Silke Notter, Dolma Choezom, Titus Griebel, Fernanda Ramos-Gomes, Wiebke Möbius, Tiago De Oliveira, Lena-Christin Conradi, Frauke Alves, Claus Feldmann
Colorectal cancer (CRC) is the third most common cancer type and second leading cause of cancer-related deaths worldwide, requiring novel drug-delivery concepts. ITC@ZrO(TocP)/ZrO(FdUMP) core@shell nanocarriers (designated ITC-FdUMP-NC) with the clinically relevant chemotherapeutics irinotecan (ITC) and fluoro-2′-deoxyuridine-5′-phosphate (FdUMP) (active derivative of 5′-fluorouracil/5-FU) are a new type of nanocarrier with high drug payload (22 wt% of lipophilic ITC: particle core; 10 wt% of hydrophilic FdUMP: particle shell). The nanocarriers are tested in different CRC cell lines, a normal cell line, and rectal cancer patient-derived organoids (PDOs). Fluorescence-labeled nanocarriers show efficient uptake by all CRC cells and allow to distinctly track the intracellular trafficking toward endolysosomal compartments. Although free chemotherapeutic drugs exhibit a greater potency in 2D cell cultures, ITC-FdUMP-NC demonstrate equivalent cytotoxic efficacies as the freely dissolved drugs in the more complex 3D rectal cancer PDOs. The sustained drug-release profile of the nanocarriers contrasts favorably with conventional free drugs, potentially enhancing the therapeutic outcome in vivo. With a chemotherapeutic cocktail comparable to the clinically applied FOLFIRI (ITC + 5-FU), the ITC-FdUMP-NC represent a novel type of nanocarrier with high anti-tumor effect and high drug payload, offering a promising strategy to circumvent chemoresistance and to improve therapy efficacy in vivo with less side effects.
{"title":"High-Load Core@Shell Nanocarriers with Irinotecan and 5-Fluorouracil for Combination Chemotherapy in Colorectal Cancer","authors":"Silke Notter, Dolma Choezom, Titus Griebel, Fernanda Ramos-Gomes, Wiebke Möbius, Tiago De Oliveira, Lena-Christin Conradi, Frauke Alves, Claus Feldmann","doi":"10.1002/smsc.202400196","DOIUrl":"https://doi.org/10.1002/smsc.202400196","url":null,"abstract":"Colorectal cancer (CRC) is the third most common cancer type and second leading cause of cancer-related deaths worldwide, requiring novel drug-delivery concepts. ITC@ZrO(TocP)/ZrO(FdUMP) core@shell nanocarriers (designated ITC-FdUMP-NC) with the clinically relevant chemotherapeutics irinotecan (ITC) and fluoro-2′-deoxyuridine-5′-phosphate (FdUMP) (active derivative of 5′-fluorouracil/5-FU) are a new type of nanocarrier with high drug payload (22 wt% of lipophilic ITC: particle core; 10 wt% of hydrophilic FdUMP: particle shell). The nanocarriers are tested in different CRC cell lines, a normal cell line, and rectal cancer patient-derived organoids (PDOs). Fluorescence-labeled nanocarriers show efficient uptake by all CRC cells and allow to distinctly track the intracellular trafficking toward endolysosomal compartments. Although free chemotherapeutic drugs exhibit a greater potency in 2D cell cultures, ITC-FdUMP-NC demonstrate equivalent cytotoxic efficacies as the freely dissolved drugs in the more complex 3D rectal cancer PDOs. The sustained drug-release profile of the nanocarriers contrasts favorably with conventional free drugs, potentially enhancing the therapeutic outcome in vivo. With a chemotherapeutic cocktail comparable to the clinically applied FOLFIRI (ITC + 5-FU), the ITC-FdUMP-NC represent a novel type of nanocarrier with high anti-tumor effect and high drug payload, offering a promising strategy to circumvent chemoresistance and to improve therapy efficacy in vivo with less side effects.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":null,"pages":null},"PeriodicalIF":12.7,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142188611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Daniela Vasquez-Muñoz, Fabian Rohne, Isabel Meier, Cevin Braksch, Nino Lomadze, Anahita Heraji Esfahani, Anne Nitschke, Andreas Taubert, Svetlana Santer, Matthias Hartlieb, Marek Bekir
Separation of equally sized particles distinguished solely by interfacial properties remains a highly challenging task. Herein, a particle fractioning method is proposed, which is suitable to differentiate between polymer-grafted microparticles that are equal in size. The separation relies on the combination of a pressure driven microfluidic flow, together with simultaneous light illumination and temperature control. Heating the solution forces thermo-responsive surface grafts to undergo a volume phase transition and therefore locally changing the interfacial properties of the microparticles. Light illumination induces the phoretic/osmotic activity of the microparticles and lifts them into a higher plane, where hovering particles experience a different shear stress proportional to the height. The light-induced hovering height depends on the interfacial properties, and this complex interaction leads to different movements of the microparticles as a function of their surface grafting. The concepts are visualized in experimental studies, where the complex physical principle provides a simple method for fractioning a binary mixture with at least one thermo-responsive polymer graft.
{"title":"Separation of Surface Grafted Microparticles via Light and Temperature","authors":"Daniela Vasquez-Muñoz, Fabian Rohne, Isabel Meier, Cevin Braksch, Nino Lomadze, Anahita Heraji Esfahani, Anne Nitschke, Andreas Taubert, Svetlana Santer, Matthias Hartlieb, Marek Bekir","doi":"10.1002/smsc.202400146","DOIUrl":"https://doi.org/10.1002/smsc.202400146","url":null,"abstract":"Separation of equally sized particles distinguished solely by interfacial properties remains a highly challenging task. Herein, a particle fractioning method is proposed, which is suitable to differentiate between polymer-grafted microparticles that are equal in size. The separation relies on the combination of a pressure driven microfluidic flow, together with simultaneous light illumination and temperature control. Heating the solution forces thermo-responsive surface grafts to undergo a volume phase transition and therefore locally changing the interfacial properties of the microparticles. Light illumination induces the phoretic/osmotic activity of the microparticles and lifts them into a higher plane, where hovering particles experience a different shear stress proportional to the height. The light-induced hovering height depends on the interfacial properties, and this complex interaction leads to different movements of the microparticles as a function of their surface grafting. The concepts are visualized in experimental studies, where the complex physical principle provides a simple method for fractioning a binary mixture with at least one thermo-responsive polymer graft.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":null,"pages":null},"PeriodicalIF":12.7,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142188600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yanan Cui, Seung Hun Park, Wesley R. Stiles, Atsushi Yamashita, Jason Dihn, Richard S. Kim, Yadong Zhang, Xiaoran Yin, Yoonji Baek, Haoran Wang, Kai Bao, Homan Kang, Hak Soo Choi
The use of ligand conjugation onto nanoparticle surfaces as an active targeting strategy has gained significant attention in the pursuit of improving tumor-specific delivery and retention. However, the chemical conjugation of targeting moieties often induces alterations in the physicochemical properties of nanoparticles, including size, conformation, charge-to-mass ratio, and hydrophilicity/lipophilicity, resulting in unexpected biodistribution and pharmacokinetic profiles. Here, the enhanced active targeting efficiency achieved by integrating cyclic arginine–glycine–aspartic acid (cRGD) peptides onto ultrasmall nanocarrier H-dot while preserving its essential physicochemical and pharmacokinetic attributes is investigated. The resulting cRGD/H-dots demonstrate improved cellular uptake via integrin αvβ3 receptors, accompanied by negligible cytotoxicity. Notably, the active targeting efficacy of cRGD/H-dots compared to unmodified H-dots (1.2%ID/g, two-fold increase) is quantitatively evaluated, validated through fluorescence imaging and histological analysis. The findings highlight that cRGD/H-dots offer enhanced tumor targetability and prolonged tumoral retention while maintaining active renal clearance of unbound molecules.
{"title":"Renal Clearable H-Dots Leveraging Ligand Complexation for Enhanced Active Tumor Targeting","authors":"Yanan Cui, Seung Hun Park, Wesley R. Stiles, Atsushi Yamashita, Jason Dihn, Richard S. Kim, Yadong Zhang, Xiaoran Yin, Yoonji Baek, Haoran Wang, Kai Bao, Homan Kang, Hak Soo Choi","doi":"10.1002/smsc.202400246","DOIUrl":"https://doi.org/10.1002/smsc.202400246","url":null,"abstract":"The use of ligand conjugation onto nanoparticle surfaces as an active targeting strategy has gained significant attention in the pursuit of improving tumor-specific delivery and retention. However, the chemical conjugation of targeting moieties often induces alterations in the physicochemical properties of nanoparticles, including size, conformation, charge-to-mass ratio, and hydrophilicity/lipophilicity, resulting in unexpected biodistribution and pharmacokinetic profiles. Here, the enhanced active targeting efficiency achieved by integrating cyclic arginine–glycine–aspartic acid (cRGD) peptides onto ultrasmall nanocarrier H-dot while preserving its essential physicochemical and pharmacokinetic attributes is investigated. The resulting cRGD/H-dots demonstrate improved cellular uptake via integrin α<sub>v</sub>β<sub>3</sub> receptors, accompanied by negligible cytotoxicity. Notably, the active targeting efficacy of cRGD/H-dots compared to unmodified H-dots (1.2%ID/g, two-fold increase) is quantitatively evaluated, validated through fluorescence imaging and histological analysis. The findings highlight that cRGD/H-dots offer enhanced tumor targetability and prolonged tumoral retention while maintaining active renal clearance of unbound molecules.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":null,"pages":null},"PeriodicalIF":12.7,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142188574","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Haitao Yu, Sampa Sarkar, Z. L. Shaw, Brendan Dyett, Xudong Cai, Sue Lyn Yap, Charlotte E. Conn, Aaron Elbourne, Calum J. Drummond, Jiali Zhai
Antimicrobial resistance (AMR) poses a global health crisis demanding innovative solutions. Traditional antibiotics, though pivotal over the past century in combating bacterial infections, face diminished efficacy against evolving bacterial defense mechanisms, especially in Gram-negative strains. This study explores self-assembled ionizable lipid nanoparticles (LNPs) with the incorporation of two ionizable lipid components (one cationic, one anionic) in nanocarriers for advanced antimicrobial drug delivery of the broad-spectrum antibiotic Piperacillin (Pip). Incorporating cationic ionizable lipid ALC-0315, recognized as a functional lipid in the Pfizer-BioNTech mRNA-based SARS-CoV-2 vaccine, into LNPs allowed mesophase transition, pH responsiveness, and ionization behavior in acidic environments found in sites of bacterial infections, to be studied using synchrotron small angle X-ray scattering, dynamic light scattering, and a 2-(p-toluidino)-6-naphthalene sulfonic acid assay. Incorporating another anionic ionizable lipid, oleic acid not only modulates the LNPs’ physicochemical properties, such as size, internal phase nanostructure, and surface charge but also synergistically enhances the antimicrobial potency together with ALC-0315 with a benefit enhancing permeability and fusion with bacterial membranes. This study introduces a strategy for tailoring ionizable lipid compositions in LNPs, providing a new approach to antimicrobial treatment contributing to the fight against AMR.
{"title":"Ionizable Lipid Containing Nanocarriers for Antimicrobial Agent Delivery","authors":"Haitao Yu, Sampa Sarkar, Z. L. Shaw, Brendan Dyett, Xudong Cai, Sue Lyn Yap, Charlotte E. Conn, Aaron Elbourne, Calum J. Drummond, Jiali Zhai","doi":"10.1002/smsc.202400145","DOIUrl":"https://doi.org/10.1002/smsc.202400145","url":null,"abstract":"Antimicrobial resistance (AMR) poses a global health crisis demanding innovative solutions. Traditional antibiotics, though pivotal over the past century in combating bacterial infections, face diminished efficacy against evolving bacterial defense mechanisms, especially in Gram-negative strains. This study explores self-assembled ionizable lipid nanoparticles (LNPs) with the incorporation of two ionizable lipid components (one cationic, one anionic) in nanocarriers for advanced antimicrobial drug delivery of the broad-spectrum antibiotic Piperacillin (Pip). Incorporating cationic ionizable lipid ALC-0315, recognized as a functional lipid in the Pfizer-BioNTech mRNA-based SARS-CoV-2 vaccine, into LNPs allowed mesophase transition, pH responsiveness, and ionization behavior in acidic environments found in sites of bacterial infections, to be studied using synchrotron small angle X-ray scattering, dynamic light scattering, and a 2-(p-toluidino)-6-naphthalene sulfonic acid assay. Incorporating another anionic ionizable lipid, oleic acid not only modulates the LNPs’ physicochemical properties, such as size, internal phase nanostructure, and surface charge but also synergistically enhances the antimicrobial potency together with ALC-0315 with a benefit enhancing permeability and fusion with bacterial membranes. This study introduces a strategy for tailoring ionizable lipid compositions in LNPs, providing a new approach to antimicrobial treatment contributing to the fight against AMR.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":null,"pages":null},"PeriodicalIF":12.7,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142188591","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Md Mofasser Mallick, Leonard Franke, Mohamed Hussein, Andres Georg Rösch, Zhongmin Long, Yolita Maria Eggeler, Uli Lemmer
Printed thermoelectric generators (TEGs) show promising potential for converting waste heat into useful electricity at a low cost but fall short of exhibiting a conversion efficiency anticipated from materials’ properties. The output power of conventionally printed TEGs in the “π-type” geometry suffers due to low thermal voltage and low current because of high thermal and electrical contact resistance, respectively. Herein, a type of printed p–n junction TEGs (PN-TEGs) as a possible remedy is explored. Two printed PN-TEGs with different thicknesses are fabricated using printed p-type Bi0.5Sb1.5Te3 and n-type Bi2Te2.7Se0.3 materials. The PN-TEGs show a promising way to minimize the influence of thermal and electrical resistance in printed TEGs. In the experimental and simulation results, the significant impact of PN-TEGs’ dimensions on their power outputs is revealed. Also, a conventional “π-type” printed TEG is fabricated and its performance is studied. The optimized PN-TEG with a single thermocouple yields ≈14 times higher power output density of 5.3 μW cm−2 at a ΔT of 25 K compared to “π-type” printed TEGs.
{"title":"Printed Lateral p–n Junction for Thermoelectric Generation","authors":"Md Mofasser Mallick, Leonard Franke, Mohamed Hussein, Andres Georg Rösch, Zhongmin Long, Yolita Maria Eggeler, Uli Lemmer","doi":"10.1002/smsc.202400257","DOIUrl":"https://doi.org/10.1002/smsc.202400257","url":null,"abstract":"Printed thermoelectric generators (TEGs) show promising potential for converting waste heat into useful electricity at a low cost but fall short of exhibiting a conversion efficiency anticipated from materials’ properties. The output power of conventionally printed TEGs in the “π-type” geometry suffers due to low thermal voltage and low current because of high thermal and electrical contact resistance, respectively. Herein, a type of printed p–n junction TEGs (PN-TEGs) as a possible remedy is explored. Two printed PN-TEGs with different thicknesses are fabricated using printed p-type Bi<sub>0.5</sub>Sb<sub>1.5</sub>Te<sub>3</sub> and n-type Bi<sub>2</sub>Te<sub>2.7</sub>Se<sub>0.3</sub> materials. The PN-TEGs show a promising way to minimize the influence of thermal and electrical resistance in printed TEGs. In the experimental and simulation results, the significant impact of PN-TEGs’ dimensions on their power outputs is revealed. Also, a conventional “π-type” printed TEG is fabricated and its performance is studied. The optimized PN-TEG with a single thermocouple yields ≈14 times higher power output density of 5.3 μW cm<sup>−2</sup> at a Δ<i>T</i> of 25 K compared to “π-type” printed TEGs.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":null,"pages":null},"PeriodicalIF":12.7,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142224586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chia-Chi Chang, Min-Hsien Shen, Yuan-Shuo Hsu, Hsisheng Teng, Jeng-Shiung Jan
Quasi-solid and composite polymer electrolytes (QSPEs and CPEs) used in lithium-ion battery (LIB) have recently been a novel strategy owing to their high-safety comparing to traditional liquid counterparts. This study reported the preparation of CPEs based on boron moiety, poly(ethylene glycol) (PEG), and octahedral polyhedral oligomeric silsesquioxane (POSS) via in situ thermal polymerization method directly onto the lithium anode to improve the interfacial contact and electrochemical performance. The synergistic effect between the incorporation of anion-trapping boron moiety and in situ polymerization rendered the QSPEs exhibiting higher electrochemical voltage window, ionic conductivity, and transference number as well as better electrochemical performance than the PEG-based counterpart. Due to the Lewis acid effect, anion-trapping boron moiety could promote the dissociation of lithium salts, allowing more lithium ions to be in the free state, thereby enhancing the lithium-ion conductivity. With an optimal addition of POSS, the as-prepared CPEs exhibited lower overpotential during the lithium plating-stripping test and better electrochemical performance than the QSPE counterparts. The optimal POSS addition could facilitate the lithium-ion conduction and establishment of continuous ion pathways, further improving their electrochemical performance. This study pointed a promising approach for developing high performance lithium-ion batteries.
{"title":"In Situ Formed Composite Polymer Electrolytes Based on Anion-Trapping Boron Moiety and Polyhedral Oligomeric Silsesquioxane for High Performance Lithium Metal Batteries","authors":"Chia-Chi Chang, Min-Hsien Shen, Yuan-Shuo Hsu, Hsisheng Teng, Jeng-Shiung Jan","doi":"10.1002/smsc.202400183","DOIUrl":"https://doi.org/10.1002/smsc.202400183","url":null,"abstract":"Quasi-solid and composite polymer electrolytes (QSPEs and CPEs) used in lithium-ion battery (LIB) have recently been a novel strategy owing to their high-safety comparing to traditional liquid counterparts. This study reported the preparation of CPEs based on boron moiety, poly(ethylene glycol) (PEG), and octahedral polyhedral oligomeric silsesquioxane (POSS) via in situ thermal polymerization method directly onto the lithium anode to improve the interfacial contact and electrochemical performance. The synergistic effect between the incorporation of anion-trapping boron moiety and in situ polymerization rendered the QSPEs exhibiting higher electrochemical voltage window, ionic conductivity, and transference number as well as better electrochemical performance than the PEG-based counterpart. Due to the Lewis acid effect, anion-trapping boron moiety could promote the dissociation of lithium salts, allowing more lithium ions to be in the free state, thereby enhancing the lithium-ion conductivity. With an optimal addition of POSS, the as-prepared CPEs exhibited lower overpotential during the lithium plating-stripping test and better electrochemical performance than the QSPE counterparts. The optimal POSS addition could facilitate the lithium-ion conduction and establishment of continuous ion pathways, further improving their electrochemical performance. This study pointed a promising approach for developing high performance lithium-ion batteries.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":null,"pages":null},"PeriodicalIF":12.7,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142188575","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Manoj Settem, Melisa M. Gianetti, Roberto Guerra, Nicola Manini, Riccardo Ferrando, Alberto Giacomello
Adopting an advanced microscopic model of the Au–graphite interaction, a systematic study of Au nanoclusters (up to sizes of 11 238 atoms) on graphene and on graphite is carried out to explore their structure and energy landscape. Using parallel tempering molecular dynamics, structural distribution as a function of temperature is calculated in the entire temperature range. Low-energy structures are identified through a combination of structural optimization and Wulff–Kaischew construction which are then used to explore the energy landscape. The potential energy surface (PES), which is energy as a function of translation and rotation, is calculated for a few Au nanoclusters along specific directions on carbon lattice. Minimum-energy pathways are identified on the PES indicating a reduced barrier for pathways involving simultaneous rotation and translation. Diffusion simulations of Au233 on graphite show that diffusion mechanism is directly related to the PES, and the information of the cluster pinning events is already present in the PES. Finally, a comparison of various interaction models highlights the importance of reasonably correct Au–C interactions which is crucial for studying the energy landscape and cluster sliding.
采用先进的金-石墨相互作用微观模型，对石墨烯和石墨上的金纳米团簇（大小可达 11 238 个原子）进行了系统研究，以探索它们的结构和能量分布。利用平行回火分子动力学，计算了整个温度范围内作为温度函数的结构分布。通过结构优化和 Wulff-Kaischew 构建相结合的方法确定了低能结构，然后利用这些低能结构探索能量分布。计算了碳晶格上几个金纳米团簇沿特定方向的势能面（PES），即能量与平移和旋转的函数关系。在势能面上确定了最小能量路径，表明涉及同时旋转和平移的路径障碍减少。Au233 在石墨上的扩散模拟表明，扩散机制与 PES 直接相关，并且簇钉住事件的信息已经存在于 PES 中。最后，对各种相互作用模型的比较强调了合理正确的 Au-C 相互作用的重要性，这对于研究能量景观和簇滑动至关重要。
{"title":"Gold Clusters on Graphene/Graphite—Structure and Energy Landscape","authors":"Manoj Settem, Melisa M. Gianetti, Roberto Guerra, Nicola Manini, Riccardo Ferrando, Alberto Giacomello","doi":"10.1002/smsc.202400078","DOIUrl":"https://doi.org/10.1002/smsc.202400078","url":null,"abstract":"Adopting an advanced microscopic model of the Au–graphite interaction, a systematic study of Au nanoclusters (up to sizes of 11 238 atoms) on graphene and on graphite is carried out to explore their structure and energy landscape. Using parallel tempering molecular dynamics, structural distribution as a function of temperature is calculated in the entire temperature range. Low-energy structures are identified through a combination of structural optimization and Wulff–Kaischew construction which are then used to explore the energy landscape. The potential energy surface (PES), which is energy as a function of translation and rotation, is calculated for a few Au nanoclusters along specific directions on carbon lattice. Minimum-energy pathways are identified on the PES indicating a reduced barrier for pathways involving simultaneous rotation and translation. Diffusion simulations of Au<sub>233</sub> on graphite show that diffusion mechanism is directly related to the PES, and the information of the cluster pinning events is already present in the PES. Finally, a comparison of various interaction models highlights the importance of reasonably correct Au–C interactions which is crucial for studying the energy landscape and cluster sliding.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":null,"pages":null},"PeriodicalIF":12.7,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142188576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Florian Mayer, Paul Schweng, Simone Braeuer, Sebastian Hummer, Gunda Koellensperger, Andreas Mautner, Robert Woodward, Alexander Bismarck
Efficient water treatment ideally combines ion exchange for the removal of hardness elements and toxic trace metals as well as ultrafiltration for the removal of particulate matter. Although promising for adsorption, many high-surface-area polymer materials cannot be easily processed into freestanding membranes or packed bed columns, due to poor solution processability and high back pressures, respectively. The preparation of hybrid membranes comprising sulfonated hypercrosslinked polymers entrapped in nanocellulose papers is described. The hybrid membranes are effective for simultaneous ultrafiltration and ion exchange. Increasing the polymer loading of the hybrid membrane produces synergy by increasing the permeance of the membranes while enhancing the ion adsorption capacity to values exceeding those of bulk hypercrosslinked polymers. The maximum ion adsorption capacity for copper is determined to be ≈100 mg g−1 outperforming that of pure polymer (71 mg g−1) and commercially available ion exchange resins. Competitive adsorption is tested in samples containing water hardness elements and trace toxic metal ions showing high ion-exchange capacities. Even when fully loaded with water hardness elements, Ba2+ and Sr2+ are still removed from solution.
{"title":"Best of Both Worlds: Adsorptive Ultrafiltration Nanocellulose-Hypercrosslinked Polymer Hybrid Membranes for Metal Ion Removal","authors":"Florian Mayer, Paul Schweng, Simone Braeuer, Sebastian Hummer, Gunda Koellensperger, Andreas Mautner, Robert Woodward, Alexander Bismarck","doi":"10.1002/smsc.202400182","DOIUrl":"https://doi.org/10.1002/smsc.202400182","url":null,"abstract":"Efficient water treatment ideally combines ion exchange for the removal of hardness elements and toxic trace metals as well as ultrafiltration for the removal of particulate matter. Although promising for adsorption, many high-surface-area polymer materials cannot be easily processed into freestanding membranes or packed bed columns, due to poor solution processability and high back pressures, respectively. The preparation of hybrid membranes comprising sulfonated hypercrosslinked polymers entrapped in nanocellulose papers is described. The hybrid membranes are effective for simultaneous ultrafiltration and ion exchange. Increasing the polymer loading of the hybrid membrane produces synergy by increasing the permeance of the membranes while enhancing the ion adsorption capacity to values exceeding those of bulk hypercrosslinked polymers. The maximum ion adsorption capacity for copper is determined to be ≈100 mg g<sup>−1</sup> outperforming that of pure polymer (71 mg g<sup>−1</sup>) and commercially available ion exchange resins. Competitive adsorption is tested in samples containing water hardness elements and trace toxic metal ions showing high ion-exchange capacities. Even when fully loaded with water hardness elements, Ba<sup>2+</sup> and Sr<sup>2+</sup> are still removed from solution.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":null,"pages":null},"PeriodicalIF":12.7,"publicationDate":"2024-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141931603","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing scalable and accurate predictive analytical methods for the classification of protein‐DNA binding is critical for advancing our understanding of molecular biology, disease mechanisms, and a wide spectrum of biotechnological and medical applications. It is discovered that histone–DNA interactions can be stratified based on stain patterns created by the deposition of various nucleoprotein solutions onto a substrate. In this study, a deep‐learning neural network is applied to categorize polarized light microscopy images of drying droplet deposits originating from different histone–DNA mixtures. These DNA stain patterns featured high reproducibility across different species and thus enabled comprehensive DNA categorization (100% accuracy) and accurate prediction of their respective binding affinities to histones. Eukaryotic DNA, which has a higher binding affinity to mammalian histones than prokaryotic DNA, is associated with a higher overall prediction accuracy. For a given species, the average prediction accuracy increased with DNA size. To demonstrate generalizability, a pre‐trained CNN is challenged with unknown images that originated from DNA samples of species not included in the training set. The CNN classified these unknown histone‐DNA samples as either strong or medium binders with 84.4% and 96.25% accuracy, respectively.
为蛋白质-DNA 结合的分类开发可扩展且准确的预测分析方法，对于促进我们对分子生物学、疾病机理以及广泛的生物技术和医学应用的理解至关重要。研究发现，组蛋白与 DNA 的相互作用可根据各种核蛋白溶液沉积在基底上形成的染色模式进行分层。在这项研究中，深度学习神经网络被用于对源自不同组蛋白-DNA 混合物的干燥液滴沉积的偏振光显微镜图像进行分类。这些DNA染色模式在不同物种之间具有很高的可重复性，因此能够进行全面的DNA分类（准确率为100%），并准确预测它们各自与组蛋白的结合亲和力。与原核 DNA 相比，真核 DNA 与哺乳动物组蛋白的结合亲和力更高，因此总体预测准确率也更高。对于特定物种，平均预测准确率随 DNA 大小的增加而提高。为了证明其通用性，预先训练好的 CNN 要面对来自未列入训练集的物种 DNA 样本的未知图像的挑战。CNN 将这些未知的组蛋白 DNA 样本分类为强粘合剂或中等粘合剂，准确率分别为 84.4% 和 96.25%。
{"title":"Deep Learning‐Based Classification of Histone–DNA Interactions Using Drying Droplet Patterns","authors":"Safoura Vaez, Bahar Dadfar, Meike Koenig, Matthias Franzreb, Joerg Lahann","doi":"10.1002/smsc.202400252","DOIUrl":"https://doi.org/10.1002/smsc.202400252","url":null,"abstract":"Developing scalable and accurate predictive analytical methods for the classification of protein‐DNA binding is critical for advancing our understanding of molecular biology, disease mechanisms, and a wide spectrum of biotechnological and medical applications. It is discovered that histone–DNA interactions can be stratified based on stain patterns created by the deposition of various nucleoprotein solutions onto a substrate. In this study, a deep‐learning neural network is applied to categorize polarized light microscopy images of drying droplet deposits originating from different histone–DNA mixtures. These DNA stain patterns featured high reproducibility across different species and thus enabled comprehensive DNA categorization (100% accuracy) and accurate prediction of their respective binding affinities to histones. Eukaryotic DNA, which has a higher binding affinity to mammalian histones than prokaryotic DNA, is associated with a higher overall prediction accuracy. For a given species, the average prediction accuracy increased with DNA size. To demonstrate generalizability, a pre‐trained CNN is challenged with unknown images that originated from DNA samples of species not included in the training set. The CNN classified these unknown histone‐DNA samples as either strong or medium binders with 84.4% and 96.25% accuracy, respectively.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":null,"pages":null},"PeriodicalIF":11.1,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141920714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fabian A C Apfelbeck, J. E. Heger, Tianle Zheng, Tianfu Guan, M. Schwartzkopf, Stephan V. Roth, Peter Müller‐Buschbaum
Electrode materials for application in lithium‐ion batteries are commonly probed by X‐ray diffraction (XRD) to investigate their crystalline structure. Grazing incidence wide‐angle X‐ray scattering (GIWAXS) is an extension to XRD since in‐plane structures are also accessible. Additionally, with grazing incidence small‐angle X‐ray scattering (GISAXS), morphological information on the nanoscale can be revealed. In this work, the nanostructure of battery electrodes, which consist of lithium iron phosphate (LiFePO4) as active material, carbon black (CB) as conducting agent, and the polymeric binders polyvinylidenefluoride (PVDF) and poly((trifluoromethane) sulfonimide lithium styrene) (PSTFSILi) is studied by performing GISAXS and GIWAXS. The chemical nature of the binder is tuned by blending PVDF and PSTFSILi. Specifically, a series of LiFePO4 electrodes with polymer blends of the common, non‐conducting PVDF and the single‐ion conducting PSTFSILi with different weight ratios as binders is investigated to understand the influence of the binder on the structure of the electrode in detail. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) complement these studies to correlate the morphology and structure with the electrochemical behavior. It is found that LiFePO4 crystallites do not exhibit any preferred orientation with respect to the substrate, irrespective of the binder composition, but their size depends on the binder composition.
用于锂离子电池的电极材料通常通过 X 射线衍射 (XRD) 来研究其晶体结构。掠入射广角 X 射线散射 (GIWAXS) 是 X 射线衍射的延伸，因为平面内结构也可以获得。此外，利用掠入射小角 X 射线散射 (GISAXS)，还可以揭示纳米级的形态信息。本研究通过 GISAXS 和 GIWAXS 对电池电极的纳米结构进行了研究，电池电极由活性材料磷酸铁锂（LiFePO4）、导电剂炭黑（CB）以及聚合物粘合剂聚偏氟乙烯（PVDF）和聚（（三氟甲烷）磺酰亚胺锂苯乙烯）（PSTFSILi）组成。通过混合 PVDF 和 PSTFSILi 调整了粘合剂的化学性质。具体而言，研究了一系列以普通非导电 PVDF 和单离子导电 PSTFSILi 的不同重量比聚合物混合物为粘合剂的磷酸铁锂电池电极，以详细了解粘合剂对电极结构的影响。扫描电子显微镜 (SEM) 和电化学阻抗光谱 (EIS) 对这些研究进行了补充，以将形貌和结构与电化学行为联系起来。研究发现，无论粘合剂成分如何，磷酸铁锂晶粒相对于基底都不表现出任何优先取向，但其大小取决于粘合剂成分。
{"title":"Influence of the Polymer Binder Composition on the Charge Transfer Resistance, Morphology, and Crystallinity of LiFePO4 Electrodes Revealed by Electrochemical Impedance Spectroscopy and Grazing Incidence Small‐ and Wide‐Angle X‐ray Scattering","authors":"Fabian A C Apfelbeck, J. E. Heger, Tianle Zheng, Tianfu Guan, M. Schwartzkopf, Stephan V. Roth, Peter Müller‐Buschbaum","doi":"10.1002/smsc.202400154","DOIUrl":"https://doi.org/10.1002/smsc.202400154","url":null,"abstract":"Electrode materials for application in lithium‐ion batteries are commonly probed by X‐ray diffraction (XRD) to investigate their crystalline structure. Grazing incidence wide‐angle X‐ray scattering (GIWAXS) is an extension to XRD since in‐plane structures are also accessible. Additionally, with grazing incidence small‐angle X‐ray scattering (GISAXS), morphological information on the nanoscale can be revealed. In this work, the nanostructure of battery electrodes, which consist of lithium iron phosphate (LiFePO4) as active material, carbon black (CB) as conducting agent, and the polymeric binders polyvinylidenefluoride (PVDF) and poly((trifluoromethane) sulfonimide lithium styrene) (PSTFSILi) is studied by performing GISAXS and GIWAXS. The chemical nature of the binder is tuned by blending PVDF and PSTFSILi. Specifically, a series of LiFePO4 electrodes with polymer blends of the common, non‐conducting PVDF and the single‐ion conducting PSTFSILi with different weight ratios as binders is investigated to understand the influence of the binder on the structure of the electrode in detail. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) complement these studies to correlate the morphology and structure with the electrochemical behavior. It is found that LiFePO4 crystallites do not exhibit any preferred orientation with respect to the substrate, irrespective of the binder composition, but their size depends on the binder composition.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":null,"pages":null},"PeriodicalIF":11.1,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141920339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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