Adjacent Sites Research Articles

Rare Head and Neck Cancers and Pathological Diagnosis Challenges: A Comprehensive Literature Review

Head and neck cancers (HNCs) arise from anatomically adjacent sites and subsites, with varying etiological factors, diagnostic strategies, prognoses, and treatment approaches. While conventional squamous cell carcinoma (SCC) is the most common histology in the head and neck district, HNCs encompass a variety of rare histopathological entities, categorized into epithelial tumors such as salivary gland cancers, sinonasal tumors, neuroendocrine tumors, malignant odontogenic tumors, and SCC variants versus non-epithelial tumors including soft tissue sarcomas, mucosal melanomas, and hematological malignancies. Rare HNCs (R-HNCs) represent a diagnostic and clinical challenge, requiring histopathological expertise, the availability of peculiar molecular analysis, and the personalization of local and systemic treatments, all guided by a multidisciplinary tumor board. Here, we provide a comprehensive literature review on R-HNCs, emphasizing key histopathological and molecular characteristics that are crucial for guiding treatment decisions. An insight about the latest developments in systemic treatments is also reported.

Interfacial Engineering Constructing TFSI- Ion-Sieve Protective Umbrella Guiding Li-Ion Selective Transport and Solid SEI Growth.

A novel strategy is proposed by constructing TFSI- ion-sieve interlayer to guide Li-ion selective transport and solid SEI growth. The uniform MgF2 seeds on the fiber surface reacts rapidly with Li+ in electrolyte to form Mg and LiF dual functional sites for the first charging process. Benefiting from the high affinity of LiF, the TFSI- ions is enriched near the anode forming an ion-sieve interlayer, which acts as a protective umbrella and guides priority penetration of Li+ due to the coordination reaction with Li+ and thus homogenize the Li+ flux. While the Mg sites induce Li nucleation with its strong lithiophilicity and facilitate uniform Li plating on fiber surface. Furthermore, as raw material of LiF, the TFSI- enrichment on anode surface is contribute to increasing LiF content in SEI, achieving the stability enhancement and densification of SEI. Of greater importance, the excess Li+ can spread to the adjacent Mg sites for nucleation by means of ultralow Li+ migration barrier on LiF and Mg. The combination of the ion-sieve homogenization of Li+ flux in electrolyte and the uniformity of Li+ transport in LiF/Mg solid medium achieves the purpose of uniform Li metal plating/stripping.

Out-of-plane coordination of iridium single atoms with organic molecules and cobalt-iron hydroxides to boost oxygen evolution reaction.

Advancements in single-atom-based catalysts are crucial for enhancing oxygen evolution reaction (OER) performance while reducing precious metal usage. A comprehensive understanding of underlying mechanisms will expedite this progress further. Here we report Ir single atoms coordinated out-of-plane with dimethylimidazole (MI) on CoFe hydroxide (Ir1/(Co,Fe)-OH/MI). This Ir1/(Co,Fe)-OH/MI catalyst, which was prepared using a simple immersion method, delivers ultralow overpotentials of 179 mV at a current density of 10 mA cm-2 and 257 mV at 600 mA cm-2 as well as an ultra-small Tafel slope of 24 mV dec-1. Furthermore, Ir1/(Co,Fe)-OH/MI has a total mass activity exceeding that of commercial IrO2 by a factor of 58.4. Ab initio simulations indicate that the coordination of MI leads to electron redistribution around the Ir sites. This causes a positive shift in the d-band centre at adjacent Ir and Co sites, facilitating an optimal energy pathway for OER.

Ecological assessment and conservation performance of the Wechiau Hippo Sanctuary: A differential assessment of protected and unprotected zones

Evaluating human impacts on the structural and functional dynamics of ecotourism sites is crucial for monitoring and managing natural ecosystems. This study assessed conservation performance in the Wechiau Hippo Sanctuary versus degradation in the adjacent unprotected forest, which is prone to human activities. Eighteen samples each of above-ground live biomass (AGL), litter, and root biomass, along with 36 soil samples (0–20 cm depth), were collected from 20 m × 20 m and 1 m × 1 m plots and subplots at both sites. The study found that the average tree density in the area was 210.00 whereas the above-ground live biomass had 524.30. Mean values for litter and root biomass, pH, N and P were 345.44 and 69.94. The protected site recorded a significantly higher (p < 0.001) concentration of total N and OM content as compared to the adjacent unprotected site whereas there was no significance (p = 0.010) in available P in both areas. Available micronutrients (Mn, Zn) were higher in the protected area compared to the unprotected while the Fe levels were higher in the unprotected site. Cu was below the detectable value in both sites. The protected and unprotected areas revealed significant differences (t(14) = 1.527, p = 0.029), with a strong positive correlation between them (r = 0.766, p = 0.001). Therefore, if the adjacent unprotected forest is not subjected to management mechanisms and protection from the fringe communities, the reserve may remain under threat of encroachment and degradation as these resources may be severely affected.

Negative outcome in cutaneous Mycobacterium marinum infection treated with surgical intervention: Two-case report.

Mycobacterium marinum (M marinum), a slow-growing nontuberculous mycobacterium (NTM), is widely distributed in aquatic environments. It is a well-known cutaneous pathogen, which causes sporotrichosis-like lesions. In this report, we describe 2 cases of subcutaneous M marinum infection. Both patients underwent several surgical procedures at local hospitals, and despite optimal surgical site healing, new lesions appeared in adjacent sites. Based on NTM culture, identification by gene sequencing, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry, the diagnosis of subcutaneous NTM infection was confirmed. The patients were treated with oral rifampicin 0.45 g/day and clarithromycin 1 g/day and oral doxycycline hydrochloride capsules (200 mg/day), respectively. Both patients were treated for 8 and 5 weeks, respectively, and the lesions healed. Surgical debridement cannot compete with or impede NTM lymphatic spread; antimicrobial therapy is the first choice for the treatment of M marinum infections.

Methylation patterns at the adjacent CpG sites within enhancers are a part of cell identity

BackgroundIt is generally accepted that methylation status of CpG sites spaced up to 50 bp apart is correlated, and accumulation of locally disordered methylation at adjacent CpG sites is involved in neoplastic transformation, acting in similar way as stochastic accumulation of mutations.ResultsWe used EPIC microarray data from 596 samples, representing 12 healthy tissue and cell types, as well as 572 blood cancer specimens to analyze methylation status of adjacent CpG sites across human genome, and subsequently validated our findings with NGS and Sanger sequencing. Our analysis showed that there is a subset of the adjacent CpG sites in human genome, with cytosine at one CpG site methylated and the other devoid of methyl group. These loci map to enhancers that are targeted by families of transcription factors involved in cell differentiation. Moreover, our results suggest that the methylation at these loci differ between alleles within a cell, what allows for remarkable level of heterogeneity of methylation patterns. However, different types of specialized cells acquire only one specific and stable pattern of methylation at each of these loci and that pattern is to a large extent lost during neoplastic transformation.ConclusionsWe identified a substantial number of adjacent CpG loci in human genome that display remarkably stable and cell type specific methylation pattern. The methylation pattern at these loci appears to reflect different methylation of alleles in cells. Furthermore, we showed that changes of methylation status at those loci are likely to be involved in regulation of the activity of enhancers and contribute to neoplastic transformation.

Mutation-Specific CRISPR Targeting with SaCas9 and AsCas12a Restores Therapeutic Sensitivity in Treatment-Resistant Melanoma.

Background: Melanoma remains one of the most challenging cancers to treat effectively with drug resistant remaining a constant concern, primarily with activating BRAF mutations. Mutations in the BRAF gene appear in approximately 50% of patients, 90% of which are V600E. Two frontline BRAF inhibitors (BRAFi), vemurafenib and dabrafenib, are frequently used to treat unresectable or metastatic BRAF V600E melanoma. Initial response rates are high, but soon thereafter, 70-80% of patients develop resistance to treatment within a year. A major mechanism of resistance is the generation of a secondary Q61K mutation in the NRAS gene. Methods: We have developed an approach in which a CRISPR-Cas complex can be designed to distinguish between mutant genes enabling resistance to standard care in tumor cells and normal genomes of healthy cells. For the first time, we demonstrated the utility of two CRISPR-directed mutation-specific editing approaches to restore BRAFi sensitivity in BRAFV600E/NRASQ61K resistant A375 cells. Results: We utilize an AsCas12a protospacer adjacent motif site created by the NRAS Q61K mutation and the Q61K mutation in the critical seed region of an SaCas9 sgRNA for Q61K-selective targeting. We show here that both approaches allow for effective NRAS targeting of only mutated-Q61K and after CRISPR-directed Q61K-targeting, previously resistant A375 cells are re-sensitized to BRAFi treatment. Conclusion: Our data support the feasibility of the development of CRISPR-Cas therapeutic approaches to the treatment of melanoma. Successful therapeutic CRISPR-directed gene editing would enable both specific and efficient editing of a mutation-specific targeting approach eliminate concern for on- and off-target damage to the genomes of healthy cells.

Strontium Doped IrOx Triggers Direct O-O Coupling to Boost Acid Water Oxidation Electrocatalysis.

The discovery of efficient and stable electrocatalysts for the oxygen evolution reaction (OER) in acidic conditions is crucial for the commercialization of proton-exchange membrane water electrolyzers. In this work, we propose a Sr(OH)2-assisted method to fabricate a (200) facet highly exposed strontium-doped IrOx catalyst to provide available adjacent iridium sites with lower Ir-O covalency. This design facilitates direct O-O coupling during the acidic water oxidation process, thereby circumventing the high energy barrier associated with the generation of *OOH intermediates. Benefiting from this advantage, the resulting Sr-IrOx catalyst exhibits an impressive overpotential of 207 mV at a current density of 10 mA cm-2 in 0.5 M H2SO4. Furthermore, a PEMWE device utilizing Sr-IrOx as the anodic catalyst demonstrates a cell voltage of 1.72 V at 1 A cm-2 and maintains excellent stability for over 500 hours. Our work not only provides guidance for the design of improved acidic OER catalysts but also encourages the development of iridium-based electrocatalysts with novel mechanisms for other electrocatalytic reactions.

Establishing a Robust Nonlinear Targeted Switch for C1 Electroproduction in Atomic Alloy Cox/Pd Bimetallenes

Establishing a targeted switch for CO2 conversion under electric drive is essential for achieving carbon‐balance by enabling selective chemicals. However, engineering the topological assembly of active sites to precisely regulate the competing pathways for various intermediates has been plagued by unclear structure‐function relationships. To tailor the CO/formate pathways, herein we established a robust nonlinear targeted switch with tunable active Cox sites integrated into Pd metallene, which involves Co1/Pd single‐atom alloy (favoring CO) and Co2/Pd diatomic alloy (favoring formate). Transitioning from Co1/Pd to Co2/Pd atomic alloy bimetallenes resulted in a nonlinear, high‐contrast flip in selectivity, surpassing 94% for CO and formate productions in both H‐cell and flow cell. Furthermore, the superior selectivity and current efficiency for CO (&gt; 80 %) and formate (&gt; 88%) were consistently maintained at ‐150 mA cm‐2 over continuous 200 h. Theoretical simulations and in‐situ spectroscopy analyses unveiled that appropriate adjacent metal site combinations (Pd‐Pd, Pd‐Co and Co‐Co) lead to tunable dz2 band center and a nonlinear shift in preferred adsorption configurations of intermediates, dictating the C1 pathways. Our finding reveals a desired switch in C1 selectivity and robust stability within Cox/Pd system, providing a new perspective for fine‐tuning energy conversion processes through specific topological assembly.

Establishing a Robust Nonlinear Targeted Switch for C1 Electroproduction in Atomic Alloy Cox/Pd Bimetallenes.

Establishing a targeted switch for CO2 conversion under electric drive is essential for achieving carbon-balance by enabling selective chemicals. However, engineering the topological assembly of active sites to precisely regulate the competing pathways for various intermediates has been plagued by unclear structure-function relationships. To tailor the CO/formate pathways, herein we established a robust nonlinear targeted switch with tunable active Cox sites integrated into Pd metallene, which involves Co1/Pd single-atom alloy (favoring CO) and Co2/Pd diatomic alloy (favoring formate). Transitioning from Co1/Pd to Co2/Pd atomic alloy bimetallenes resulted in a nonlinear, high-contrast flip in selectivity, surpassing 94% for CO and formate productions in both H-cell and flow cell. Furthermore, the superior selectivity and current efficiency for CO (> 80 %) and formate (> 88%) were consistently maintained at -150 mA cm-2 over continuous 200 h. Theoretical simulations and in-situ spectroscopy analyses unveiled that appropriate adjacent metal site combinations (Pd-Pd, Pd-Co and Co-Co) lead to tunable dz2 band center and a nonlinear shift in preferred adsorption configurations of intermediates, dictating the C1 pathways. Our finding reveals a desired switch in C1 selectivity and robust stability within Cox/Pd system, providing a new perspective for fine-tuning energy conversion processes through specific topological assembly.

Identification of the TRPA1 cannabinoid-binding site

Chronic pain accounts for nearly two-thirds of conditions eligible for medical cannabis licenses, yet the mechanisms underlying cannabis-induced analgesia remain poorly understood. The principal phytocannabinoids, the psychoactive Δ9-tetrahydrocannabinol (THC) and non-psychoactive cannabidiol (CBD), exhibit comparable efficacy in pain management. Notably, THC functions as an agonist of cannabinoid receptor 1 (CB1), whereas CBD shows minimal activity on CB1 and CB2 receptors. Elucidating the molecular targets through which phytocannabinoids modulate the pain system is required for advancing our understanding of the pain pathway and optimizing medical cannabis therapies. Transient receptor potential ankyrin 1 (TRPA1), a pivotal chemosensor in the pain pathway, has been identified as a phytocannabinoid target. Unlike most TRPA1 activators, phytocannabinoid activation is not mediated through the electrophilic binding site, suggesting an alternative mechanism. Here, we identified the human TRPA1 channel cannabinoid-binding site (CBS) and demonstrated that mutations at residue Y840 abolished responses to both THC and CBD at saturating concentrations, indicating a shared primary binding site. Molecular modeling revealed distinct interactions of THC and CBD with the Y840 residue within the CBS. Additionally, CBD binds to the adjacent general anesthetic binding site at oversaturating concentrations. Our findings define the CBS of TRPA1 as overlapping with and adjacent to binding sites for other allosteric activators, suggesting that TRPA1 possesses a highly adaptable domain for binding non-electrophilic activators. This underscores its unique role as a chemosensor in the pain pathway. Furthermore, our results provide new insights into the molecular mechanisms of cannabinoid-induced analgesia and identify novel targets for pain management therapies.

Mild and rapid construction of Ti electrodes for efficient and corrosion-resistant oxidative catalysis at industrial-grade intensity

The development of cost-effective and corrosion-resistant catalytic electrodes for chlorine/oxygen evolution reaction (CER/OER) in large-scale industrial applications is a significant challenge. Herein, the sol–gel method is employed to achieve a uniform coating of ruthenium (Ru) doping copper (Cu) on titanium sheet (Ru + 20 %Cu@Ti), and the highly efficient industrial grade stable Ti dimensional stable anode can be quickly constructed at 723.15 K for 2 h. Cu doping reduces the vacancy formation energy of surface oxygen, promotes additional lattice oxygen vacancy assisted hydrolysis dissociation pathway, improves the selectivity and specific activity of CER at high concentration doping, and reduces the binding energy of OER intermediates (e.g., *OH, *O, and *OOH) at adjacent Ru active sites. The overpotentials require to reach the current density of 10 mA cm−2 for CER and OER were only 365 mV and 232 mV at the conditions of 5.0 M NaCl (pH = 7.0) and 1.0 M KOH + 0.5 M NaCl. More importantly, Ru + 20 %Cu@Ti demonstrates excellent stability, operates continuously for over 340h at industrial current density in neutral and alkaline electrolytes, and its strengthening life reaches 64 h, with ultra-low performance attenuation. Impressively, the designed applied electrode (8.0 cm ✕ 15.0 cm) achieves long-term CER at 0.2–0.3 A cm−2. Further industrial grade evaluation of CER shows that its chlorine extraction polarizability, enhances life and weight loss meet the requirements of industrial applications.

Fabrication of Hofmann-type metal-organic framework based mixed-matrix membranes for efficient CH4/N2 separation

The analogous physical and chemical properties of methane (CH4) and nitrogen (N2) pose a great challenge for their separation. Mixed-matrix membranes (MMMs), combining the good separation performance of fillers and easy processability of polymers, are expected to address this challenging task. In this work, one Hofmann-type metal-organic framework (MOF), CoNi-DABCO, featuring abundant oppositely adjacent open metal sites, narrow pore size, and strong binding affinity toward CH4, is introduced into the polymer of polydimethylsiloxane to fabricate MMMs. The presence of CoNi-DABCO in the membranes could enhance the adsorption capacity for CH4, thus facilitating the transport of CH4 molecules through the membranes. Specially, the MMM containing 20 wt% CoNi-DABCO displays a high CH4 permeability of 1285 Barrer and maintains a good CH4/N2 mixed-gas selectivity of 3.7. Furthermore, the MMMs show good pressure resistance (up to 10 bar) and long-term stability for 30 days. This study suggests the potential of Hofmann-type MOF in the development of high-performance membranes for CH4/N2 separation.

Bayesian statistical analysis reveals spatial heterogeneity in Cyclone Thane deposits from Southeast India

Modern and geological records of storm sedimentary deposits preserved on siliciclastic coastlines are important archives to evaluate the past and current magnitude and impacts of.storms. Examination of modern storm deposits also offers the opportunity to evaluate the similarities and differences between storm and other coastal overwash processes and hazards.We examined the stratigraphy and sedimentary characteristics of the 31st December 2012 Cyclone Thane and underlying coastal units from 14 pits from six sites from the coastal zone of Tamil Nadu Province, southeast India. We analysed the grain size parameters, grain shape, and heavy mineral proportions of each deposit in high resolution and examined the sedimentary structures of each unit. For the first time, we use Bayesian factors to quantitatively evaluate the similarities and differences between the storm sedimentary deposits and other co-located coastal sedimentary deposits. At several sites, the storm deposits differ in several parameters from the underlying coastal deposits, but at some locations, distinguishing between different depositional units cannot be achieved. In comparing the storm deposits from the different sites, mean grain size results in the most coherent pattern with closely located sites having similar mean grain size, and more southerly sites being finer grained. The other measured parameters show a far less coherent pattern with adjacent sites often preserving larger differences than more distal sites attesting to very local hydrodynamic variations during sediment deposition. As with the sedimentary parameters, the sedimentary structures formed during sediment deposition preserved at each site are highly variable. To date, the presence of terminal foresets at the landward edge of washover fans remains the only diagnostic feature of storm deposition, but that this feature is not ubiquitous across all storm deposits. Our findings demonstrate the spatially heterogeneous nature of storm sediment deposition and the challenges of identifying storm deposits in coastal siliciclastic sequences. The use of Bayesian statistical approaches also offers a robust method for evaluating and discriminating between coastal sediment deposits that has many advantages over traditional frequentist approaches. This method can easily be applied to other sedimentary depositional environments.

Coral Community Composition Linked to Hypoxia Exposure.

Tropical reef ecosystems are strongly influenced by the composition of coral species, but the factors influencing coral diversity and distributions are not fully understood. Here we demonstrate that large variations in the relative abundance of three major coral species across adjacent Caribbean reef sites are strongly related to their different low O2 tolerances. In laboratory experiments designed to mimic reef conditions, the cumulative effect of repeated nightly low O2 drove coral bleaching and mortality, with limited modulation by temperature. After four nights of repeated low O2, species responses also varied widely, from > 50% bleaching in Acropora cervicornis to no discernable sensitivity of Porites furcata. A simple metric of hypoxic pressure that combines these experimentally derived species sensitivities with high-resolution field data accurately predicts the observed relative abundance of species across three reefs. Only the well-oxygenated reef supported the framework-building hypoxia-sensitive Acropora cervicornis, while the hypoxia-tolerant weedy species Porites furcata was dominant on the most frequently O2-deplete reef. Physiological exclusion of acroporids from these O2-deplete reefs underscores the need for hypoxia management to reduce extirpation risk.

Tip-like copper sites on high curvature supports for non-covalent to covalent interaction tuning in CO2 photoreduction

Single-atom engineering offers a promising method to transform CO2 into high-value chemicals. The local coordination structure design of the metal-support is crucial for overcoming slow reaction kinetics. In this study, Cu single atoms are immobilized on curved Bi12O17Br2 surface to create a tip-like metal site structure named Cutip-Bi12O17Br2. Due to the high curvature Bi12O17Br2 surface with tensile strain, the tip Cu creates significant electronegativity differences between adjacent Bi atomic sites, creating the vigorous polarization centers. The strong charge redistribution character of tip asymmetric Cu-Bi site favor the polarization of CO bond in nonpolar CO2 and adjust the noncovalent to covalent interaction of reaction intermediates. Benefiting from these features, the optimized Cutip-Bi12O17Br2 enhance the CO production rate by a factor of 34 relative to bulk-Bi12O17Br2, reaching a rate of 96.99 μmol g−1 h−1. This work provides a comprehensive understanding of the structural regulation of single-atom on high curvature surface for CO2 photoreduction.

Hydroclimatic change and vegetation response in Tropical African alpine environments over the Holocene

Future precipitation is highly uncertain, particularly in East Africa where model projections contradict modern observational trends. Climate changes in East Africa's mountains are even less well understood, yet these mountains are threatened by warming, extreme flooding, fires, and the rapid disappearance of glaciers. Paleoclimatic and paleoenvironmental records can contextualize ongoing and future changes; however, proxy records from East African mountains disagree with each other and, in some cases, differ from nearby lowland sites. It is unclear if these discrepancies are due to geographic or altitudinal gradients in climate or processes that impact the fidelity of climate proxies in these mountains. To better understand past mountain precipitation and vegetation change, we produced three new records of the hydrogen and carbon isotopic composition of terrestrial leaf waxes (δ2Hwax and δ13Cwax) spanning the Holocene using lake sediment cores collected from Lake Mahoma (2990 m asl), Lake Africa (3895 m asl), and Lake Kopello (4017 m asl) in the Rwenzori Mountains, Uganda-Democratic Republic of Congo. We find similar trends at all three sites in reconstructed precipitation hydrogen isotopic composition (δ2Hprecip), which we interpret to reflect precipitation amount. Our records show drying occurred during the Younger Dryas (∼12 cal ka BP), enhanced precipitation during the African Humid Period (∼10-5 cal ka BP) and drying in the mid to late Holocene (∼5-0 cal ka BP), similar to adjacent lowland sites. We observe a gradual termination of the African Humid Period in the Rwenzori, consistent with many regional records. We also observe distinct patterns of Holocene precipitation change in Eastern and Western Africa, indicating differences in the delivery of moisture from the Atlantic and Indian Oceans. Despite changes in precipitation over the Holocene, the carbon isotopic composition of the waxes in Rwenzori lakes indicates constant C3 vegetation and eco-hydrological stability, in contrast to sites from lower elevations. This likely indicates climate remained humid and cool enough throughout the Holocene to maintain forest and alpine plant communities at these high-elevation mountain sites.

Structure engineering and surface reconstruction enabling MoNi4 hollow nanocube for efficient urea-assisted water electrolysis

Nickel-based electrocatalysts are identified as the promising candidates for both urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) in urea-assisted water electrolysis to accelerate energy saving hydrogen production. However, the high occupation of Ni 3d orbital leads to their constrained adsorption for reactant and multiple intermediates during UOR process. Herein, considering the d-band electron complementation, the bimetallic MoNi4 hollow nanocubes self-assembled with numerous ultrathin nanosheets was constructed by introducing molybdenum with relatively empty d orbital and synergistically boost UOR/HER activities. Notably, the MoNi4 requires a lower cell voltage of 1.462 V to drive a current density of 10 mA cm−2 in urea electrolyzer, superior to that in water electrolyzer (1.796 V) and most of the reported nickel-based electrocatalysts, as well as the urea degradation rate is impressive. In situ technologies including electrochemical impedance spectroscopies and Raman spectra reveal that the favorable UOR pathway can be initiated directly by the reconstructed NiOOH species. Density functional theory (DFT) calculations prove that the urea molecular are preferential absorbed on Ni site and then collaborate with the adjacent Mo site to carry out the subsequently dehydrogenation, N-N coupling, and desorption in energetically favorable pathways, proving their dual site mechanism (synergy between Mo and Ni).

Adjacent Fe-Pt atomic site synergistically boosting wearable biosensor performance in sweat analysis

Wearable electrochemical sensors have enormous potential in real-time and continuous monitoring of an individual’s physiological and biological state. In electrocatalysis, single-atom catalysts (SACs) with Fe-N4 active centers are attracting interest for their nearly complete metal utilization rate and unique unsaturated coordination configuration. Yet, their reliance on a single active site leads to a fixed adsorption mode for oxygen intermediates such as OH, greatly constraining design flexibility and catalytic performance. This study explores the synergistic effects between Fe-N4 and Pt-N4 active sites and their impact on the electrocatalytic activity towards uric acid (UA) and dopamine (DA). Proximal Pt-N4 atoms facilitate the activation of OH species on the Fe-N4 site and modulate the rehybridization of Fe d orbitals, thereby enhancing the adsorption of oxygen intermediates. This mechanism accelerates the overall electrocatalytic process for both UA and DA. Moreover, a non-swelling double network hydrogel is designed by combining chitosan with the P(AA-MEA)-Fe network. As a practical application, the non-swelling hydrogel channel, when combined with FeN4/PtN4 catalyst, successfully achieves real-time on-site detection of skin sweat biomarkers.

Geometric constraints regulated regioselectivity: Pd-catalyzed α-deuteration of pyridines with secondary phosphine oxide.

A Pd-catalyzed regioselective H/D exchange at the α-position of pyridines was achieved by employing secondary phosphine oxide as an internal base. The proposed five-membered structure enabled the reaction to overcome its conventional ortho-directing feature, allowing the efficient deuteration of pyridines and quinolines at adjacent sites of N-atoms.