Development of Lysosome-Targeted Fluorescent Probes for Cys by Regulating the Boron-dipyrromethene (BODIPY) Molecular Structure

Our previous discovery suggested that substituents on the 1,7 positions delicately modulate the sensing ability of the meso-arylmercapto boron-dipyrromethene (BODIPY) to biothiols. In this work, the impact of delicate modulations on the sensing ability is investigated. Therefore, 1,7-dimethyl, 3,5-diaryl substituted BODIPY is designed and developed and its conformationally restricted species with a meso-arylmercapto moiety ( DM-BDP-SAr and DM-BDP-R-SAr ) as selective fluorescent probes for Cys. Moreover, the lysosome-target probes ( Lyso-S and Lyso-D ) based on DM-BDP-SAr carrying one or two morpholinoethoxy moieties were developed. They were able to detect Cys selectively in vitro with low detection limits. Both Lyso-S and Lyso-D localized nicely in lysosomes in living HeLa cells and exhibited red fluorescence for Cys. Moreover, a novel fluorescence quenching mechanism was proposed from the calculations by density functional theory (DFT). The probes may go through intersystem crossing (from singlet excited state to triplet excited state) to result in fluorescence quenching.     

A generalization of lifting non-proper tropical intersections

Let X and $X^{\prime }$ be closed subschemes of an algebraic torus T over a non-archimedean field. We prove the rational equivalence as tropical cycles in the sense of [11, §2] between the tropicalization of the intersection product $X?X^{\prime }$ and the stable intersection $\mathrm{trop}(X)?\mathrm{trop}(X^{\prime })$, when restricted to (the inverse image under the tropicalization map of) a connected component C of $\mathrm{trop}(X)\cap \mathrm{trop}(X^{\prime })$. This requires possibly passing to a (partial) compactification of T with respect to a suitable fan. We define the compactified stable intersection in a toric tropical variety, and check that this definition is compatible with the intersection product in [11, §2]. As a result we get a numerical equivalence between $\stackrel{￣}{X}?{\stackrel{￣}{X}}^{\prime }{|}_{\stackrel{￣}{C}}$ and $\stackrel{￣}{\mathrm{trop}(X)?\mathrm{trop}(X^{\prime }){|}_C}$ via the compactified stable intersection, where the closures are taken inside the compactifications of T and ${\mathbb{R}}^n$. In particular, when X and $X^{\prime }$ have complementary codimensions, this equivalence generalizes [15, Theorem 6.4], in the sense that $X\cap X^{\prime }$ is allowed to be of positive dimension. Moreover, if $\stackrel{￣}{X}\cap {\stackrel{￣}{X}}^{\prime }$ has finitely many points which tropicalize to $\stackrel{￣}{C}$, we prove a similar equation as in [15, Theorem 6.4] when the ambient space is a reduced subscheme of T (instead of T itself).     

Selective Excitation of Band Extrema in Valley Photonic Crystals

Flexible control of building blocks of photonic crystals enables achieving desirable band structures. Exploration of photonic band extrema has brought many fantastic features to design artificial optical materials, such as Brillouin‐zone‐corner extrema for valley photonic materials and zone‐center extremum for zero‐index metamaterials. However, two such kinds of extrema are always found independently in different photonic crystals. In this work, a kind of valley photonic crystals possessing both zone‐center and zone‐corner band extrema almost at the same frequency is proposed. Inspired by antennas theory, a three‐antenna array (TAA) source is devoted to individually manipulate each extremum. The correlation coefficient is given to determine the coupling efficiency between the TAA source and extrema eigenmodes. By using a source with a high correlation coefficient, these extrema bulk states are selectively excited consistent with their eigenfields. Furthermore, three control cases are shown that multiple extrema points are simultaneously excited, in order to confirm the validity of the correlation coefficient. Finally, a potential application of a beam‐steering device is proposed through selective excitation of ternary extrema. This work develops binary valley states into ternary mix states, rendering more degrees of freedom for on‐chip optical information transport, particularly for beam steering and mode division multiplexing.     

Utilizing the Space‐Charge Region of the FeNi‐LDH/CoP p‐n Junction to Promote Performance in Oxygen Evolution Electrocatalysis

The modulation of electron density is an effective option for efficient alternative electrocatalysts. Here, p‐n junctions are constructed in 3D free‐standing FeNi‐LDH/CoP/carbon cloth (CC) electrode (LDH=layered double hydroxide). The positively charged FeNi‐LDH in the space‐charge region can significantly boost oxygen evolution reaction. Therefore, the j at 1.485 V (vs. RHE) of FeNi‐LDH/CoP/CC achieves ca. 10‐fold and ca. 100‐fold increases compared to those of FeNi‐LDH/CC and CoP/CC, respectively. Density functional theory calculation reveals OH^? has a stronger trend to adsorb on the surface of FeNi‐LDH side in the p‐n junction compared to individual FeNi‐LDH further verifying the synergistic effect in the p‐n junction. Additionally, it represents excellent activity toward water splitting. The utilization of heterojunctions would open up an entirely new possibility to purposefully regulate the electronic structure of active sites and promote their catalytic activities.     

Semiconducting Polymer Dots with Dual-Enhanced NIR-IIa Fluorescence for Through-Skull Mouse-Brain Imaging

Fluorescence probes in the NIR-IIa region show drastically improved imaging owing to the reduced photon scattering and autofluorescence in biological tissues. Now, NIR-IIa polymer dots (Pdots) are developed with a dual fluorescence enhancement mechanism. First, the aggregation induced emission of phenothiazine was used to reduce the nonradiative decay pathways of the polymers in condensed states. Second, fluorescence quenching was minimized by different levels of steric hindrance to further boost the fluorescence. The resulting Pdots displayed a fluorescence QY of ca. 1.7 % in aqueous solution, suggesting an enhancement of ca. 21 times in comparison with the original polymer in tetrahydrofuran (THF) solution. Small-animal imaging by using the NIR-IIa Pdots exhibited a remarkable improvement in penetration depth and signal to background ratio, as confirmed by through-skull and through-scalp fluorescent imaging of the cerebral vasculature of live mice.     

Rapid and Scalable Access to Sequence-Controlled DHDM Multiblock Copolymers by FLP Polymerization

An immortal N-(diphenylphosphanyl)-1,3-diisopropyl-4,5-dimethyl-1,3-dihydro-2H-imidazol-2-imine/diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum (P(NIⁱPr)Ph₂/(BHT)AlⁱBu₂)-based frustrated Lewis pair (FLP) polymerization strategy is presented for rapid and scalable synthesis of the sequence-controlled multiblock copolymers at room temperature. Without addition of extra initiator or catalyst and complex synthetic procedure, this method enabled a tripentacontablock copolymer (n=53, k=4, dp_n=50) to be achieved with the highest reported block number (n=53) and molecular weight (M_n=310 kg mol⁻¹) within 30 min. More importantly, this FLP polymerization strategy provided access to the multiblock copolymers with tailored properties by precisely adjusting the monomer sequence and block numbers.     

Route to hyperchaos and chimera states in a network of modified Hindmarsh-Rose neuron model with electromagnetic flux and external excitation

Analyzing the chaos and bursting phenomenon of neurons has been of interest in the past decade. In this paper, we discuss an extended Hindmarsh-Rose neuron model by taking into consideration the slowly interacting cell phenomenon due to the calcium ions. In the extended model, we consider the effect of an external forcing current, and the electromagnetic coupling between the magnetic flux and the membrane potential of the neuron. We analyze the modified neuron model in the presence of periodic and quasi-periodic excitations. A more complex chaotic behavior (hyperchaos) is identified in the neuron model. The results also demonstrate the multistable nature, which was not explored earlier. To discuss the dynamical behavior of the modified neuron in a network, we construct a ring network of neurons and capture the spatiotemporal patterns of the neuron in the network, in the presence of different excitations.

     

Effect of mechanical force on domain switching in BiFeO_3 ultrathin films

Ferroelectric polarization can be switched by an external applied electric field and may also be reversed by a mechanical force via flexoelectricity from the strain gradient.In this study,we report the mechanical writing of an epitaxial BiFeO3(BFO)thin film and the combined action of an applied mechanical force and electric field on domain switching,where the mechanical force and electric field are applied using the tip of atomic force microscopy.When the applied force exceeds the threshold value,the upward polarization of the BFO thin film can be reversed by pure mechanical force via flexoelectricity;when an electric field is simultaneously applied,the mechanical force can reduce the coercive electric field because both the piezoelectricity from the homogeneous strain and the flexoelectricity from strain gradient contribute to the internal electric field in the film.The mechanically switched domains exhibit a slightly lower surface potential when compared with that exhibited by the electrically switched domains due to no charge injection in the mechanical method.Furthermore,both the mechanically and electrically switched domains exhibit a tunneling electroresistance in the BFO ferroelectric tunnel junction.