Steering Photooxidation of Methane to Formic Acid over A Priori Screened Supported Catalysts.

Efficient methane photooxidation to formic acid (HCOOH) has emerged as a sustainable approach to simultaneously generate value-added chemicals and harness renewable energy. However, the persistent challenge lies in achieving a high yield and selectivity for HCOOH formation, primarily due to the complexities associated with modulating intermediate conversion and desorption after methane activation. In this study, we employ first-principles calculations as a comprehensive guiding tool and discover that by precisely controlling the O2 activation process on noble metal cocatalysts and the adsorption strength of carbon-containing intermediates on metal oxide supports, one can finely tune the selectivity of methane photooxidation products. Specifically, a bifunctional catalyst comprising Pd nanoparticles and monoclinic WO3 (Pd/WO3) would possess optimal O2 activation kinetics and an intermediate oxidation/desorption barrier, thereby promoting HCOOH formation. As evidenced by experiments, the Pd/WO3 catalyst achieves an exceptional HCOOH yield of 4.67 mmol gcat-1 h-1 with a high selectivity of 62% under full-spectrum light irradiation at room temperature using molecular O2. Notably, these results significantly outperform the state-of-the-art photocatalytic systems operated under identical condition.

Designing Heterocyclic Covalent Organic Frameworks with Tunable Electronic Structures for Efficient Electrosynthesis of Hydrogen Peroxide.

The electrocatalytic production of hydrogen peroxide (H2O2) through the two-electron oxygen reduction reaction (2e- ORR) has garnered significant research attention in recent years due to its numerous appealing advantages, such as being eco-friendly and exhibiting high energy conversion efficiency. Metal-free carbon materials with specific catalytic sites have been recognized as potential electrocatalysts for 2e- ORR; however, the design of highly efficient catalysts with well-defined structures and long-term stability for large-scale H2O2 production remains unsatisfactory. In this study, three covalent organic frameworks (COFs) - imine-linked LZU-1, oxazole-linked LZU-190, and thiazole-linked LZU-190(S), are successfully synthesized to explore their catalytic activity in electrocatalytic H2O2 production. Among these, the carbon sites LZU-190(S) are predominantly activated by the introduced adjacent heteroatoms via electronic effects, resulting in much higher H2O2 selectivity compared to the oxazole and imine linkages. This work provides new insights into developing COFs-based electrocatalysts for efficient H2O2 generation.

Flexible Full-Inorganic Ultrathin Films with Stable Circularly Polarized Luminescence Covering the Visible to Near-Infrared Region.

Circularly polarized luminescence (CPL) materials hold significant value in various fields, including information storage, secure communication, three-dimensional displays, biological detection, and optoelectronic devices. Using the Langmuir-Schaeffer (LS) assembly technique, we successfully construct a series of large-area flexible optical ultrathin films. Impressively, the inorganic assembled ultrathin films exhibit excellent CPL optical activity covering the visible to near-infrared (NIR) region, with the luminescence asymmetry factor glum ranging from 0.59 to 0.72. Moreover, such ultrathin films also display outstanding mechanical flexibility, the optical activity of which even after 240 bending cycles shows almost no difference compared to the unbent samples. Owing to the ultra-broadband optical activity and ultra-stable optical activity of such full-inorganic assembled materials on flexible substrates, coupled with their excellent processability and outstanding mechanical flexibility, we anticipate they will find use in many fields such as communication technology and flexible optoelectronics.

Customized Photoelectrochemical C-N and C-P Formation Enabled by Tailored Deposition on Photoanodes.

Photoelectrochemistry (PEC) is burgeoning as an innovative solution to organic synthesis. However, the current PEC system suffers limited reaction types and unsatisfactory performances. Herein, we employ efficient BiVO4 photoanode with tailored deposition layers for customizing two PEC approaches toward C-N and C-P formation. Notably, our process proceeds under mild reaction conditions, easily available substrates, and ultra-low potentials. Beyond photocatalysis and electrocatalysis, customized PEC offers high efficiency, good functional group tolerance, and substantial applicability for decorating drug molecules, highlighting its promising potential to enrich the synthetic toolbox for broader organic chemistry of practical applications.

Photoelectrochemical Ni-catalyzed cross-coupling of aryl bromides with amine at ultra-low potential.

Photoelectrochemical (PEC) cell is an ideal platform for organic transformation because of its green benefits and minimal energy consumption. As an emerging methodology, the reaction types of photoelectrocatalytic organic synthesis (PECOS) are limited to simple oxidation and C-H activation at current stage. Metal catalysis for the construction of C(sp2)-N bonds has not been touched yet in PECOS. We introduce here a PEC method that successfully engages Ni catalysis for the mild production of aniline derivatives. Experimental and computational investigations elucidate that the addition of photoanode-generated amine radical to Ni catalyst avoids the sluggish nucleophilic attack, enabling the reaction to proceed at an ultra-low potential (-0.4 V vs. Ag/AgNO3) and preventing the overoxidation of products in conventional electrochemical synthesis. This synergistic catalysis strategy exhibits good functional group tolerance and wide substrate scope on both aryl halides and amines, by which some important natural products and pharmaceutical chemicals have been successfully modified.

Molecular subtypes of colorectal cancer in the era of precision oncotherapy: Current inspirations and future challenges.

BACKGROUND: Colorectal cancer (CRC) is among the most hackneyed malignancies. Even patients with identical clinical symptoms and the same TNM stage still exhibit radically different clinical outcomes after receiving equivalent treatment regimens, indicating extensive heterogeneity of CRC. Myriad molecular subtypes of CRC have been exploited for decades, including the most compelling consensus molecular subtype (CMS) classification that has been broadly applied for patient stratification and biomarker-drug combination formulation. Encountering barriers to clinical translation, however, CMS classification fails to fully reflect inter- or intra-tumor heterogeneity of CRC. As a consequence, addressing heterogeneity and precisely managing CRC patients with unique characteristics remain arduous tasks for clinicians. REVIEW: In this review, we systematically summarize molecular subtypes of CRC and further elaborate on their clinical applications, limitations, and future orientations. CONCLUSION: In recent years, exploration of subtypes through cell lines, animal models, patient-derived xenografts (PDXs), organoids, and clinical trials contributes to refining biological insights and unraveling subtype-specific therapies in CRC. Therapeutic interventions including nanotechnology, clustered regulatory interspaced short palindromic repeat/CRISPR-associated nuclease 9 (CRISPR/Cas9), gut microbiome, and liquid biopsy are powerful tools with the possibility to shift the immunologic landscape and outlook for CRC precise medicine.