Investigation of a Photochromic Diarylethene with Electron-acceptor Attached

In this contribution, an electron acceptor attached diarylethene derivative was synthesized and fully characterized. The photochromic behavior was investigated in THF. Under exposure of UV and visible light cycles, the solution color can be switched between colorless and yellow smoothly. Fatigue resistance measurements could be repeated 50 times with an acceptable degradation. Due to the electron acceptor attached to the framework of diarylethene, the photo- and thermal-stability were enhanced both. A full-photo mode switch can be established based on the well-defined states by external excitation. The molecular structures of ring-open and ring-closed form were optimized by Dmol³. The distance between photocyclizing atoms in aptiparallel conformation meets the requirement for photochromic reaction. And the calculated absorption wavelengths were also in agreement with the experimental values.     

Exceedingly Fast Copper(II)‐Promoted ortho CH Trifluoromethylation of Arenes using TMSCF3

The direct ortho‐trifluoromethylation of arenes, including heteroarenes, with TMSCF₃ has been accomplished by a copper(II)‐promoted C? H activation reaction which completes within 30 minutes. Mechanistic investigations are consistent with the involvement of C? H activation, rather than a simple electrophilic aromatic substitution (S_EAr), as the key step.     

Transfer of Aryl Halide to Alkyl Halide: Reductive Elimination of Alkylhalide from Alkylpalladium Halides Containing syn‐β‐Hydrogen Atoms

β‐Hydride abstraction is a well‐accepted elementary step for catalytic cycles in organometallic chemistry. It is usually anticipated that alkylpalladium halides containing syn‐β‐hydrogen atoms will undergo β‐hydride abstraction to afford the Heck‐type products. However, this study discloses that the above general knowledge is only conditionally correct. Our experimental results demonstrate that the reductive elimination of alkylhalides from alkylpalladium halides containing syn‐β‐hydrogen atoms may surpass the β‐hydride abstraction or even become exclusive in certain cases.     

Bioconversion of Corncob Acid Hydrolysate into Microbial Oil by the Oleaginous Yeast Lipomyces starkeyi

For the first time, corncob acid hydrolysate was used for microbial oil production by the oleaginous yeast Lipomyces starkeyi. After hydrolysis by dilute sulfuric acid, corncob could turn into an acid hydrolysate with a sugar concentration of about 42.3 g/L. Detoxified by overliming and absorption with activated carbon, the corncob hydrolysate could be used by L. starkeyi efficiently that a total biomass of 17.2 g/L with a lipid content of 47.0 % (corresponding to a lipid yield of 8.1 g/L) and a lipid coefficient of 20.9 could be obtained after cultivation on the corncob hydrolysate for 8 days. Therefore, L. starkeyi is a promising strain for microbial oil production from lignocellulosic biomass. Glucose and xylose were used by L. starkeyi simultaneously during lipid fermentation while arabinose could not be utilized by it. Besides, the lipid composition of L. starkeyi was similar to that of vegetable oils; thus, it is a promising feedstock for biodiesel production.     

Light-Driven Crawling of Molecular Crystals by Phase-Dependent Transient Elastic Lattice Deformation

The light-driven crawling of a molecular crystal that can form three phases, (α, β, and γ) is presented. Laser irradiation of the molecular crystal can generate phase-dependent transient elastic lattice deformation. The resulting elastic lattice deformation that follows scanning irradiation of a laser can actuate the different phases of molecular crystal to move with different velocity and direction. Because the γ phase has a large Young's modulus (ca. 26 GPa), a force of 0.1 μN can be generated under one laser spot. The generated force is sufficient to actuate the γ-formed molecular crystals in a wide dimensional range to move longitudinally at a velocity of about 60 μm min⁻¹, which is two orders of magnitude faster than the α and β phases.     

Palladium-Catalyzed Asymmetric [8+2] Dipolar Cycloadditions of Vinyl Carbamates and Photogenerated Ketenes

Higher-order cycloadditions, particularly [8+2] cycloadditions, are a straightforward and efficient strategy for constructing significant medium-sized architectures. Typically, configuration-restrained conjugated systems are utilized as 8π-components for higher-order concerted cycloadditions. However, for this reason, 10-membered monocyclic skeletons have never been constructed via catalytic asymmetric [8+2] cycloaddition with high peri- and stereoselectivity. Here, we accomplished an enantioselective [8+2] dipolar cycloaddition via the merger of visible-light activation and asymmetric palladium catalysis. This protocol provides a new route to 10-membered monocyclic architectures bearing chiral quaternary stereocenters with high chemo-, peri-, and enantioselectivity. The success of this strategy relied on the facile in situ generation of Pd-containing 1,8-dipoles and their enantioselective trapping by ketene dipolarophiles, which were formed in situ via a photo-Wolff rearrangement.     

Programmable Live-Cell CRISPR Imaging with Toehold-Switch-Mediated Strand Displacement

The widespread application of CRISPR-Cas9 has transformed genome engineering. Nevertheless, the precision to control the targeting activity of Cas9 requires further improvement. We report a toehold-switch-based approach to engineer the conformation of single guide RNA (sgRNA) for programmable activation of Cas9. This activation circuit is responsive to multiple inputs and can regulate the conformation of the sgRNA through toehold-switch-mediated strand displacement. We demonstrate the orthogonal suppression and activation of Cas9 with orthogonal DNA inputs. Combination of toehold switches leads to a variety of intracellular Cas9 activation programs with simultaneous and orthogonal responses, through which multiple genome loci are displayed in different colors in a controllable manner. This approach provides a new route for programing CRISPR in living cells for genome imaging and engineering.     

Integrating bimetallic AuPd nanocatalysts with a 2D aza-fused π-conjugated microporous polymer for light-driven benzyl alcohol oxidation

Efficient catalytic system with low energy consumption exhibits increasing importance due to the upcoming energy crisis.Given this situation,it should be an admirable strategy for reducing energy input by effectively utilizing incident solar energy as a heat source during catalytic reactions.Herein,aza-fused7 r-conjugated microporous polymer(aza-CMP)with broad light absorption and high photothermal conversion efficiency was synthesized and utilized as a support for bimetallic AuPd nanocatalysts in light-driven benzyl alcohol oxidation.The AuPd nanoparticles anchored on aza-CMP(aza-CM P/Au_xPdy)exhibited excellent catalytic performance for benzyl alcohol oxidation under 50 mW/cm^2 light irradiation.The improved catalytic performance by the aza-CMP/Au_xPdy is attributed to the unique photothermal effect induced by aza-CMP,which can promote the catalytic benzyl alcohol oxidation occurring at Au Pd.This work presents a novel approach to effectively utilize solar energy for conventional catalytic reactions through photothermal effect.