Precision Chemistry最新文献

Cancer, a globally prevalent and life-threatening disease, remains a major area of focus in biomedical research. However, its substantial heterogeneity and complex pathogenesis continue to pose significant challenges for accurate diagnosis and effective treatment. The rapid advancement of epigenomic sequencing technologies has opened avenues by uncovering the epigenetic hallmarks and underlying pathology of cancer. As a result, these technologies have become invaluable tools in advancing cancer diagnostics and connecting research with clinical applications. This review briefly overviews epigenomic modifications and their significance in cancer diagnostics, highlighting potential epigenomic biomarkers with clinical applicability. We also examine emerging techniques in bulk and single-cell sequencing approaches, alongside spatial tools, highlighting their integration with multiomics technologies for cancer diagnostics. Particular attention is given to the analysis of key epigenetic characteristics, such as DNA methylation, histone modifications, and chromatin accessibility. Additionally, we summarize the diagnostic applications of these technologies and evaluate their current adoption in clinical settings. Challenges, limitations, and future directions for advancing epigenomic sequencing toward routine clinical diagnostics are also discussed. This review aims to provide scientists and clinicians with a comprehensive resource, encouraging further exploration and adoption of epigenomic sequencing technologies to drive progress in precision medicine.

Heteroatom doping has the potential to alter the electronic structure and optical properties of nanographenes, thereby expanding the scope of their utility in various applications. In this work we demonstrate a strategy to introduce an oxygen atom directly and precisely into backbone of the already formed metal-nanographene complexes. Treating metal-nanographene complexes HBCP-M (M = Cu, Ag, Au) with Davis’ oxaziridine produces oxygen-doped complexes HBCP-OM (M = Cu, Ag, Au) with adj-CONN coordination in one step. Compared with original metal complexes, the electronic structure, photophysical properties and molecular conformations of HBCP-OM show sharp changes, as indicated by steady and fs-transient absorption (TA) spectroscopies, DFT calculations and crystal structure analysis. Moreover, the reduction of coordination cavity of HBCP-OM due to oxygen insertion affects the metal–ligand interaction. This leads that HBCP-OCu, possessing a relatively small Cu(III) cation, exhibits an extended near-infrared (NIR) absorption beyond 1300 nm that is not observed in HBCP-OAg and HBCP-OAu.

Searching for novel carbon allotropes with excellent mechanical and interesting electronic properties is valuable, but such a large structural search remains a challenge if purely based on the traditional density functional theory (DFT) combined with Monte-Carlo (MC) methods. Herein, the neural network potential is utilized to accelerate the sampling of the stochastic surface walking algorithm for a global structural search of ordered carbons from carbon nanotubes (CNTs) under pressure. A variety of unreported ordered carbons are obtained, among which CNTs with diameters smaller than 0.7 nm are more sensitive to pressure than bigger tubes. Most ordered carbons obtained show great thermodynamical and kinetic stability, verified by ab initio molecular dynamics simulations and phonon spectra. The ordered carbons demonstrate direct or indirect band gaps in the range of 0 to 4.4 eV, including 13 superhard (H_v > 40 GPa) structures and 1 ductile (Pugh's Ratio G/B < 0.57) structure, in which the modulus of ordered carbons exhibits a linear correlation with the density. Our study provides a pathway to create new carbons from nanotubes and a deeper understanding of the structural evolution of CNTs under pressure.

Various phenomena have been observed in molecule-cavity coupled systems, which are believed to hold potential for applications in transistors, lasers, and computational units, among others. However, theoretical methods for simulating molecules in optical cavities still require further development due to the complex couplings between electrons, phonons, and photons within the cavity. In this study, motivated by recent advances in quantum algorithms and quantum computing hardware, we propose a quantum computing algorithm tailored for molecules in optical cavities. Our method, based on a variational quantum algorithm and variational boson encoders, has its effectiveness validated on both quantum simulators and hardware. For aggregates within the cavity, described by the Holstein-Tavis-Cummings model, our approach demonstrates clear advantages over other quantum and classical methods, as proved by numerical benchmarks. Additionally, we apply this method to study the H₂ molecule in a cavity using a superconducting quantum computer and the Pauli-Fierz model. To enhance accuracy, we incorporate error mitigation techniques, such as readout and reference-state error mitigation, resulting in an 86% reduction in the average error.

Photocatalytic carbon dioxide (CO₂) reduction shows great potential as an important approach to tackling global energy and environmental challenges. In recent years, zirconium-based metal–organic frameworks (Zr-MOFs), as an emerging class of crystalline porous solid materials, have attracted much attention in the field of photocatalytic CO₂ reduction due to their unique tailorable structures, high surface areas, and exceptional stability. In this Review, we first provide an in-depth discussion on the semiconductor-like behavior of Zr-MOFs and their fundamental mechanisms in photocatalytic CO₂ reduction. Subsequently, we systematically summarize current frontier strategies for enhancing the photocatalytic activity of Zr-MOFs, which include but are not limited to improving light absorption and utilization efficiency, promoting effective separation and transportation of photogenerated charges, and optimizing the surface redox reaction process. Furthermore, we elaborate on some advanced characterization techniques that can precisely track reaction intermediates and profoundly reveal the photocatalytic reaction kinetics within the Zr-MOF system. Finally, we propose possible future challenges and potential research directions for the development of Zr-MOFs in photocatalytic CO₂ reduction, aiming to provide valuable insights for researchers in related fields.

Platinum is a cornerstone catalyst for various chemical and electrochemical transformations. Atomically precise platinum nanoclusters, located at the transition stage between smaller platinum-ligand coordination molecules (<∼1 nm) and larger platinum colloidal nanoparticles (>∼3 nm), can combine the advantages of both homogeneous and heterogeneous catalysts, serving as model systems for understanding catalytic processes. However, compared to significant advances in coinage metal nanoclusters, atomically precise platinum nanoclusters remain largely unexplored. Here, we introduce the rich history and highlight the recent renaissance of atomically precise Pt clusters, focusing on their synthesis, structures, and properties. We discuss (i) how the sizes can be precisely controlled through the redox chemistry of one-dimensional platinum carbonyl clusters, (ii) how the core structures can be diversified in three-dimensional Pt_n(CO)_m clusters, (iii) how the surface properties can be tailored by using various types of ligands, and (iv) recent progress in evaluating these clusters in electrochemical and thermal catalytic reactions. By bridging the gaps among conventional coordination, cluster, colloidal, and catalytic chemistry, we expect to provide some fundamental insights that are crucial for designing more efficient platinum cluster catalysts with atomic precision.

The emerging of ultrasmall gold nanoparticles (nanoclusters) with atomic precision provides opportunities for precisely studying crystalline-amorphous heterostructures, despite the construction of such structures being challenging. In this work, we developed an acid-induction method and synthesized a Au₅₂(TBBT)₃₀ (TBBTH = 4-tert-butylbenzenelthiol) nanocluster with the kernel composed of two parts: the amorphous Au₂₂ part and the fcc Au₂₁ part, which represents the first construction of fcc-amorphous homometal heterojunction with ∼1 nm size. Density function theory (DFT) revealed that the HOMO-LUMO majorly distributed in the amorphous part and the HOMO-LUMO gap was dominated by the amorphous part, indicating the redox activity of the amorphous Au₂₂ part in contrast to the fcc Au₂₁ part, which was experimentally confirmed by differential pulse voltammetry, antioxidation test and anti-Galvanic reaction. But for electro-catalyzing reduction of CO₂ to CO, the crystalline surface sites were revealed to be more catalytically active than the amorphous surface sites in catalyzing the reduction of CO₂ to CO, and the most active sites were assigned to the cosurface sites of amorphous Au₂₂ and fcc Au₂₁, which is also responsible for the high performance of Au₅₂(TBBT)₃₀ relative to the pure fcc-structured Au₅₂(TBBT)₃₂ (the highest CO FE: 96.7% at -0.67 V vs 73.3% at -0.57 V; CO partial current density at the corresponding potential: -7.3 vs -2.7 mA cm^-2).