Archive for the ‘Community Board Picks’ Category

Time’s dance with gold: tracking the isomeric fluctuations of Au clusters

Face-centered cubic (fcc) metals, such as Au and Ag, usually adopt a packed crystal structure in bulk. However, the equilibrium structure could differ when only a handful of atoms compose a nanocluster. Theories have predicted that particles less than a few nanometers would favor a decahedral packing with a five-fold symmetry; when even fewer atoms are present, say less than two hundred, a 20-fold icosahedral packing would become the lowest-energy configuration. Such fluctuations of the nuclei/seeds may have played a critical role in defining the shape of colloidal nanoparticles in many wet chemical syntheses.

In recent work, a cross-institutional team led by Richard E. Palmer and Thomas J. A. Slater reported the direct observation of such fluctuations on a nearly second-by-second basis. The team synthesized Au nanoclusters containing 309±15 atoms on an amorphous carbon film through mass-selected magnetron sputtering. Subsequently, aberration-corrected scanning transmission electron microscopy (STEM) was employed to track the atomic structures of Au nanoclusters with a frame rate of 0.4–0.7 per second (Fig. 1). To identify the cluster type in each frame, the team compared them to a collection of simulated images with different cluster structures and tilt angles. The clusters exhibited highly dynamic switching between decahedral, icosahedral, and single-crystalline structures under the electron beam, which is sufficiently strong to overcome the energy barriers between such transitions.

Fig. 1 Au309±15 clusters fluctuating under the electron beam. High-angle annular dark field (HAADF) imaging on an aberration-corrected scanning transmission electron microscope (STEM) resolved the atomic structure of these Au nanoclusters frame by frame. Adapted from the supporting data DOI: 10.5281/zenodo.10522408, CC-BY 4.0.

 

Notably, the authors showed that the Au309±15 clusters favor the decahedral structure the most, followed by icosahedral and then single-crystalline structures (Fig. 2a). This result is consistent with the probabilities obtained from a snapshot of an ensemble. In theory, the lower-energy structures would have a higher probability of appearance. The ranking of isomeric preferences observed in this study indicates that the cluster size is within a range where the energy ranks in fcc > icosahedral > decahedral (Fig. 2b). Taken together, this work illustrates the possibility of atomic-resolution electron microscopy, when combined with image simulations, to track the isomeric evolution of metal nanoclusters and may shed light on how we understand and regulate nanostructures with atomic precision.

Fig. 1 (a) Histogram of isomer abundances from dynamic movies compared with a static image of a cluster ensemble. Reproduced from DOI: 10.1039/D3NH00291H with permission from the Royal Society of Chemistry. (b) Schematic energy landscape of cluster structures for fcc metals. A red shade indicates the cluster size range in the current study. Ih: icosahedral. Dh: decahedral. Adapted from DOI: 10.1002/anie.202015166 with permission from Wiley-VCH.

 

To find out more, please read:

Frame-by-frame observations of structure fluctuations in single mass-selected Au clusters using aberration-corrected electron microscopy
Malcolm Dearg, Cesare Roncaglia, Diana Nelli, El Yakout El Koraychy, Riccardo Ferrando, Thomas J. A. Slater, and Richard E. Palmer
Nanoscale Horiz., 2024, 9, 143-147

 


About the blogger


 

Jingshan S. Du is a Washington Research Foundation Postdoctoral Fellow at Pacific Northwest National Laboratory and a member of the Nanoscale Horizons Community Board. His research spans crystal formation and transformation pathways, in situ electron microscopy, and hybrid organic/inorganic nanostructures. Du received a Ph.D. in Materials Science and Engineering from Northwestern University in 2021. At Northwestern, he worked on complex nanoparticle systems, correlative electron microscopy of hybrid nanostructures, and nanoscale thermodynamics. Du received a Certificate for Management for Scientists and Engineers from Northwestern’s Kellogg School of Management in 2021 and a B.Sc. in Engineering from Zhejiang University Chu Kochen Honors College in 2015. You can follow him on Twitter @JingshanDu.

The views expressed in this article do not necessarily reflect those of the author’s employer or the US government.

 

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Injectable hydrogel reinforces cancer immunotherapy

In the last few years, immunotherapy has paved new paths for effective treatment of different cancers. Specifically, immunotherapy stimulates T cells, a type of white blood cell called lymphocytes that help to fight germs and destroy tumours. Immunotherapy can be used as a monotherapy or combined with chemotherapy and surgery. Unfortunately, cancer cells and their microenvironment have many sophisticated defence mechanisms that pose considerable challenges to immunotherapy effectiveness and progress. Current strategies to boost cancer immunotherapy include increasing the infiltration of T cells at the tumour site or blocking immune checkpoint-producing immune evasion.

In this regard, an exciting immunotherapy combination approach has been developed by Guixiang Xu and team based on an injectable hydrogel as a carrier to deliver a drug called linagliptin which is capable of inhibiting dipeptidyl peptidases 4 (DPP4) degradation. This leads to prolonged half-life of CXCL10 chemokines and thus, increases recruitment of T cells in the tumour site. Small molecule immune checkpoint blocker (BMS-202) particles were also loaded onto the developed drug carrier to block the programmed cell death-ligand (PD-L1), avoiding immune evasion. The team demonstrated that the application of hydrogel construct (S@LB) suppresses chemokine CXCL10 degradation, increasing T-cell infiltration, while BMS-202 particles inactivate PD-L1 checkpoint in vivo.

Fig. 1 Preparation and mechanism scheme of S@LB. (A) The preparation process of the S@LB solution. (B) Schematic illustration of an injectable hydrogel to reinforce cancer immunotherapy by promoting infiltration of T cells and regulating immune evasion. Reproduced from DOI: 10.1039/D3NH00401E with permission from the Royal Society of Chemistry.

The team tested the in vivo anti-tumour ability, immune response, and lung anti-metastatic effect of the S@LB in combination with chemotactic CXCL10 (S@LB + CXCL10). Their recent report shows that after 18 days of tumour removal, an immune memory effect was detected for the group treated with S@LB + CXCL10.

Overall, this study shows how nano-based hydrogel immunotherapy can be used as an innovative “weapon” against primary and distant tumours, along with efficient inhibition of lung metastasis, indicating tremendous potential for developing transformative clinical applications.

 

To find out more, please read:

Hydrogel-mediated tumor T cell infiltration and immune evasion to reinforce cancer immunotherapy
Guixiang Xu, Kai Liu, Xiangwu Chen, Yang Lin, Cancan Yu, Xinxin Nie, Wenxiu He, Nathan Karinc and  Yuxia Luan
Nanoscale Horiz., 2024, Advance Article

 


About the blogger


 

Susel Del Sol Fernández is a Marie Skłodowska-Curie Postdoctoral fellow at Aragon Nanoscience and Materials Institute (INMA-CSIC), Spain and a member of the Nanoscale Horizons Community Board. Dr Del Sol’s research focuses on designing smart functionalized magnetic nanoparticles for biomedical applications, including magnetic-optical hyperthermia treatment and magnetogenetics. You can follow her on X @SuselDelSol

 

 

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Measuring Carrier Density and Mobility in Single-Walled Carbon Nanotubes via Nuclear Magnetic Resonance

The rapidly expanding energy and computing sectors are driving demand for high-performance semiconductor materials. Organic Semiconductors (OSCs) have emerged as attractive candidates for opto-electronic devices, thanks to their high carrier mobility, stability and tunability. However, accurate and independent quantification of charge carrier density and mobility has been an ongoing challenge in the OSC community. Working to overcome this challenge, recent research by Hermosilla-Palacios et al. presents a novel method for determining charge carrier characteristics in semiconducting single-walled carbon nanotubes (s-SWCNTs), a subtype of OSCs.

In this study, a nuclear magnetic resonance (NMR)-based approach is proposed to directly quantify charge carrier density and indirectly quantify carrier mobility (Fig. 1). The study puts forward a combined method utilizing 19F NMR and optical absorption measurements on s-SWCNTs in the presence of F-containing molecular dopants. The researchers demonstrated that changes in carrier density affect charge delocalization, resulting in a carrier density-dependent mobility, in contrary to that expected for mobility limited by ionized impurity scattering. This combined approach simplifies the measurement of carrier density in doped s-SWCNTs, constituting a valuable tool to the OSC community.

 

Fig. 1 (a) Cartoon showing the NMR tube sample composition: polymer dispersed s-SWCNT, excess polymer (in blue) and DDB-F72 molecules associated with a hole on the doped s-SWCNTs. Repeating unit of the polymer PF-PD is also presented for clarity. (b) Spectra corresponding to 19F NMR for neutral DDB-F72 dopant in d8-toluene (6 mM, bottom), PF-PD polymer used to disperse s-SWCNTs with added DDB-F72 (6 mM, middle), and dispersed s-SWCNTs with added DDB-F72 (6 mM, top). Numbers show specific chemical shift. (c) Spectra corresponding to 19F NMR for doping series of s-SWCNT. Spectra are arbitrarily displaced along the y axis to show the different doping steps clearly. Lower dopant concentration (red) to higher dopant concentrations (blue). Reproduced from DOI: 10.1039/D3NH00480E with permission from the Royal Society of Chemistry.

While this study presents significant strides in measuring carrier density in s-SWCNTs, whether it can be effectively applied to a wide range of OSCs beyond s-SWCNTs remains to be seen. It should also be noted that the downfield shift observed with increasing dopant concentration may be complicated by factors other than charge delocalization of the hole distribution, such as dopant binding dynamics. The mechanistic origin of the chemical shift changes in the presence of dopants with NMR -active nuclei may refine our understanding of the local micro-environment around the redox-doped s-SWCNTs, prompting further investigations in this area.

In summary, this study develops an NMR-based method to quantify charge carrier density in s-SWCNTs and illustrates that the hole mobility in doped s-SWCNT networks increases with growing carrier density. The ability to tune, quantify, and optimize carrier density opens new avenues for applications such as photovoltaics, sensors, light-emitting diodes, field-effect transistors, and thermoelectric devices. The method’s potential applicability to various p-conjugated semiconductors using suitable NMR-active dopants makes it a versatile tool for the field. As the scientific community embraces this innovative approach, it heralds a new chapter in the design and development of high-performance semiconductor materials.

 

To find out more, please read:

Carrier density and delocalization signatures in doped carbon nanotubes from quantitative magnetic resonance
M. Alejandra Hermosilla-Palacios, Marissa Martinez, Evan A. Doud, Tobias Hertel, Alexander M. Spokoyny, Sofie Cambré, Wim Wenseleers, Yong-Hyun Kim, Andrew J. Ferguson and Jeffrey L. Blackburn
Nanoscale Horiz., 2024, Advance Article

 


About the blogger


 

Albert Liu is an Assistant Professor at the University of Michigan, and a member of the Nanoscale Horizons Community Board. Prof. Liu’s research group studies the effects of micro-confinement in nano-structured low dimensional materials, to address challenges in sustainability, robotics, and healthcare. You can follow Albert on Twitter @Albert_T_Liu

 

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NIR-triggered multifunctional CuS-embedded nanogels for advanced chronic wounds therapy

Chronic wounds are considered a major healthcare problem all over the world. Long-term infections and/or suppressed immune responses may cause chronic wounds with slower healing, resulting in increased mortality. Although antibiotics, skin disinfectants, and hydrogels are currently being used to combat microbial pathogenesis, they still have some significant limitations when used in clinical wound healing. Therefore, researchers have been exploring alternative approaches, such as combining antimicrobial, antioxidant, and anti-inflammatory agents for advanced chronic wound therapy.

Recently, nanomaterial-based antimicrobials have gained popularity thanks to catalytic and near-infrared (NIR) irradiation treatments, which induce controlled oxidative stress (photodynamic and catalytic therapies) and hyperthermia (photothermal therapies) to eradicate bacteria. However, little research into nanomaterial-based antimicrobial activity against biofilms and chronic wound healing in vivo has previously been reported.

Fig. 1 An overview of the properties of CuS/Qu–CNGs and their role in wound healing. Reproduced from DOI: 10.1039/D3NH00275F with permission from the Royal Society of Chemistry.

In this regard, an NIR-triggered multifunctional quercetin carbonized nanogel embedded with copper sulfide nanoclusters (CuS/Qu-CNG) was reported by Nain et al. for advanced therapy of chronic wounds. Polymerization and mild carbonation procedures were used to prepare quercetin carbonized nanogels (Qu-CNGs), which were subsequently used as templates to grow CuS in situ forming CuS/Qu-CNGs. The resulting CuS/Qu–CNGs are photoreactive and contain antioxidant and catalytic properties (oxidase- and peroxidase-like activities). As a result of their photo-responsive properties, CuS/Qu-CNGs significantly amplified their antimicrobial activity when exposed to NIR-II light. A CuS/Qu–CNGs MIC90 value of 6–9 mg mL-1 is ~125-fold lower than Qu or Qu–CNGs under NIR-II irradiation and was further improved by ~30-fold (ca. 0.2 mg mL-1) in the presence of H2O2. Besides, CuS/Qu-CNGs demonstrated exceptional penetration ability, eliminating MRSA biofilms caused by diabetic wounds in diabetic mice. By suppressing pro-inflammatory cytokines (IL-1β) and boosting anti-inflammatory cytokines (IL-10 and TGF-β1), CuS/Qu-CNGs significantly accelerated wound healing by promoting angiogenesis, epithelialization and collagen synthesis. Finally, CuS/Qu–CNGs showed superior in vivo efficacy in treating bacterial infections and enhancing wound healing in diabetic mice.

In summary, a “Three in One” multifunctional CuS/Qu-CNGs with excellent antimicrobial/antioxidative/anti-inflammatory properties demonstrate great potential in treating bacterial infections and promoting chronic wound healing. This work is expected to provide new solutions for wound treatment complicated by microbial pathogenesis.

 

To find out more, please read:

NIR-activated quercetin-based nanogels embedded with CuS nanoclusters for the treatment of drug-resistant biofilms and accelerated chronic wound healing
Amit Nain, Yu-Ting Tseng, Akash Gupta, Yu-Feng Lin, Sangili Arumugam, Yu-Fen Huang, Chih-Ching Huang and Huan-Tsung Chang
Nanoscale Horiz., 2023, 8, 1652-1664

 


About the blogger


 

Jiangjiexing Wu is an Associate Professor at Tianjin University and a member of the Nanoscale Horizons Community Board. Dr Wu’s research focuses on the rational design and synthesis of functional nanomaterials (such as nanozymes) for analytical, biomedical, and environmental applications.

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Defect engineering enhances CO2 reducing photocatalysts

Recycling CO2 molecules through photocatalysis represents an innovative technology to mitigate the emission of CO2 gas. The deliberate introduction of defects into a photocatalyst plays a crucial role in optimizing photocatalytic performance, since the defects regulate the electronic structure, fine-tune selectivity by enhancing catalytic activity, and reduce the activation barrier of the catalyst.

A team of researchers based in Australia have recently developed a photocatalytic system for CO production by CO2 reduction. In this study, defect-rich g-C3N4 serves as a semiconducting substrate, and it was further loaded with Ag nanoparticles (NPs) to act as a plasmonic source, resulting in the creation of the g-C3N4-Ag photocatalyst. The defects within the g-C3N4 were known as the active sites that enhance the efficiency of photocatalytic CO2 conversion. In addition, these defects are strategically positioned alongside the loaded Ag NPs, which improves the effectiveness of injected hot electrons from the Ag NPs, thereby synergistically enhancing the activity of photocatalytic CO2 reduction.

In the experiments involving defect-rich g-C3N4, different photodeposition times, including 10 minutes, 1 hour, 3 hours, and 5 hours, were performed to load Ag particles, denoted the as-preared photocatalyst as g-C3N4-Ag 10m, 1h, 3h, and 5h, respectively. These variants were evaluated for their photocatalytic performance in CO production via CO2 reduction (Fig. 1a). The optimal performance was achieved with g-C3N4-Ag 1h, and the production of CO was confirmed through isotopic experiments (Fig. 1b). The g-C3N4-Ag photocatalysts were characterized using scanning transmission electron microscopy, as typical image is presented in Fig. 1c and the corresponding elemental mapping were presented in Fig. 1d to 1g.

Fig 1. (a) CO production rate based on various g-C3N4 based photocatalysts. (b) Isotope labelling experiments tested under 13CO2 and 12CO2, and the mass spectrometry signals at m/z = 28 and m/z = 29 are 13CO and 12CO, respectively. (c) STEM dark field image and (d)–(g) elemental mapping of g-C3N4-Ag 1h catalyst. Scale bar: 300 nm. Reproduced from DOI: 10.1039/D3NH00348E with permission from the Royal Society of Chemistry.

To elucidate the mechanism behind the defect engineering scenario, Ag NPs were initially loaded onto g-C3N4 via photodeposition. Due to the electron-rich environment of the point defects on g-C3N4, Ag+ ions selectively grow on these defect sites. The resulting g-C3N4-Ag composite was subsequently annealed. During this process, the new defects formed on the g-C3N4 substrate owing to the strain induced by the differing thermal expansion rates between the Ag and g-C3N4. These new defects were found to be located around the Ag NPs, representing a significant change in the pristine g-C3N4 following the introduction of Ag.

Furthermore, density functional theory (DFT) calculations were conducted to gain a deeper understanding of how the defects in g-C3N4 improve performance. Three models of photocatalysts were considered, including pristine g-C3N4, g-C3N4 with N vacancies, and N vacancies in g-C3N4 with O sites on the surface. In the models of pristine g-C3N4 and g-C3N4 with N vacancies, the formation of *COOH intermediates was identified as the rate-limiting step (RDS), and moreover, N vacancies in g-C3N4 were found to enhance the activity in this conversion (Fig 2a). For N vacancies in g-C3N4 with additional surface O sites (Fig. 2b), the initial reaction step favored the formation of *COOH intermediates from a thermodynamic perspective. Subsequently, the reduction of *COOH intermediates to *CO species occurred by reacting with protons, releasing H2O molecules. In the case of O-enriched g-C3N4, this conversion became the RDS. DFT calculations indicated that the ΔG values for *COOH and *H to form *CO and H2O at the C defect active sites were 0.96 eV, which determined the reaction rate (Fig. 2c). These results provide insight into the reasons behind the improved performance in CO production through CO2 reduction.

Fig 2. Optimized configurations of reaction intermediates *COOH and *CO on the C atom and N vacancy active sites of (a) g-C3N4 with N vacancy and (b) N vacancies in g-C3N4 with O sites on the surface. (Red ball is oxygen atom, white ball is hydrogen atom, gray is carbon atom, and blue is nitrogen atom) (c) Gibbs free energy diagrams for photocatalytic CO2 reduction to CO on g-C3N4, g-C3N4 with N vacancy and O-occupied g-C3N4. Reproduced from DOI: 10.1039/D3NH00348E with permission from the Royal Society of Chemistry.

In summary, the deliberate introduction of active defects into g-C3N4 photocatalysts, strategically positioned near the plasmon centers of Ag NPs, optimizes the utilization efficiency of plasmonic hot electrons, resulting in an enhanced efficiency for CO2 photoreduction. Importantly, this strategy has the potential for extension to various systems based on polymers, hard materials, and hybrid materials, offering promising applications that harness the functionalities of defects in a wide range of fields.

 

To find out more, please read the full article:

Defect engineering enhances plasmonic-hot electrons exploitation for CO2 reduction over polymeric catalysts
Hang Yin, Zhehao Sun, Kaili Liu, Ary Anggara Wibowo, Julien Langley, Chao Zhang, Sandra E. Saji, Felipe Kremer, Dmitri Golberg, Hieu T. Nguyen, Nicholas Cox and Zongyou Yin
Nanoscale Horiz., 2023, Advance Article

 


About the blogger


Photo of Yuanxing Fang.

 

Yuanxing Fang is a Professor at Fuzhou University, and a member of the Nanoscale Horizons Community Board. Prof. Fang’s research lab focuses on the synthesis of metal-free semiconductors for photoelectrochemical systems for energy and environmental applications, including water splitting, hydrogen peroxide synthesis, organic transformations and others.

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Enhancing SERS activity with a pyroelectric-induced charge transfer effect

Surface-enhanced Raman scattering (SERS) is known to be driven by two mechanisms: electromagnetic enhancement (e.g., plasmon excitation) and chemical enhancement (e.g., charge transfer). Although numerous SERS substrates have been reported and commercialized, distinguishing between these two mechanisms and controlling their contributions in real time remains a significant challenge. The challenge arises from the difficulty of accurately estimating the contribution of charge transfer and the limited ability to adjust SERS enhancement once the substrate has been prepared.

Now, a team of Chinese researchers have developed pyroelectric-responsive SERS substrates by combining a pyroelectric material, Pb(Mg,Nb)O3-PbTiO3 (PMN-PT), with plasmonic silver nanoparticles (Ag NPs). Their strategy takes advantage of the pyroelectric effect, which converts temperature fluctuations into electricity, thus modifying the charge on the surface of the SERS substrates (Fig. 1). Heating the substrates (dT/dt > 0) generates a downward electric field on the substrate surface, whereas cooling them (dT/dt < 0) generates an upward electric field. In both cases, the SERS signals can be significantly amplified due to the piezoelectric-induced charge transfer between the LUMO level of the analyte molecule and the Fermi level of Ag. During the heating and cooling processes, the intensity of SERS signals undergoes temporal changes, which can be modulated by adjusting the heating and cooling rate. Such chemical enhancement can further amplify SERS signals by over 100 times, compared to recordings obtained under steady temperature conditions based solely on plasmon excitation.

Schematic depiction of the SERS substrate based on a pyroelectric material and silver nanoparticles.

Fig. 1 Schematic depiction of the SERS substrate based on PMN-PT and Ag NPs, illustrating the signal enhancement during heating (dT/dt > 0), steady temperature (dT/dt = 0), and cooling (dT/dt < 0). Reproduced from DOI: 10.1039/D3NH00053B with permission from the Royal Society of Chemistry.

The researchers conducted systematic experimental characterizations and theoretical calculations to understand the SERS performance of these substrates in a variable temperature environment. Different analytes were used to demonstrate the universal applicability of this method. Density functional theory calculations were performed for the Ag NP-molecular system to reveal the redistribution of charge density in response to an upward or downward electric field. In order to verify the role of chemical enhancement, the researchers used a thin layer of aluminium oxide (Al2O3) as a barrier layer to prevent charge transfer between the Ag NPs and the analytes (Fig. 2). Overall, although the electromagnetic enhancement was not optimized in this strategy, the researchers provided an in-depth understanding of the SERS mechanism and the role of charge transfer in chemical enhancement.

Schematic illustration of the SERS experiment setup for understanding the SERS enhancement mechanism.

Fig. 2 Schematic illustration of the SERS experiment setup for understanding the SERS enhancement mechanism of PMN-PT/Ag NPs by depositing a 5-nm Al2O3 layer to block the charge transfer between the Ag NPs and the analyte molecules. Reproduced from DOI: 10.1039/D3NH00053B with permission from the Royal Society of Chemistry.

Furthermore, the researchers successfully demonstrated a nanocavity structure with PMN-PT/Ag/Al2O3/Ag nanocubes (Ag NCs) (Fig. 3), which can be heated by simulated sunlight irradiation and achieve SERS enhancement, obviating the need for a temperature control platform. This development could have practical benefits for real-world applications.

The SERS measurement schematic diagram, temperature distribution images and SERS spectra before and after simulated sunlight irradiation.

Fig. 3 (a) The SERS measurement schematic diagram of PMN-PT/Ag/Al2O3/Ag NC substrate under simulated sunlight irradiation. (b) The temperature distribution images of PMN-PT/Ag/Al2O3/Ag NC after the simulated sunlight turned on and off. The SERS spectra of R6G (10–7 M) (c) and CV (10–7 M) (d) before and after simulated sunlight irradiation. Reproduced from DOI: 10.1039/D3NH00053B with permission from the Royal Society of Chemistry.

In summary, the novel combination of PMN-PT and Ag NPs allows for a straightforward observation of chemical SERS enhancement and its active tuning, both of which are traditionally challenging in this field. These findings will facilitate a deeper understanding of the SERS mechanism and the development of other SERS substrates to improve the detection sensitivity.

 

To find out more, please read:

Giant enhancement of the initial SERS activity for plasmonic nanostructures via pyroelectric PMN-PT
Mingrui Shao, Di Liu, Jinxuan Lu, Xiaofei Zhao, Jing Yu, Chao Zhang, Baoyuan Man, Hui Pan and Zhen Li
Nanoscale Horiz., 2023, 8, 948–957

 


About the blogger


Photo of Xiaolu Zhuo.

 

Xiaolu Zhuo is an Assistant Professor at The Chinese University of Hong Kong, Shenzhen, and a member of the Nanoscale Horizons Community Board. Dr Zhuo’s research lab focuses on the synthesis of plasmonic and dielectric nanoparticles, their optical behaviors, and their applications.

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Electrifying H2O2 synthesis with g-C3N4-based single atom catalysts

Electrifying the synthesis of commodity chemicals can play a critical role in achieving carbon neutrality, as well as addressing global energy and environmental problems. Among the diverse range of chemicals, hydrogen peroxide (H2O2) has emerged as a promising green oxidant and liquid hydrogen carrier. However, H2O2 is currently produced by the anthraquinone autooxidation process under harsh conditions with huge energy consumption. Consequently, researchers have been actively exploring alternative approaches for the synthesis of H2O2 using renewable resources under milder conditions.

In this regard, extensive studies have focused on the green synthesis of H2O2 using renewable electricity and employing either electrocatalysts or photocatalysts directly powered by sunlight. Most conventional studies on electrochemical H2O2 production have been conducted under alkaline conditions, which are known to facilitate efficient H2O2 production. However, it is important to note that H2O2 becomes unstable at high pHs. Moreover, from an environmental standpoint, there is a strong desire to develop electrocatalysts that can operate at neutral pH.

In this context, a recent paper by Yang et al. reports very interesting results. The researchers prepared graphitic carbon nitride (g-C3N4) nanosheets (CNNS) embedded with various transition metal single atoms (TM SAs) and discovered that TM SA-embedded CNNS show high electrocatalytic activity for H2O2 production at neutral pHs. Among the various TM SAs tested, Ni SAs on CNNS were particularly effective and showed the highest mass-specific activity of ∼503 mmol gcat1 h1 and H2O2 selectivity of ~98%. According to their mechanistic analysis, the introduction of TM SA promotes the formation of N-C=N sites, which are beneficial for H2O2 production via a two-electron oxygen reduction reaction (2e ORR), while suppressing the formation of C-C/C=C sites, which are beneficial for H2O production via a 4e ORR. This suggests the excellent function of g-C3N4 as a support for TM SAs in selectively producing H2O2.

Scheme showing H2O2 production from H2O and O2 on a modified graphitic carbon nitride sheet.

Fig. 1 Schematic of H2O2 production from H2O and O2 on a transition metal embedded graphitic carbon nitride sheet. Reproduced from DOI: 10.1039/D2NH00564F with permission from the Royal Society of Chemistry.

Notably, this paper is also intriguing from an academic perspective, as it demonstrates the efficient use of g-C3N4 as a support material for electrocatalysts, deviating from its traditional application as a photocatalyst in conventional studies. The findings offer new insights into the potential of g-C3N4 in catalytic systems and open avenues for further research in the field of sustainable chemical synthesis.

 

To find out more, please read:

Transition metal single atom-optimized g-C3N4 for the highly selective electrosynthesis of H2O2 under neutral electrolytes
Hongcen Yang, Fei Ma, Niandi Lu, Shuhao Tian, Guo Liu, Ying Wang, Zhixia Wang, Di Wang, Kun Tao, Hong Zhang and Shanglong Peng
Nanoscale Horiz., 2023, 8, 695–704

 


About the blogger


Photo of Jungki Ryu.

 

Jungki Ryu is a ​P​rofessor at ​Ulsan National Institute of Science and Technology (UNIST) and member of the Nanoscale Horizons Advisory Board. Prof. Ryu’s research focuses on developing innovative electrochemical and photoelectrochemical systems using nanomaterials​ for hydrogen production, CO2 conversion and biomass/waste utilization. You can follow Jungki on Twitter @jungki1981

 

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siRNA-loaded DNA nanostructures restore endothelial leakiness

Drug delivery and targeted treatment of diseases is one of the prominent focus areas of recent research. Development of new therapeutic approaches involving novel drug delivery materials (e.g., nanomaterials) requires validation that these materials do not affect the existing properties of the cellular environment. Now, researchers from the Third Military Medical University (China) and National University of Singapore (Singapore) have found that DNA-nanostructure-based drug delivery vehicles do not affect the cellular environment as previously thought, but in fact aid in restoring endothelial leakiness in vascular diseases.

For proper cellular function, endothelial barriers maintain vascular permeability by which essential nutrients and oxygen reaches the target tissues. Several diseases and inflammations cause endothelial leakiness, which in turn leads to disease progress and ineffective treatments. Now, researchers use cell and mouse models of pulmonary arterial hypertension (PAH), a lung disease, to demonstrate that DNA-based therapeutic carriers can effectively restore the endothelial barrier. They developed a triangular DNA structure and loaded small-interfering RNA (siRNA) molecules that target specific disease-associated genes. In this case, the researchers targeted the Atg101 gene that causes autophagy and in turn affects endothelial leakiness. They found that the siRNA-loaded DNA carriers were taken up by cells and reduced endothelial gaps to 0.3% compared to untreated cells that showed 10% endothelial gaps, thus providing a 30-fold improvement. This treatment was specific to the siRNA cargo loaded in the structure. When they used a random siRNA sequence loaded on to the DNA structures, there was no improvement in endothelial gaps. The group then tested the siRNA-loaded DNA structures in mice and found that the drug-loaded DNA structures provided protection against right ventricular and pulmonary artery dysfunction, a promising step forward to creating a treatment strategy for such diseases.

Fig. 1 (A) Design of DNA aptamer and Atg101 siRNA (siAtg101) conjugated DNA nanostructures. DNA aptamers are positioned either at the protruding points (DTA-V1) or the corners of the structure core (DTA-V2). (B) Aptamer-decorated DNA nanostructures bind to HPAECs and are subsequently internalized (C and D). The DNA nanostructures might be internalized through aptamer-mediated endocytosis. The embedded siRNA takes effect and restores endothelial integrity similar to the reversal of “NanoEL”. Reproduced from DOI: 10.1039/D2NH00348A with permission from the Royal Society of Chemistry.

This study provides new information on how nanomaterials interact with biological systems and affect cellular environment such as endothelial leakiness which is typically associated with tumor regions. As DNA structures could successfully delivery siRNA molecules to suppress endothelial leakiness related to a vascular disease, this study opens up the possibility of using DNA-based drug delivery carriers in therapeutics approaches beyond just cancer.

 

To find out more, please read:

Attenuating endothelial leakiness with self-assembled DNA nanostructures for pulmonary arterial hypertension
Qian Liu, Di Wu, Binfeng He, Xiaotong Ding, Yu Xu, Ying Wang, Mingzhou Zhang, Hang Qian, David Tai Leong and Guansong Wang
Nanoscale Horiz., 2023, 8, 270–278

 


About the blogger


Photo of Arun Richard Chandrasekaran.

 

Arun Richard Chandrasekaran is a Senior Research Scientist at The RNA Institute at the University at Albany, State University of New York, and member of the Nanoscale Horizons Community Board. Dr Chandrasekaran’s research lab focusses on using DNA as a material to build nanoscale structures, with applications in drug delivery, data storage and crystallography. You can follow Arun on Twitter @arunrichardc

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