Engineering the Charge-Transfer State to Facilitate Spin–Orbit Charge Transfer Intersystem Crossing in Spirobis[anthracene]diones

Spiro conjugation has been proposed to dictate the efficiency of charge transfer, which could directly affect the spin–orbit charge transfer intersystem crossing (SOCT-ISC) process. However, this process has yet to be exemplified. Herein, we prepared three spirobis[anthracene]diones, in which two benzophenone moieties are locked in close proximity and differentially functionalized to fine-tune the charge transfer state. Its feasibility for SOCT-ISC was theoretically predicted, then experimentally evaluated. Through fine-tuning the spiro conjugation coupling and varying the solvent dielectric constants, ISC rate constants were engineered to vary in a dynamic range of three orders of magnitude, from 7.8×10⁸ s⁻¹ to 1.0×10¹¹ s⁻¹, which is the highest ISC rate reported for SOCT-ISC system to our knowledge. Our findings substantiate the key factors for effective SOCT-ISC and offer a new avenue for the rational design of heavy atom free triplet sensitizers.     

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.     

A discussion on mass resolution in secondary ion mass spectrometry

Mass resolution is a very important parameter for mass spectrometry. It is necessary to compare the mass resolution between the newly developed TOF-SIMS and the conventionally high-performance magnetic SIMS. However, the definitions of mass resolution for these two types of instruments are quite different. Whether it is possible to compare mass resolution and how to do such comparison is a challenge. This problem was raised officially during the 2012 ISO/TC 201 meeting at Tampa, Florida, the United States and the long-term cooperation with ISO started afterwards. The definition of mass resolution is one of the most important and fundamental problems for mass spectrometry and should attract significant attention. Here, some detail discussions on mass resolution as well as the related experimental studies in the past few years, including the collaborations with ISO/TC 201/SC6 and SC1 are summarized. This summary covers the common problem for almost all the current existing and still used definitions of mass resolution. A reasonable new definition for mass resolution considering the peak shape or resolution function has been proposed, which has also been confirmed by using experimental studies of the mass resolution comparison between TOF and magnetic SIMS. This study lays a foundation for the future mass resolution comparisons between different mass spectrometry.     

线性响应和两种态特定方法模拟AF350电子跃迁的溶剂效应

在极化连续模型框架下比较了线性响应与两种不同态特定方法计算的溶液中Alexa Fluor 350(AF350)分子激发能和光谱移动值的差异. AF350的第一激发态S0→S1电子跃迁属于π→π^*跃迁, 主要对应于最高占据分子轨道(HOMO)到最低空轨道(LUMO)的跃迁. 该分子激发态偶极矩大于基态偶极矩, 激发态时溶质溶剂相互作用比基态时更强, 随着溶剂极性增大, 会发生光谱红移的现象. 与实验值相比, 线性响应和两种态特定方法均高估了激发能, 其中以IBSF(Improta-Barone-Scalmani-Frisch)方法得到的激发能最小, 矫正的基态反应场方法(cGSRF)得到的激发能最大. 对于光谱移动值, 3种方法与实验值相比都偏小, 线性响应方法(LR)计算出的误差最大, 而IBSF方法得到的结果与实验值最吻合, 是预测溶液中AF350分子激发能和光谱移动值最准确的方法. 对比了Marcus传统理论和基于约束平衡的非平衡溶剂化理论的结果, 发现后者得到的激发能和光谱移动值更接近于实验值.     

The miracle role of lattice imperfections in benzene alkylation with methanol over mordenite

Mordenite (MOR) has demonstrated potential as a catalyst for alkylation due to high variability, intrinsic porosity, and outstanding stability. However, the contact probability of benzene and methanol has been limited by typical layered structures of MOR and there is no connection between layers. Here, we report the preparedness of H-MOR via a sequential post-treatment method based on a commercial MOR. H-MOR sample had appeared lattice imperfections inferred from characterization means. The samples were tested with benezene methylation reaction. Results show that the high conversion of benzene and the high selectivity of toluene were obtained from the miracle role of lattice imperfections in the H-MOR sample. Sequentially, based on the study of all catalyst structure and physical properties, a plausible reaction mechanism for the selectivity of the desired toluene was proposed.     

Metal-reinforced sulfonic-acid-modified zirconia for the removal of trace olefins from aromatics

Metal-reinforced sulfonic-acid-modified zirconia catalysts were successfully prepared and used to remove trace olefins from aromatics in a fixed-bed reactor. Catalysts were characterized by ICP-OES, N₂ adsorption–desorption, X-ray diffraction, thermogravimetric analysis (TGA), and pyridine-FTIR spectroscopy. Different metals and calcination temperatures had great influence on the catalytic activity. Alumina-reinforced sulfated zirconia exhibited outstanding catalytic performance, stable regeneration activity, and giant surface area, and are promising in industrial catalysis. TGA showed that the decomposition of methyl could be attributed to Brønsted acid sites, and pyridine-FTIR spectroscopy proved the weak Brønsted sites on these synthesized metal-reinforced sulfated zirconia. Also, a relation between the reaction rate and weak Brønsted acid density is proposed.     

Single-Molecule Magnetism in Dy2 Cluster Based on a Schiff Base Ligand

Two dinuclear Ln^III-based clusters, namely [Dy₂L₂(NO₃)₂(DME)₄] ( 1 ) and [Gd₂L₂(NO₃)₂(DME)₄] ( 2 ) [H₂L = (E)-2-((2-hydroxybenzylidene)amino)phenol] were obtained under hydrothermal condition. Two Ln^III ions are bridged by two phenolic hydroxyl oxygen atoms, and the distances of them are 3.829 Å (Dy1–Dy1A) and 3.860 Å (Gd1–Gd1A). Two Dy1–O–Dy1A and Gd1–O–Gd1A angles are 109.4° and 109.8°, respectively. Magnetic studies reveal a weak antiferromagnetic interaction between Gd ions in complex 2 , and single-molecule magnet behavior for 1 with U_eff = 49.9 K and τ₀ = 1.54 × 10^–6 s.     

Effect of ammonia,ammonia-water,and sulfuric acid on the HO2 + HO2 → H2O2 + 3O2 reaction in troposphere: Competition between stepwise and one-step mechanisms

A detailed theoretical study on the reaction mechanisms for the formations of H₂O₂ + ³O₂ from the self-reaction of HO₂ radicals under the effect of NH₃, H₃N···H₂O, and H₂SO₄ catalysts was performed using the CCSD(T)/CBS//M06-2X/aug-cc-pVTZ method. The rate constant was computed using canonical variational transition state theory (CVT) with small curvature tunneling (SCT). Our results indicate that NH₃-, H₃N···H₂O-, and H₂SO₄-catalyzed reactions could proceed through both one-step and stepwise routes. Calculated rate constants show that the catalyzed routes in the presence of the three catalysts all prefer stepwise pathways. Compared to the catalytic efficiency of H₂O, the efficiencies of NH₃, H₃N···H₂O, and H₂SO₄ are much lower due to their smaller relative concentrations. The present results have provided a definitive example of how basic and acidic catalysts influence the atmospheric reaction of HO₂ + HO₂ → H₂O₂ + ³O₂. These results further encourage one to consider the effects of basic and acidic catalysts on the related atmospheric reactions. Thus, the present investigation should have broad implications in the gas-phase reactions of the atmosphere.     

Substrate-Induced Dimerization Assembly of Chiral Macrocycle Catalysts toward Cooperative Asymmetric Catalysis

An artificial system of substrate-induced dimerization assembly of chiral macrocycle catalysts enables a highly cooperative hydrogen-bonding activation network for efficient enantioselective transformation. These macrocycles contain two thiourea and two chiral diamine moieties and dimerize with sulfate to form a sandwich-like assembly. The macrocycles then adopt an extended conformation and reciprocally complement the hydrogen-bonding interaction sites. Inspired by the guest-induced dynamic assembly, these macrocycles catalyze the decarboxylative Mannich reaction of cyclic aldimines containing a sulfamate heading group. The imine substrate can be activated toward nucleophilic attack of β-ketoacid by a cooperative hydrogen-bonding network enabled by sulfamate-induced dimerization assembly of the macrocycle catalysts. Highly efficient (>95 % yield in most cases) and enantioselective (up to 97.5:2.5 er) transformation of a variety of substrates using only 5 mol % macrocycle was achieved.     

Surface-Polarity-Induced Spatial Charge Separation Boosts Photocatalytic Overall Water Splitting on GaN Nanorod Arrays

Photocatalytic overall water splitting has been recognized as a promising approach to convert solar energy into hydrogen. However, most of the photocatalysts suffer from low efficiencies mainly because of poor charge separation. Herein, taking a model semiconductor gallium nitride (GaN) as an example, we uncovered that photogenerated electrons and holes can be spatially separated to the nonpolar and polar surfaces of GaN nanorod arrays, which is presumably ascribed to the different surface band bending induced by the surface polarity. The photogenerated charge separation efficiency of GaN can be enhanced significantly from about 8 % to more than 80 % via co-exposing polar and nonpolar surfaces. Furthermore, spatially assembling reduction and oxidation cocatalysts on the nonpolar and polar surfaces remarkably boosts photocatalytic overall water splitting, with the quantum efficiency increased from 0.9 % for the film photocatalyst to 6.9 % for the nanorod arrays photocatalyst.