European Journal of Inorganic Chemistry最新文献

With the advent of photoredox catalysis, new synthetic paradigms have been established with many novel transformations being achieved. Nevertheless, modern photoredox chemistry has several drawbacks, namely, deficiencies in reaction efficiency and scalability. Furthermore, wavelengths of light in excess of the energy required for a chemical reaction are often used. In this Review, we document recent developments of low-energy light-absorbing catalysts and their cognate photochemical methods, advantageously mitigating off-cycle photochemical reactivity of excited-state species in the reaction mixture and improving batch scalability of photochemical reactions. Finally, developments in red-light photoredox catalysis are leading the next-generation applications to polymer science and biochemistry–chemical biology, enabling catalytic reactions within media composites — including mammalian tissue — that are historically recalcitrant with blue-light photoredox catalysis.

Olefin metathesis, as a powerful metal-catalysed carbon–carbon bond-forming method, has achieved considerable progress in recent years. However, the complexity originating from multicomponent interactions has long impeded a complete mechanistic understanding of olefin metathesis, which hampers further optimization of the reaction. Here, we clarify both productive and hidden degenerate pathways of ring-closing metathesis by focusing on one individual catalyst, using a sensitive single-molecule electrical detection platform. In addition to visualizing the full pathway, we found that the conventionally unwanted degenerate pathways have an unexpected constructive coupling effect on the productive pathway, and both types of pathway can be regulated by an external electric field. We then pushed forward this ability to ring-opening metathesis polymerization involving more interactive components. With single-monomer-insertion-event resolution, precise on-device synthesis of a single polymer was achieved by online manipulation of monomer insertion dynamics, intramolecular chain transfer, stereoregularity, degree of polymerization and block copolymerization. These results offer a comprehensive mechanistic understanding of olefin metathesis, exemplifying infinite opportunities for practical precise manufacturing.

In-sensor computing, which integrates sensing, memory and processing functions, has shown substantial potential in artificial vision systems. However, large-scale monolithic integration of in-sensor computing based on emerging devices with complementary metal–oxide–semiconductor (CMOS) circuits remains challenging, lacking functional demonstrations at the hardware level. Here we report a fully integrated 1-kb array with 128 × 8 one-transistor one-optoelectronic memristor (OEM) cells and silicon CMOS circuits, which features configurable multi-mode functionality encompassing three different modes of electronic memristor, dynamic OEM and non-volatile OEM (NV-OEM). These modes are configured by modulating the charge density within the oxygen vacancies via synergistic optical and electrical operations, as confirmed by differential phase-contrast scanning transmission electron microscopy. Using this OEM system, three visual processing tasks are demonstrated: image sensory pre-processing with a recognition accuracy enhanced from 85.7% to 96.1% by the NV-OEM mode, more advanced object tracking with 96.1% accuracy using both dynamic OEM and NV-OEM modes and human motion recognition with a fully OEM-based in-sensor reservoir computing system achieving 91.2% accuracy. A system-level benchmark further shows that it consumes over 20 times less energy than graphics processing units. By monolithically integrating the multi-functional OEMs with Si CMOS, this work provides a cost-effective platform for diverse in-sensor computing applications.

Biosensors play key roles in medical research and diagnostics. However, the development of biosensors for new biomolecular targets of interest often involves tedious optimization steps to ensure a high signal response at the analyte concentration of interest. Here we show a modular nanosensor platform that facilitates these steps by offering ways to decouple and independently tune the signal output as well as the response window. Our approach utilizes a dynamic DNA origami nanostructure to engineer a high optical signal response based on fluorescence resonance energy transfer. We demonstrate mechanisms to tune the sensor’s response window, specificity and cooperativity as well as highlight the modularity of the proposed platform by extending it to different biomolecular targets including more complex sensing schemes. This versatile nanosensor platform offers a promising starting point for the rapid development of biosensors with tailored properties.

Photodynamic therapy (PDT) — which combines light, oxygen and photosensitizers (PS) to generate reactive oxygen species — has emerged as an effective approach for targeted ablation of pathogenic cells with reduced risk of inducing resistance. Some organic PS are now being applied for PDT in the clinic or undergoing evaluation in clinical trials. A limitation of the first-generation organic PS was their potential off-target toxicity. This shortcoming prompted the design of constructs that can be activated by the presence of specific biomolecules — from small biomolecules to large enzymes — in the target cells. Here, we review advances in the design and synthesis of activatable organic PS and their contribution to PDT in the past decade. Important areas of research include novel synthetic methodologies to engineer smart PS with tuneable singlet oxygen generation, their integration into larger constructs such as bioconjugates, and finally, representative examples of their translational potential as antimicrobial and anticancer therapies.

Nerve–cancer crosstalk has gained substantial attention owing to its impact on tumour growth, metastasis and therapy resistance. Effective therapeutic strategies targeting tumour-associated nerves within the intricate tumour microenvironment remain a major challenge in pancreatic cancer. Here we develop Escherichia coli Nissle 1917-derived outer membrane vesicles conjugated with nerve-binding peptide NP41, loaded with the tropomyosin receptor kinase (Trk) inhibitor larotrectinib (Lar@NP-OMVs) for tumour-associated nerve targeting. Lar@NP-OMVs achieve efficient nerve intervention to diminish neurite growth by disrupting the neurotrophin/Trk signalling pathway. Moreover, OMV-mediated repolarization of M2-like tumour-associated macrophages to an M1-like phenotype results in nerve injury, further accentuating Lar@NP-OMV-induced nerve intervention to inhibit nerve-triggered proliferation and migration of pancreatic cancer cells and angiogenesis. Leveraging this strategy, Lar@NP-OMVs significantly reduce nerve infiltration and neurite growth promoted by gemcitabine within the tumour microenvironment, leading to augmented chemotherapy efficacy in pancreatic cancer. This study sheds light on a potential avenue for nerve-targeted therapeutic intervention for enhancing pancreatic cancer therapy.