Annihilation.

Visible-light-driven enantiodifferentiating photodimerization of 2-anthracenecarboxylic acid (AC) sensitized by Schiff base Pt(II) complex-grafted γ-cyclodextrins leads the first triplet-triplet annihilation-based catalytic photochirogenesis. The syn-head-to-tail (HT) photodimer 2 was achieved in up to 31.4% ee at 61.0% conversion in the presence of 0.5% equiv of the photocatalyst.

Enhanced Triplet-Triplet Energy Transfer and Upconversion Fluorescence through Host-Guest Complexation.

Perylene-tethered pillar[5]arenes and C60-boron-dipyrromethene (BODIPY) dyads were synthesized acting as emitters and organic triplet photosensitizers, respectively, for the purpose of improving the efficiency of triplet-triplet annihilation upconversion (TTA-UC). The photophysical properties of the sensitizers (guests) and the emitters (hosts) were not greatly influenced by the chemical modifications except for a notable decrease in the fluorescence quantum yields of the perlyene emitters due to the high local concentration. The perylene-tethered pillar[5]arenes form stable 1:1 complexes with a nitrile-bearing C60-BODIPY dyad, showing association constants as high as 4.0 × 104 M-1. Through host-guest complexation, the efficiencies of both triplet-triplet energy transfer and TTA were significantly enhanced, which overcompensated for the loss of the fluorescence quantum yield of the emitters (hosts). Thus, an improved TTA-UC efficiency of 3.2% was observed even at a diluted concentration of 6 × 10-5 M, demonstrating for the first time the effectiveness of the supramolecular motif for enhancing TTA-UC without varying the inherent photophysical properties of sensitizers and emitters.

Role of miR-211 in Neuronal Differentiation and Viability: Implications to Pathogenesis of Alzheimer's Disease.

Alzheimer's disease (AD) is an age-related irreversible neurodegenerative disorder characterized by extracellular ß Amyloid(Aß) deposition, intracellular neurofibrillary tangles and neuronal loss. The dysfunction of neurogenesis and increased degeneration of neurons contribute to the pathogenesis of AD. We now report that miR-211-5p, a small non-coding RNA, can impair neurite differentiation by directly targeting NUAK1, decrease neuronal viability and accelerate the progression of Aß-induced pathologies. In this study, we observed that during embryonic development, the expression levels of miR-211-5p were down-regulated in the normal cerebral cortexes of mice. However, in APPswe/PS1ΔE9 double transgenic adult mice, it was up-regulated from 9 months of age compared to that of the age-matched wild type mice. Studies in primary cortical neuron cultures demonstrated that miR-211-5p can inhibit neurite growth and branching via NUAK1 repression and decrease mature neuron viability. The impairments were more obvious under the action of Aß. Our data showed that miR-211-5p could inhibit cortical neuron differentiation and survival, which may contribute to the synaptic failure, neuronal loss and cognitive dysfunction in AD.

Determination of log P by dispersive liquid/liquid microextraction coupled with derivatized magnetic nanoparticles predispersed in 1-octanol phase.

A new direct method for log P determination by dispersive liquid/liquid microextraction (DLLME) coupled with derivatized magnetic nanoparticles (DMNPs) predispersed in 1-octanol phase is discussed. First, the aim of DMNPs predispersed into 1-octanol phase was to provide the magnetic force when an ultrastrong magnet was used to separate the two phases. Second, the interaction of 1-octanol with inner DMNPs nuclei prevented emulsion formation in the DLLME process. Moreover, interruption of absorption of DMNPs due to the partition equilibrium of the model compound was negligible. The equilibrium of model compound between the two phases was reached in less than 3 min. The two phases were separated quickly by a super magnet because model compounds in the two phases did not interfere with each other. Fourteen model compounds of varied log P values were measured using this method. The log P values fall in the range of 0.6 to 4.8, which are in agreement with the published results. This method is a rapid, efficient and facile method for direct measurement of log P values.