Halogen doped graphene quantum dots modulate TDP-43 phase separation and aggregation in the nucleus.

TDP-43 is implicated in the dynamic formation of nuclear bodies and stress granules through phase separation. In diseased states, it can further condense into pathological aggregates in the nucleus and cytoplasm, contributing to the onset of amyotrophic lateral sclerosis. In this study, we evaluate the effect of graphene quantum dots (GQDs) with different functional groups on TDP-43's phase separation and aggregation in various cellular locations. We find that halogen atom-doped GQDs (GQDs-Cl, Cl-GQDs-OH) penetrate the nuclear envelope, inhibiting the assembly of TDP-43 nuclear bodies and stress granules under oxidative stress or hyperosmotic environments, and reduce amyloid aggregates and disease-associated phosphorylation of TDP-43. Mechanistic analysis reveals GQDs-Cl and Cl-GQDs-OH modulate TDP-43 phase separation through hydrophobic and electrostatic interactions. Our findings highlight the potential of GQDs-Cl and Cl-GQDs-OH in modulating nuclear protein condensation and pathological aggregation, offering direction for the innovative design of GQDs to modulate protein phase separation and aggregation.

Synergistic Effects of Amine Functional Groups and Enriched-Atomic-Iron Sites in Carbon Dots for Industrial-Current-Density CO2 Electroreduction.

Metal phthalocyanine molecules with Me-N4 centers have shown promise in electrocatalytic CO2 reduction (eCO2R) for CO generation. However, iron phthalocyanine (FePc) is an exception, exhibiting negligible eCO2R activity due to a higher CO2 to *COOH conversion barrier and stronger *CO binding energy. Here, amine functional groups onto atomic-Fe-rich carbon dots (Af-Fe-CDs) are introduced via a one-step solvothermal molecule fusion approach. Af-Fe-CDs feature well-defined Fe-N4 active sites and an impressive Fe loading (up to 8.5 wt%). The synergistic effect between Fe-N4 active centers and electron-donating amine functional groups in Af-Fe-CDs yielded outstanding CO2-to-CO conversion performance. At industrial-relevant current densities exceeding 400 mA cm-2 in a flow cell, Af-Fe-CDs achieved >92% selectivity, surpassing state-of-the-art CO2-to-CO electrocatalysts. The in situ electrochemical FTIR characterization combined with theoretical calculations elucidated that Fe-N4 integration with amine functional groups in Af-Fe-CDs significantly reduced energy barriers for *COOH intermediate formation and *CO desorption, enhancing eCO2R efficiency. The proposed synergistic effect offers a promising avenue for high-efficiency catalysts with elevated atomic-metal loadings.

Aminated graphene quantum dots/CdS nanobelts for enhanced photocatalytic degradation of RhB dye under visible light.

CdS nanoparticles have wide applications as photocatalysts for degradation of organic pollutants, but due to their limited turnover number and off-pathway charge recombination processes, their degradation efficiency is low. Herein, aminated graphene quantum dots/CdS (GQDs/CdS) nanobelts were successfully fabricated by solvothermal and hydrothermal processes. The prepared GQDs/CdS were characterized by physical methods to investigate their structure, morphology, optical properties, specific surface area, element composition, and chemical state. GQDs/CdS materials promoted efficient charge separation, and showed high efficiency in the photocatalytic degradation of the organic dye Rhodamine B (RhB) under visible light. The degradation efficiency of RhB samples over 0.05 g of catalysts reached 97.40% after 150 min, a much higher efficiency in comparison to pure CdS. Electron paramagnetic resonance (EPR) spectroscopy provided direct evidence for ˙OH and ˙O2- as the reactive oxidative species using DMPO as a spin trap. Consistent with the experimental results, a possible mechanism of RhB photocatalytic degradation by GQDs/CdS under visible light was proposed. This work may provide environmentally friendly photocatalysts for degrading organic dyes and purifying water.

Gram-Scale Mechanochemical Synthesis of Atom-Layer MoS2 Semiconductor Electrocatalyst via Functionalized Graphene Quantum Dots for Efficient Hydrogen Evolution.

The development of advanced and efficient synthetic methods is pivotal for the widespread application of 2D materials. In this study, a facile and scalable solvent-free mechanochemical approach is approached, employing graphene quantum dots (GQDs) as exfoliation agents, for the synthesis and functionalization of nearly atom-layered MoS2 nanosheets (ALMS). The resulting ALMS exhibits an ultrathin average thickness of 4 nm and demonstrates high solvent stability. The impressive yield of ALMS reached 63%, indicating its potential for scalable production of stable nanosheets. Remarkably, the ALMS catalyst exhibits excellent HER performance. Moreover, the ALMS catalyst showcases exceptional long-term durability, maintaining stable performance for nearly 200 h, underscoring its potential as a highly efficient and durable electrocatalyst. Significantly, the catalytic properties of ALMS are significantly influenced by ball milling production conditions. The GQD-assisted large-scale machinery synthesis pathway provides a promising avenue for the development of efficient and high-performance ultrathin 2D materials.

Amide Covalent Bonding Engineering in Heterojunction for Efficient Solar-Driven CO2 Reduction.

Inefficient charge separation and slow interfacial reaction dynamics significantly hamper the efficiency of photocatalytic CO2 reduction. Herein, a facile EDC/NHS-assisted linking strategy was developed to enhance charge separation in heterojunction photocatalysts. Using this approach, we successfully synthesized amide-bonded carbon quantum dot-g-C3N4 (CQD-CN) heterojunction photocatalysts. The formation of amide covalent bonds between CN and CQDs in the CN-CQD facilitates efficient carrier migration, CO2 adsorption, and activation. Exploiting these advantages, the CN-CQD photocatalysts exhibit high selectivity with CO and CH4 evolution rates of 79.2 and 2.7 µmol g-1 h-1, respectively. These rates are about 1.7 and 3.6 times higher than those of CN@CQD and bulk CN, respectively. Importantly, the CN-CQD photocatalysts demonstrate exceptional stability, even after 12 h of continuous testing. The presence of the COOH* signal is identified as a crucial intermediate species in the conversion of CO2 to CO. This study presents a covalent bonding engineering strategy for developing high-performance heterojunction photocatalysts for efficient solar-driven reduction of CO2.

Graphene Quantum Dot-Mediated Atom-Layer Semiconductor Electrocatalyst for Hydrogen Evolution.

The hydrogen evolution reaction performance of semiconducting 2H-phase molybdenum disulfide (2H-MoS2) presents a significant hurdle in realizing its full potential applications. Here, we utilize theoretical calculations to predict possible functionalized graphene quantum dots (GQDs), which can enhance HER activity of bulk MoS2. Subsequently, we design a functionalized GQD-induced in-situ bottom-up strategy to fabricate near atom-layer 2H-MoS2 nanosheets mediated with GQDs (ALQD) by modulating the concentration of electron withdrawing/donating functional groups. Experimental results reveal that the introduction of a series of functionalized GQDs during the synthesis of ALQD plays a crucial role. Notably, the higher the concentration and strength of electron-withdrawing functional groups on GQDs, the thinner and more active the resulting ALQD are. Remarkably, the synthesized near atom-layer ALQD-SO3 demonstrate significantly improved HER performance. Our GQD-induced strategy provides a simple and efficient approach for expanding the catalytic application of MoS2. Furthermore, it holds substantial potential for developing nanosheets in other transition-metal dichalcogenide materials.

Functional Group Modulation in Carbon Quantum Dots for Accelerating Photocatalytic CO2 Reduction.

This study investigates the mechanism behind the enhanced photocatalytic performance of carbon quantum dot (CQD)-induced photocatalysts. Red luminescent CQDs (R-CQDs) were synthesized using a microwave ultrafast synthesis strategy, exhibiting similar optical and structural properties but varying in surface functional group sites. Model photocatalysts were synthesized by combining R-CQDs with graphitic carbon nitride (CN) using a facile coupling technique, and the effects of different functionalized R-CQDs on CO2 reduction were investigated. This coupling technique narrowed the band gap of R1-CQDs/CN, made the conduction band potentials more negative, and made photogenerated electrons and holes less likely to recombine. These improvements greatly enhanced the deoxygenation ability of the photoinduced carriers, increased light absorption of solar energy, and raised the carrier concentration, resulting in excellent stability and remarkable CO production. R1-CQDs/CN demonstrated the highest photocatalytic activity, with CO production up to 77 µmol g-1 within 4 h, which is approximately 5.26 times higher than that of pure CN. Our results suggest that the superior photocatalytic performance of R1-CQDs/CN arises from its strong internal electric field and high Lewis acidity and alkalinity, attributed to the abundant pyrrolic-N and oxygen-containing surface groups, respectively. These findings offer a promising strategy for producing efficient and sustainable CQD-based photocatalysts to address global energy and environmental problems.

Solvent Engineering of Oxygen-Enriched Carbon Dots for Efficient Electrochemical Hydrogen Peroxide Production.

The development of cost-effective and reliable metal-free carbon-based electrocatalysts has gained significant attention for electrochemical hydrogen peroxide (H2 O2 ) generation through a two-electron oxygen reduction reaction. In this study, a scalable solvent engineering strategy is employed to fabricate oxygen-doped carbon dots (O-CDs) that exhibit excellent performance as electrocatalysts. By adjusting the ratio of ethanol and acetone solvents during the synthesis, the surface electronic structure of the resulting O-CDs can be systematically tuned. The amount of edge active CO group was strongly correlated with the selectivity and activity of the O-CDs. The optimum O-CDs-3 exhibited extraordinary H2 O2 selectivity of up to 96.55% (n = 2.06) at 0.65 V (vs RHE) and achieved a remarkably low Tafel plot of 64.8 mV dec-1 . Furthermore, the realistic H2 O2 productivity yield of flow cell is measured to be as high as 111.18 mg h-1  cm-2 for a duration of 10 h. The findings highlight the potential of universal solvent engineering approach for enabling the development of carbon-based electrocatalytic materials with improved performance. Further studies will be undertaken to explore the practical implications of the findings for advancing the field of carbon-based electrocatalysis.

Graphene Quantum Dots Modulate Stress Granule Assembly and Prevent Abnormal Phase Transition of Fused in Sarcoma Protein.

Protein liquid-liquid phase separation (LLPS) plays a crucial role in mediating dynamic assembly of different membraneless organelles such as stress granules (SGs). Dysregulation of dynamic protein LLPS leads to aberrant phase transition and amyloid aggregation which is closely associated with neurodegenerative diseases. In this study, we found that three types of graphene quantum dots (GQDs) exhibit potent activity in preventing SG formation and promoting SG disassembly. We next demonstrate that GQDs can directly interact with the SGs-containing protein fused in sarcoma (FUS), inhibit and reverse FUS LLPS, and prevent its abnormal phase transition. Moreover, GQDs display superior activity in preventing amyloid aggregation of FUS and disaggregating preformed FUS fibrils. Mechanistic study further demonstrates that GQDs with different edge-site exhibit distinct binding affinity to FUS monomers and fibrils, which accounts for their distinct activities in modulating FUS LLPS and fibrillation. Our work reveals the potent capability of GQDs in modulating SG assembly, protein LLPS, and fibrillation and sheds light on rational design of GQDs as effective modulators of protein LLPS for therapeutics application.

Insights into the Use of Te-O Pairs as Active Centers of Carbon Nanosheets for Efficient Electrochemical Oxygen Reduction.

Previous theoretical calculations have predicted that the incorporation of tellurium (Te) into carbon materials can significantly enhance their catalytic activity. Nevertheless, the experimental realization of efficient Te-doped carbon materials remains challenging. Here, we employed theoretical calculations to deduce the possible structure of Te-doped carbon materials. Our findings unveil that the formation of Te-O pairs in carbon materials with a relatively low oxygen coordination microenvironment can impart strong electron-donating capabilities, thereby boosting the electrocatalytic activity of oxygen reduction reaction (ORR). To verify our theoretical predictions, we synthesized Te-O pair-doped carbon materials using a tandem hydrothermal dehydration-pyrolysis strategy. This approach enabled efficient infiltration of Te into carbon materials. Our unconventional Te-O pair-doped carbon materials exhibit expanded interlayer distances and graphene-like nanosheet architectures, which provide enlarged active areas. These structural features contribute to the enhanced ORR catalytic performance of the as-prepared carbon catalyst. Our findings provide molecular-level insights into the design of various carbon-based electrocatalysts with binary-heteroatom-doped active sites.

Rational Design of Nitrogen-Doped Carbon Dots for Inhibiting ß-Amyloid Aggregation.

The fibrillization and abnormal aggregation of ß-amyloid (Aß) peptides are commonly recognized risk factors for Alzheimer's disease (AD) brain, and require an effective strategy to inhibit the Aß deposition and treat AD. Herein, we designed and synthesized nitrogen-doped carbon dots (N-CDs) as an Aß-targeted probe, which exhibits the capacity of inhibiting the 1-42 Aß (Aß1-42) self-assembly in vitro. The N-CDs exhibited orange emission with an emission wavelength of 570 nm, which demonstrates their excellent optical properties with excitation-independent behavior. Meanwhile, the N-CDs have spherical morphologies with an average size of 2.2 nm, whose surface enriches the amino, carboxyl, and hydroxyl groups. These preparties are conducive to improving their biological water solubility and provide a large number of chemical bonds for further interaction with proteins. Contrary to this, the kinetic process, size evolutions, and morphologies changes of Aß1-42 were inhibited in the presence of N-CDs in the determination of a thioflavin T assay, dynamic light scattering, transmission electron microscope, etc. Finally, the safety application of N-CDs on Aß1-42-induced cytotoxicity was further demonstrated via in vitro cytotoxicity experiments. This work demonstrates the effective outcome of suppressing Aß aggregation, which provides a new view into the high-efficiency and low-cytotoxicity strategy in AD theranostics.

Surface state engineering of carbon dot/carbon nanotube heterojunctions for boosting oxygen reduction performance.

Platinum-based (Pt) catalysts are the most common commercial catalysts for oxygen reduction reactions (ORR). Unfortunately, their high price, scarcity and poor durability hinder their further development. Therefore, the development of effective and economical ORR electrocatalysts has received increasing attention. Here, carbon dots (CDs) enriched in amino functional groups were successfully loaded onto carbon nanotubes (CNTs) with a large surface area and helical structure through a surface state engineering strategy. The resulting composites (CD/CNTs) are 0D/1D nano heterojunction structures. The CD/CNTs showed superior ORR activity compared with CNTs and CDs (Eoneset = 0.95 V, E1/2 = 0.81 V and limiting current density = 4.74 mA cm-2). In addition, the stability of CD/CNTs in an alkaline medium was up to 30000 s. The excellent ORR performance of CD/CNTs can be attributed to the dominant role of amino-N, the synergistic effect of heterojunctions formed by CDs and CNTs, and the high Lewis basicity. The composite electrocatalyst synthesized by the CD-regulated CNT strategy is expected to be a reliable cathode candidate for future energy conversion devices.

Isolated transition metal nanoparticles anchored on N-doped carbon nanotubes as scalable bifunctional electrocatalysts for efficient Zn-air batteries.

Accelerating the sluggish anode reaction in a Zn-air battery can improve its energy efficiency, but the large-scale development of this battery is hindered by the lack of bifunctional catalysts. Herein, we designed a one-step carbonization strategy for synthesizing monodispersed Co nanoparticles supported on N-doped carbon nanotube (Co/CNT), which shows excellent bifunctional electrocatalytic performance with long-term durability for oxygen reduction reaction/oxygen evolution reaction. The formation of carbon substrates from the carbonization of nitrogenous organic molecules are benefit to capture more Co nanoparticles though strong metal-substrate interaction, then construct high-density effective active sites of the Lewis base for accelerating the electrocatalytic reaction process. To verify its superior performance, a rechargeable Zn-air battery with a Co/CNT air electrode was subsequently constructed. The battery exhibits an open-circuit voltage of 1.41 V and a specific discharge capacity of 835.2 mAh/gZn, which can be continuously charged and discharged with good cycle stability. Our study provides a new strategy for developing various practical carbon-based non-noble metallic bifunctional electrocatalysts with promising performance in electrocatalysis and batteries to achieve the target of carbon neutrality.

Elastic Buffering Layer on CuS Enabling High-Rate and Long-Life Sodium-Ion Storage.

The latest view suggests the inactive core, surface pulverization, and polysulfide shuttling effect of metal sulfides are responsible for their low capacity and poor cycling performance in sodium-ion batteries (SIBs). Whereas overcoming the above problems based on conventional nanoengineering is not efficient enough. In this work, erythrocyte-like CuS microspheres with an elastic buffering layer of ultrathin polyaniline (PANI) were synthesized through one-step self-assembly growth, followed by in situ polymerization of aniline. When CuS@PANI is used as anode electrode in SIBs, it delivers high capacity, ultrahigh rate capability (500 mAh g-1 at 0.1 A g-1, and 214.5 mAh g-1 at 40 A g-1), and superior cycling life of over 7500 cycles at 20 A g-1. A series of in/ex situ characterization techniques were applied to investigate the structural evolution and sodium-ion storage mechanism. The PANI swollen with electrolyte can stabilize solid electrolyte interface layer, benefit the ion transport/charge transfer at the PANI/electrolyte interface, and restrain the size growth of Cu particles in confined space. Moreover, finite element analyses and density functional simulations confirm that the PANI film effectively buffers the volume expansion, suppresses the surface pulverization, and traps the polysulfide.

Construction of Co,N-Coordinated Carbon Dots for Efficient Oxygen Reduction Reaction.

For the sake of the oxygen reduction reaction (ORR) catalytic performance, carbon dots (CDs) doped with metal atoms have accelerated their local electron flow for the past few years. However, the influence of CDs doped with metal atoms on binding sites and formation mechanisms is still uncertain. Herein, Co,N-doped CDs were facilely prepared by the low-temperature polymerization-solvent extraction strategy from EDTA-Co. The influence of Co doping on the catalytic performance of Co-CDs was explored, mainly in the following aspects: first, the pyridinic N atom content of Co-CDs significantly increased from 4.2 to 11.27 at% compared with the CDs, which indicates that the Co element in the precursor is advantageous in forming more pyridinic-N-active sites for boosting the ORR performance. Second, Co-CDs are uniformly distributed on the surface of carbon black (CB) to form Co-CDs@CB by the facile hydrothermal route, which can expose more active sites than the aggregation status. Third, the highest graphite N content of Co-CDs@CB was found, by limiting the current density of the catalyst towards the ORR. Composite nanomaterials formed by Co and CB are also used as air electrodes to manufacture high-performance zinc-air batteries. The battery has good cycle stability and realizes stable charges and discharges under different current densities. The outstanding catalytic activity of Co-CDs@CB is attributed to the Co,N synergistic effect induced by Co doping, which pioneer a new metal doping mechanism for gaining high-performance electrocatalysts.

Stabilization of crystal and interfacial structure of Ni-rich cathode material by vanadium-doping.

Stable structure and interface of nickel-rich metal oxides is crucial for practical application of next generation lithium-ion batteries with high energy density. Bulk doping is the promising strategy to improve the structural and interfacial stability of the materials. Herein, we report the impact of vanadium-doping on the structure and electrochemical performance of LiNi0.88Co0.09Al0.03O2 (NCA88). Vanadium doped in high oxidation state (+5) would lead to alteration of the crystal lattice and Li+/Ni2+ cation mixing. Those are the main factors determining the cycling and rate capability of the materials. With optimization of vanadium-doping, the preservation of the integrity of the secondary particles of the materials, the enhancement of the diffusion of Li+ ions, and alleviation of the side reactions of the electrolyte can be efficiently achieved. As a result, NCA88 doped with vanadium of 1.5 mol % can provide superior cycling stability with capacity retention of 84.3% after 250 cycles at 2C, and rate capability with capacity retention of 65.5% at 10C, as compared to the corresponding values of 58.6% and 55% for the pristine counterpart, respectively. The results might be helpful to the selection of dopants in the design of the nickel-rich materials.

Femoral artery aneurysm with large hematoma from Pasteurella: case report and literature review.

BACKGROUND: Pasteurella multocida is a well-known gram-negative facultative anaerobe well known for its ability to cause soft tissue infections following animal bite or scratch. Here we present a case with mycotic aneurysm of the superficial femoral artery due to P. multocida infection. CASE PRESENTATION: A 62 year old male patient presented with worsening right leg pain and swelling. On examination, he was found to have profound swelling and erythema of the right medial thigh and tenderness to palpation. Computerized tomography showed findings suggestive of right femoral pseudoaneurysm with a large right medial thigh hematoma. Blood cultures grew P. multocida. Patient underwent emergent open resection of the mycotic aneurysm and vascular bypass surgery. Intraoperatively, the site was noted to be grossly infected with multiple pockets of pus which were drained and pus cultures grew P. multocida. The diagnosis of P. multocida bacteremia with right femoral mycotic aneurysm and thigh abscess was made. Patient received 6 weeks of intravenous ceftriaxone and recovered. CONCLUSION: Our case is the first report on infection of peripheral vessel with Pasteurella and highlights the importance of prompt surgical intervention and effective antibiotic treatment.

Amine-Functionalized Carbon Nanodot Electrocatalysts Converting Carbon Dioxide to Methane.

The electrochemical conversion of carbon dioxide (CO2 ) to methane (CH4 ), which can be used not only as fuel but also as a hydrogen carrier, has drawn great attention for use in supporting carbon capture and utilization. The design of active and selective electrocatalysts with exceptional CO2 -to-CH4 conversion efficiency is highly desirable; however, it remains a challenge. Here a molecular tuning strategy-in situ amine functionalization of nitrogen-doped graphene quantum dots (GQDs) for highly efficient CO2 -to-CH4 conversion is presented. Amine functionalized nitrogen-doped GQDs achieve a CH4 Faradic efficiency (FE) of 63% and 46%, respectively, at CH4 partial current densities of 170 and 258 mA cm-2 , approximating to or even outperforming state-of-the-art Cu-based electrocatalysts. These GQDs also convert CO2 to C2 products mainly including C2 H4 and C2 H5 OH with a maximum FE of ≈10%. A systematic analysis reveals that the CH4 yield varies linearly with amine group content, whereas the C2 production rate is positively dependent on pyridinic N dopant content. This work provides insight into the rational design of carbon catalysts with CO2 -to-CH4 conversion efficiency at the industrially relevant level.

Regulation of functional groups on graphene quantum dots directs selective CO2 to CH4 conversion.

A catalyst system with dedicated selectivity toward a single hydrocarbon or oxygenate product is essential to enable the industrial application of electrochemical conversion of CO2 to high-value chemicals. Cu is the only known metal catalyst that can convert CO2 to high-order hydrocarbons and oxygenates. However, the Cu-based catalysts suffer from diverse selectivity. Here, we report that the functionalized graphene quantum dots can direct CO2 to CH4 conversion with simultaneous high selectivity and production rate. The electron-donating groups facilitate the yield of CH4 from CO2 electro-reduction while electron-withdrawing groups suppress CO2 electro-reduction. The yield of CH4 on electron-donating group functionalized graphene quantum dots is positively correlated to the electron-donating ability and content of electron-donating group. The graphene quantum dots functionalized by either -OH or -NH2 functional group could achieve Faradaic efficiency of 70.0% for CH4 at -200 mA cm-2 partial current density of CH4. The superior yield of CH4 on electron-donating group- over the electron-withdrawing group-functionalized graphene quantum dots possibly originates from the maintenance of higher charge density of potential active sites (neighboring C or N) and the interaction between the electron-donating group and key intermediates. This work provides insight into the design of active carbon catalysts at the molecular scale for the CO2 electro-reduction.

Classification and review of free PCR primer design software.

MOTIVATION: Polymerase chain reaction (PCR) has been a revolutionary biomedical advancement. However, for PCR to be appropriately used, one must spend a significant amount of effort on PCR primer design. Carefully designed PCR primers not only increase sensitivity and specificity, but also decrease effort spent on experimental optimization. Computer software removes the human element by performing and automating the complex and rigorous calculations required in PCR primer design. Classification and review of the available software options and their capabilities should be a valuable resource for any PCR application. RESULTS: This article focuses on currently available free PCR primer design software and their major functions (https://pcrprimerdesign.github.io/). The software are classified according to their PCR applications, such as Sanger sequencing, reverse transcription quantitative PCR, single nucleotide polymorphism detection, splicing variant detection, methylation detection, microsatellite detection, multiplex PCR and targeted next generation sequencing, and conserved/degenerate primers to clone orthologous genes from related species, new gene family members in the same species, or to detect a group of related pathogens. Each software is summarized to provide a technical review of their capabilities and utilities.