Wiley最新文献

In this approach, low-dimensional Fe₂O₃ nanoparticles (NPs) synthesized using wet-chemical methods in an alkaline medium were comprehensively characterized using Fourier transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy (FESEM), cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and X-ray diffraction (XRD) before their application in nitrite sensing. These analyses detailed the nanoparticles morphology, optical properties, crystallinity, elemental composition, and electro-catalytic behavior. Fabricated with a 5% Nafion coating on a glassy carbon electrode (GCE), the Fe₂O₃ NPs facilitated efficient electrochemical oxidation of nitrite through two-electron transfer, enabling precise detection. The sensor demonstrated high sensitivity of 1.66 µAmM⁻¹cm⁻², reproducibility, and reliability, surpassing conventional detection methods. Nitrite concentration detection with a wide linear dynamic range (LDR) from 2.4 to 13.4 mM, displayed a clear linear current response with increasing applied potential. The sensor also exhibited a low limit of detection (LOD) of 8.6 × 10⁻⁶ M, limit of quantification (LOQ) of 26.1 × 10⁻⁶ M, enhanced sensitivity, selectivity, and stability, with consistent performance in repeated tests over 50 cycles using LSV. This work introduces an effective approach for nitrite detection using low-dimensional Fe₂O₃ nanostructures, validated through real environmental samples with RSD between 0.415% and 0.866%, whereas recoveries were recorded between 98% and 99.38%, providing a robust and sustainable solution for environmental monitoring.

tert-Butyl ((3R,6R)-6-methylpiperidin-3-yl)carbamate is a pivotal pharmaceutical intermediate and active pharmacophore in drug synthesis, encompassing applications in orexin receptor antagonist and IRAK4 inhibitor. To date, a simple and efficient synthetic route remains a challenging issue for chemists in constructing chiral centers. In this study, we present a practical process for the preparation of tert-butyl ((3R,6R)-6-methylpiperidin-3-yl)carbamate, the key chiral intermediate via a chemoenzymatic strategy from commercially available ethyl N-Boc-D-pyroglutamate, which undergoes transamination-spontaneous cyclization process by transaminase (ATA) biocatalyst. Our study outlines a shortened-step streamlined procedure circumventing a significant amount of toxic chemicals and hazardous reaction conditions, and features cost-effective and high optical purity with >99.9% enantiomeric excess. The process features great prospect of industrialization application.

Spatially resolved characterization of proteoforms has substantial potential to significantly advance the understanding of physiological and disease mechanisms. However, challenges remain regarding throughput and coverage. A robust method is developed for high-throughput proteoform imaging (HTPi) by combining matrix-assisted laser desorption ionization mass spectrometry imaging (MALDI MSI) and region-specific top-down proteomic analysis. MALDI MSI enables the imaging of proteoforms on tissue sections at a rate of 7 h cm^-2 (100-µm spatial resolution), and the identification sensitivity of the proteoforms is improved by narrow-bore monolithic columns with low adsorption, yielding 366 annotated proteoform images from the mouse brain. The obtained proteoform images reveals differential expression of individual proteoforms across the brain regions, and distinct spatial distribution patterns of various proteoforms generated from a single gene. Given its ability to visualize proteoform, HTPi is further applied to explore spatial pathological changes associated with Alzheimer's disease (AD) in 5 × FAD mice. 158 annotated proteoform images are obtained in hippocampal regions at 50-µm spatial resolution, illuminating 14 differential proteoforms in the subiculum region and highlighting their significant associations with amyloid-β pathology in AD. The results highlight the power of HTPi in unraveling the intricate molecular landscape of brain tissues and its potential in elucidating disease mechanisms.

Cerebrospinal fluid (CSF) dynamics hold implications for neurological health. Despite its importance, accurate quantification of the CSF secretion rate remains a challenge due to methodological controversies and the influence of anesthesia. A novel technique is established to determine CSF dynamics in awake and freely moving rats, and the CSF secretion is quantified with three different methodologies. The CSF secretion rate is higher in awake rats than in anesthetized rats, the latter demonstrating no requirement for mechanical ventilation for optimal CSF quantification. The CSF secretion rate is ≈10-fold lower with the "direct method" than with the ventriculo-cisternal perfusion assay, although the relative acetazolamide-mediated reduction in CSF secretion is similar across three tested methods. The findings demonstrate the importance of awake models for optimal quantification of the absolute rate of CSF secretion but highlight the versatility of methodologies for the determination of relative changes in CSF secretion associated with inhibitors, age, sex, and various pathologies.

Decentralized molecular detection of pathogens remains an important goal for public health. Although polymerase chain reaction (PCR) remains the gold-standard molecular detection method, thermocycling using Peltier heaters presents challenges in decentralized settings. Recent work has demonstrated plasmonic PCR, where nanomaterials on a surface or nanoparticles in solution heat upon stimulation by light, as a promising method for rapid thermocycling. Heating of a solution via nanoparticles suspended in solution has been demonstrated in PCR tubes, but not on microfluidic chips. We developed a volumetric, microfluidic plasmonic reverse transcription (RT)-PCR method. A microfluidic chip is fabricated with an integrated thermocouple to measure internal temperature, feeding into a proportional-integral-derivative (PID) algorithm that modulates an infrared LED for closed-loop control. Gold nanorods are dispersed in solution with RT-PCR reagents. We created an instrument for plasmonic RT-PCR using an infrared LED for heating, fan for cooling, and fluorometer for end-point fluorescence detection. Rapid thermocycling and amplification of SARS-CoV-2 within 16 min (5 min for RT, 45 cycles in 11 min) is achieved. This paper demonstrates volumetric, plasmonic PCR in a microfluidic chip, using an integrated thermocouple for closed-loop control. This work points to the promise of using microfluidics and nanomaterials to achieve rapid, compact detection of pathogens in decentralized settings.

Cancer Vaccine

In article number 2412654, Qianqian Ni, Xiaoyuan Chen, Longjiang Zhang, and their team present a novel STING-activating polymer (PD) to enhance mRNA vaccine immunogenicity. By incorporating PD polymer into lipid nanoparticle, the resulted vehicle (PD LNP) improved lymphatic delivery and immune activation of mRNA cancer vaccine, demonstrating the promising potential of PD LNPs for cancer immunotherapy.

Plant-plant interactions are often overlooked when assessing carbon (C) cycling in plant community. Limited research exists on how nutrient competition influences soil organic carbon (SOC) dynamics via modifying rhizosphere C turnover. To address this issue, quantitative model of plant-plant interactions was established in three intercropping systems across 4 years. Key variables, including plant growth rate, relative interaction intensity, C retention, root and microbial-driven C emissions, rhizosphere priming effects (RPE), and extracellular enzyme activities, were quantified. Superior species exhibited significantly higher growth rate, photosynthetic fixed C retained in roots and rhizodeposition, and root respiration, but lower RPE (31.9%) relative to monocultures. Such trend was tightly associated with significant reduction of microbial mineralization caused by rhizosphere nitrogen and phosphorus enrichment. In contrast, due to low nitrogen and phosphorus availability in rhizosphere soils, the activities of rhizosphere extracellular hydrolase of inferior species increased, resulting in significant increase in RPE (21.9%) and decrease in photosynthetic fixed C from rhizodeposition. Therefore, plant-plant interactions are crucial in regulating SOC turnover in rhizosphere soils, and superior species can enhance soil C conservation by increasing root C inputs and suppressing RPE. These findings confirm the role of plant-plant interactions in SOC turnover in dryland intercropping systems.

The heterogeneity in prognostic survival and treatment response of hepatocellular carcinoma (HCC) limits the accurate assessment of HCC-specific mortality. This study aimed to identify potential HCC subtypes through latent class analysis (LCA) to improve HCC-specific mortality prediction and optimize treatment recommendations. We analyzed data from 7746 HCC patients in the Surveillance, Epidemiology, and End Results (SEER) databases, incorporating demographic and clinicopathological information and applying LCA to identify HCC subtypes. Prognostic survival and treatment response across different HCC subtypes were evaluated utilizing Cox proportional hazards regression and competing risks models. The classification was externally validated with data from 6791 patients. Four HCC subtypes (LCAC1-LCAC4) were determined. Compared with LCAC1, both LCAC2 (HR = 1.887, p < .001) and LCAC4 (HR = 1.317, p < .001) were associated with significantly shorter overall survival. LCAC2 had the highest HCC-specific mortality (HR: 2.395, p < .001), followed by LCAC4 (HR: 1.531, p < .001), and LCAC3 (HR: 1.424, p < .001). LCAC3 was associated with the lowest risk of non-HCC-specific mortality (HR: 0.613, p < .001). Surgical treatment, particularly preoperative systemic therapy, significantly improved survival across all HCC subtypes, whereas chemotherapy and radiotherapy had limited efficacy in LCAC1 and LCAC3 patients. External validation corroborated these findings. This study provides a classification system that differentiates HCC-specific mortality, facilitating accurate survival stratification and treatment recommendations, and provides valuable insight for clinical decision-making.

The conjugation-driven stability and reactivity of bis-imine formation from the reaction of substituted aromatic aldehydes and amines bearing electron donor and acceptor groups were studied in two approaches involving aldehydes and amines with the substituents either conjugated (para position) or non-conjugated (meta position) to the reacting functional groups. The bis-imine from the reaction of a bis-amine (B) with different types of aldehydes (A) constituted an ABA module, whereas the reaction of bis-aldehydes with different amines resulted in a BAB module. The competitive reactions were also studied for a specified bis-amine (B1 or B2) in similar conditions with a mixture of different aldehydes, and the time-dependent generations of dynamic covalent libraries were followed. The results indicated that conjugation modulated the bis-imine formation. The reaction of the conjugated bis-amine B1 with a mixture of two different aldehydes A1 and A2 favoured the formation of the bis-imine A1B1A2 involving different aldehydes. The results of the study provide insights into the effect of conjugation on the reactivity and stability of bis-imines and provide a basis for inducing selectivity features in the formation of bis-imines from different types of aldehyde and amine groups. They provide an entry into the design of dynamic covalent libraries generated from extended multicomponent systems.

The efficient conversion of carbon dioxide (CO2) into valuable products remains a keystone of sustainable energy research. Achieving this goal requires catalytic methodologies that can adapt to diverse energy sources such as light, heat, or electricity. This concept highlights the remarkable versatility of tetradentate PNNP-ligated iridium complexes, (PNNP)Ir, as multifunctional catalysts, which demonstrate outstanding performance in CO2 reduction across photochemical, thermal, and electrochemical systems. By fine-tuning the ligand structure for each system, (PNNP)Ir complexes achieved remarkable efficiency, selectivity, and durability across all applications.