Asymmetric Coupling of Carbon-Centered Radicals Adjacent to Nitrogen: Copper-Catalyzed Cyanation and Etherification of Enamides

The first copper-catalyzed asymmetric cyanation and etherification reactions of enamides have been established, where a carbon-centered radical adjacent to a nitrogen atom (CRAN) is enantioselectively trapped by a chiral copper(II) species. Moreover, the asymmetric cyanation of vinyl esters was disclosed as well. These reactions feature very mild reaction conditions and high functional group tolerance, and give a series of chiral α-cyano amides, α-cyano esters and α-hemiaminals in good yields with excellent enantioselectivity. The chiral α-cyano amides can be easily converted into enantioenriched 1,2-diamines and amino acids.     

Rapid Capillary-Assisted Solution Printing of Perovskite Nanowire Arrays Enables Scalable Production of Photodetectors

Despite recent progress in producing perovskite nanowires (NWs) for optoelectronics, it remains challenging to solution-print an array of NWs with precisely controlled position and orientation. Herein, we report a robust capillary-assisted solution printing (CASP) strategy to rapidly access aligned and highly crystalline perovskite NW arrays. The key to the CASP approach lies in the integration of capillary-directed assembly through periodic nanochannels and solution printing through the programmably moving substrate to rapidly guide the deposition of perovskite NWs. The growth kinetics of perovskite NWs was closely examined by in situ optical microscopy. Intriguingly, the as-printed perovskite NWs array exhibit excellent optical and optoelectronic properties and can be conveniently implemented for the scalable fabrication of photodetectors.     

Chromophore-Assisted Proximity Labeling of DNA Reveals Chromosomal Organization in Living Cells

The spatial arrangement of chromosome within the nucleus is linked to genome function and gene expression regulation. Existing genome-wide mapping methods often rely on chemically crosslinking DNA with protein baits, which raises concerns of artifacts being introduced during cell fixation. By genetically targeting a photosensitizer protein to specific subnuclear locations, we achieved blue-light-activated labeling of local DNA with a bioorthogonal functional handle for affinity purification and sequence identification through next-generation sequencing. When applied to the nuclear lamina in human embryonic kidney 293T cells, it revealed lamina-associated domains (LADs) that cover 37.6 % of the genome. These LADs overlap with heterochromatin hallmarks and are depleted with CpG islands. This simple labeling method avoids the harsh treatment of chemical crosslinking and is generally applicable to the genome-wide high-resolution mapping of the spatial chromosome organization in living cells.     

A Layered Cationic Aluminum Oxyhydroxide as a Highly Efficient and Selective Trap for Heavy Metal Oxyanions

Cationic framework materials, especially pure inorganic cationic frameworks that can efficiently and selectively capture harmful heavy metal oxyanions from aqueous solution are highly desired yet scarcely reported. Herein, we report the discovery of a 2D cationic aluminum oxyhydroxide, JU-111, which sets a new benchmark for heavy metal oxyanion sorbents, especially for Cr^VI. Its structure was solved based on 3D electron diffraction tomography data. JU-111 shows fast sorption kinetics (ca. 20 min), high capture capacity (105.4 mg g⁻¹), and broad working pH range (3–10) toward Cr^VI oxyanions. Unlike layered double hydroxides (LDHs), which are poorly selective in the presence of CO₃²⁻, JU-111 retains excellent selectivity for Cr^VI even under a large excess of CO₃²⁻. These superior features coupled with the ultra-low cost and environmentally benign nature make JU-111 a promising candidate for toxic metal oxyanion remediation as well as other potential applications.     

Benzofuran-isatin conjugates as potent VEGFR-2 and cancer cell growth inhibitors

A series of benzofuran-isatin conjugates 6a-l and 7a,b tethered by various alkyl linkers were synthesized and evaluated for their VEGFR-2 inhibitory activity and in vitro activity against a panel of cancer cell lines. Seven of them were comparable with or better than Sunitinib against all tested cancer cells, demonstrating benzofuran-isatin conjugates were potential anticancer candidates. The mechanism study revealed that VEGFR-2 was at least one of the targets for this kind of conjugates. The structure-activity relationship demonstrated that the carbon spacer between benzofuran and isatin moieties, substituents on the C-2 position of benzofuran moiety, and substituents on C-3 as well as C-5 position of isatin motif influenced the anticancer activity significantly, and the enriched structure-activity relationship may provide an insight for rational design of more effective conjugates.     

溶剂诱导翻转Pickering乳液用于原位循环使用酶催化剂

Separation and recycling of catalysts are crucial for realizing the objectives of sustainable and green chemistry but remain a great challenge, especially for enzyme biocatalysts. In this work, we report a new solvent-induced reversible inversion of Pickering emulsions stabilized by Janus mesosilica nanosheets (JMSNs), which is then utilized as a strategy for the in situ separation and recycling of enzymes. The interfacial active solid particle JMSNs is carefully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption experiments, Fourier transform infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA).The JMSNs are demonstrated to show order-oriented mesochannels with a large specific surface area, and the hydrophobic octylgroup is selectively modified on one side of the nanosheets. Furthermore, the inversion is found to be a fast process that is strongly dependent on the interfacial activity of the solid emulsifier JMSNs. Such a phase inversion is also a general process that can be realized in various oil/water phasic systems, including ethyl acetate-water, octane-water, and cyclohexane-water systems. By carefully analyzing the capacity of JMSNs with different surface wettabilities for phase inversion, a triphase contact angle (θ) close to 90° and a critical oil-water ratio of 1 : 2 are identified as the key factors to achieve solvent-induced phase inversion via a catastrophic phase inversion mechanism. Importantly, this reversible phase inversion is suitable for the separation and recycling of enzyme biocatalysts that are sensitive to changes in the reaction medium. Specifically, during the reaction, the organic substrates are dissolved in the oil droplets and the water-soluble catalysts are dispersed in the water phase, while a majority of the product is released into the upper oil phase and the enzyme catalyst is confined inside the water droplets in the bottom layer after phase inversion. The perpendicular mesochannels of JMSNs provide a highly accessible reaction interface, and their excellent interfacial activity allows for more than 10 rounds of consecutive phase inversions by simply adjusting the ratio of oil to water in the system. Using the enzymatic hydrolysis kinetic resolution of racemic acetate as an example, our Pickering emulsion system shows not only a 3-fold enhanced activity but also excellent recyclability. Because no sensitive chemical reagents are used in this phase inversion process, the intrinsic activities of the catalysts can be preserved even after seven cycles. The current study provides an alternative strategy for the separation and recycling of enzymes, in addition to revealing a new innovative application for Janus-type nanoparticles.     

基于上转换纳米粒子的低损伤神经界面技术

Optogenetics is a neuromodulation technology that combines light control technology with genetic technology, thus allowing the selective activation and inhibition of the electrical activity in specific types of neurons with millisecond time resolution. Over the past several years, optogenetics has become a powerful tool for understanding the organization and functions of neural circuits, and it holds great promise to treat neurological disorders. To date, the excitation wavelengths of commonly employed opsins in optogenetics are located in the visible spectrum. This poses a serious limitation for neural activity regulation because the intense absorption and scattering of visible light by tissues lead to the loss of excitation light energy and also cause tissue heating. To regulate the activity of neurons in deep brain regions, it is necessary to implant optical fibers or optoelectronic devices into target brain areas, which however can induce severe tissue damage. Non- or minimally-invasive remote control technologies that can manipulate neural activity have been highly desirable in neuroscience research. Upconversion nanoparticles (UCNPs) can emit light with a short wavelength and high frequency upon excitation by light with a long wavelength and low frequency. Therefore, UCNPs can convert low-frequency near-infrared (NIR) light into high-frequency visible light for the activation of light-sensitive proteins, thus indirectly realizing the NIR optogenetic system. Because NIR light has a large tissue penetration depth, UCNP-mediated optogenetics has attracted significant interest for deep-tissue neuromodulation. However, in UCNP-mediated in vivo optogenetic experiments, as the up-conversion efficiency of UCNPs is low, it is generally necessary to apply high-power NIR light to obtain up-converted fluorescence with energy high enough to activate a photosensitive protein. High-power NIR light can cause thermal damage to tissues, which seriously restricts the applications of UCNPs in optogenetic technology. Therefore, the exploration of strategies to increase the up-conversion efficiency, fluorescence intensity, and biocompatibility of UCNPs is of great significance to their wide applications in optogenetic systems. This review summarizes recent developments and challenges in UCNP-mediated optogenetics for deep-brain neuromodulation. We firstly discuss the correspondence between the parameters of UCNPs and employed opsins in optogenetic experiments, which mainly include excitation wavelengths, emission wavelengths, and luminescent lifetimes. Thereafter, we introduce the methods to enhance the conversion efficiency of UCNPs, including optimizing the structure of UCNPs and modifying the organic dyes in UCNPs. In addition, we also discuss the future opportunities in combining UCNP-mediated optogenetics with flexible microelectrode technology for the long-term detection and regulation of neural activity in the case of minimal injury.     

Remote regioselective organocatalytic asymmetric [3+2] cycloaddition of N-2,2,2-trifluoroethyl isatin ketimines with cyclic 2,4-dienones

An organocatalytic asymmetric [3+2] cycloaddition of trifluoromethyl-containing azomethine ylides with cyclic 2,4-dienones was developed.The process enables efficient incorporation of CF3 groups into functionalized spiro [pyrro lid in-3,2'-oxindoles] in high yields with good to excellent enantio-and diastereoselectivities.     

Constructing spin-adiabatic states for the modeling of spin-crossing reactions. I. A shared-orbital implementation

In the modeling of spin-crossing reactions, it has become popular to directly explore the spin-adiabatic surfaces. Specifically, through constructing spin-adiabatic states from a two-state Hamiltonian (with spin-orbit coupling matrix elements) at each geometry, one can readily employ advanced geometry optimization algorithms to acquire a “transition state” structure, where the spin crossing occurs. In this work, we report the implementation of a fully-variational spin-adiabatic approach based on Kohn-Sham density functional theory spin states (sharing the same set of molecular orbitals) and the Breit-Pauli one-electron spin-orbit operator. For three model spin-crossing reactions (predissociation of N₂O, singlet-triplet conversion in CH₂, and CO addition to Fe(CO)₄), the spin-crossing points were obtained. Our results also indicated the Breit-Pauli one-electron spin-orbit coupling can vary significantly along the reaction pathway on the spin-adiabatic energy surface. On the other hand, due to the restriction that low-spin and high-spin states share the same set of molecular orbitals, the acquired spin-adiabatic energy surface shows a cusp (ie, a first-order discontinuity) at the crossing point, which prevents the use of standard geometry optimization algorithms to pinpoint the crossing point. An extension with this restriction removed is being developed to achieve the smoothness of spin-adiabatic surfaces.     

De Novo Construction of Catenanes with Dissymmetric Cages by Space‐Discriminative Post‐Assembly Modification

Considerable efforts have been made to increase the topological complexity of mechanically interlocked molecules over the years. Three‐dimensional catenated structures composed of two or several (usually symmetrical) cages are one representative example. However, owing to the lack of an efficient universal synthetic strategy, interlocked structures made up of dissymmetric cages are relatively rare. Since the space volume of the inner cavity of an interlocked structure is smaller than that outside it, we developed a novel synthetic approach with the voluminous reductant NaBH(OAc)₃ that discriminates this space difference, and therefore selectively reduces the outer surface of a catenated dimer composed of two symmetric cages, thus yielding the corresponding catenane with dissymmetric cages. Insight into the template effect that facilitates the catenation of cages was provided by computational and experimental techniques.