Maryam Asadikorayem, Lucia G Brunel, Patrick Weber, Sarah C Heilshorn, Marcy Zenobi-Wong
Granular hydrogels comprised of jammed, crosslinked microgels offer great potential as biomaterial scaffolds for cell-based therapies, including for cartilage tissue regeneration. As stiffness and porosity of hydrogels affect the phenotype of encapsulated cells and the extent of tissue regeneration, the design of tunable granular hydrogels to control and optimize these parameters is highly desirable. We hypothesized that chondrogenesis could be modulated using a granular hydrogel platform based on biocompatible, zwitterionic materials with independent intra- and inter-microgel crosslinking mechanisms. Microgels are made with mechanical fragmentation of photocrosslinked zwitterionic carboxybetaine acrylamide (CBAA) and sulfobetaine methacrylate (SBMA) hydrogels, and secondarily crosslinked in the presence of cells using horseradish peroxide (HRP) to produce cell-laden granular hydrogels. We varied the intra-microgel crosslinking density to produce microgels with varied stiffnesses (1-3 kPa) and swelling properties. These microgels, when resuspended at the same weight fraction and secondarily crosslinked, resulted in granular hydrogels with distinct porosities (5-40%) due to differing swelling properties. The greatest extent of chondrogenesis was achieved in scaffolds with the highest microgel stiffness and highest porosity. However, when scaffold porosity was kept constant and just microgel stiffness varied, cell phenotype and chondrogenesis were similar across scaffolds. These results indicate the dominant role of granular scaffold porosity on chondrogenesis, whereas microgel stiffness appears to play a relatively minor role. These observations are in contrast to cells encapsulated within conventional bulk hydrogels, where stiffness has been shown to significantly affect chondrocyte response. In summary, we introduce chemically-defined, zwitterionic biomaterials to fabricate versatile granular hydrogels allowing for tunable scaffold porosity and microgel stiffness to study and influence chondrogenesis.
{"title":"Porosity dominates over microgel stiffness for promoting chondrogenesis in zwitterionic granular hydrogels.","authors":"Maryam Asadikorayem, Lucia G Brunel, Patrick Weber, Sarah C Heilshorn, Marcy Zenobi-Wong","doi":"10.1039/d4bm00233d","DOIUrl":"10.1039/d4bm00233d","url":null,"abstract":"<p><p>Granular hydrogels comprised of jammed, crosslinked microgels offer great potential as biomaterial scaffolds for cell-based therapies, including for cartilage tissue regeneration. As stiffness and porosity of hydrogels affect the phenotype of encapsulated cells and the extent of tissue regeneration, the design of tunable granular hydrogels to control and optimize these parameters is highly desirable. We hypothesized that chondrogenesis could be modulated using a granular hydrogel platform based on biocompatible, zwitterionic materials with independent intra- and inter-microgel crosslinking mechanisms. Microgels are made with mechanical fragmentation of photocrosslinked zwitterionic carboxybetaine acrylamide (CBAA) and sulfobetaine methacrylate (SBMA) hydrogels, and secondarily crosslinked in the presence of cells using horseradish peroxide (HRP) to produce cell-laden granular hydrogels. We varied the intra-microgel crosslinking density to produce microgels with varied stiffnesses (1-3 kPa) and swelling properties. These microgels, when resuspended at the same weight fraction and secondarily crosslinked, resulted in granular hydrogels with distinct porosities (5-40%) due to differing swelling properties. The greatest extent of chondrogenesis was achieved in scaffolds with the highest microgel stiffness and highest porosity. However, when scaffold porosity was kept constant and just microgel stiffness varied, cell phenotype and chondrogenesis were similar across scaffolds. These results indicate the dominant role of granular scaffold porosity on chondrogenesis, whereas microgel stiffness appears to play a relatively minor role. These observations are in contrast to cells encapsulated within conventional bulk hydrogels, where stiffness has been shown to significantly affect chondrocyte response. In summary, we introduce chemically-defined, zwitterionic biomaterials to fabricate versatile granular hydrogels allowing for tunable scaffold porosity and microgel stiffness to study and influence chondrogenesis.</p>","PeriodicalId":65,"journal":{"name":"Biomaterials Science","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11441418/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142337430","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Retraction of 'Glycolipid nanotube templates for the production of hydrophilic/hydrophobic and left/right-handed helical polydiacetylene nanotubes' by Naohiro Kameta et al., Chem. Commun., 2021, 57, 464-467, https://doi.org/10.1039/D0CC07387C.
{"title":"Retraction: Glycolipid nanotube templates for the production of hydrophilic/hydrophobic and left/right-handed helical polydiacetylene nanotubes.","authors":"Naohiro Kameta, Wuxiao Ding, Mitsutoshi Masuda","doi":"10.1039/d4cc90368d","DOIUrl":"https://doi.org/10.1039/d4cc90368d","url":null,"abstract":"<p><p>Retraction of 'Glycolipid nanotube templates for the production of hydrophilic/hydrophobic and left/right-handed helical polydiacetylene nanotubes' by Naohiro Kameta <i>et al.</i>, <i>Chem. Commun.</i>, 2021, <b>57</b>, 464-467, https://doi.org/10.1039/D0CC07387C.</p>","PeriodicalId":67,"journal":{"name":"Chemical Communications","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453604","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mingzhu Ye, Yirui Fan, Caihong Fu, Huixia He, Jianxi Xiao
Treating sunburn and other UV-induced skin damage issues remains a significant challenge in the field of dermatology. In this study, we synthesized a highly bioactive recombinant type III collagen (rCol III) to accelerate the healing of UV-damaged skin. The high-purity rCol III demonstrated excellent biocompatibility and bioactivity, significantly promoting the adhesion, proliferation, and migration of HFF-1 cells. In a mouse UV-damage model, Combo evaluations demonstrated that rCol III contributed to restore transepidermal water loss (TEWL) values of UV-damaged skin to normal levels. Histological analysis further confirmed that rCol III substantially accelerated skin repair by enhancing collagen regeneration. Additionally, rCol III facilitated the regeneration of zebrafish tail fin tissue and alleviated shrinkage caused by excessive UV exposure. The biocompatible and bioactive rCol III offers a novel strategy for treating UV-induced skin damage, holding immense potential for applications in skin tissue engineering.
治疗晒伤和其他紫外线引起的皮肤损伤问题仍然是皮肤科领域的一项重大挑战。在这项研究中,我们合成了一种高生物活性的重组 III 型胶原蛋白(rCol III),以加速紫外线损伤皮肤的愈合。高纯度的 rCol III 具有良好的生物相容性和生物活性,能显著促进 HFF-1 细胞的粘附、增殖和迁移。在小鼠紫外线损伤模型中,Combo 评估表明,rCol III 有助于将紫外线损伤皮肤的经表皮失水(TEWL)值恢复到正常水平。组织学分析进一步证实,rCol III 通过促进胶原蛋白再生,大大加快了皮肤修复速度。此外,rCol III 还促进了斑马鱼尾鳍组织的再生,并缓解了过度紫外线照射造成的萎缩。具有生物相容性和生物活性的 rCol III 为治疗紫外线引起的皮肤损伤提供了一种新策略,在皮肤组织工程方面具有巨大的应用潜力。
{"title":"Biocompatible recombinant type III collagen enhancing skin repair and anti-wrinkle effects.","authors":"Mingzhu Ye, Yirui Fan, Caihong Fu, Huixia He, Jianxi Xiao","doi":"10.1039/d4bm01284d","DOIUrl":"https://doi.org/10.1039/d4bm01284d","url":null,"abstract":"<p><p>Treating sunburn and other UV-induced skin damage issues remains a significant challenge in the field of dermatology. In this study, we synthesized a highly bioactive recombinant type III collagen (rCol III) to accelerate the healing of UV-damaged skin. The high-purity rCol III demonstrated excellent biocompatibility and bioactivity, significantly promoting the adhesion, proliferation, and migration of HFF-1 cells. In a mouse UV-damage model, Combo evaluations demonstrated that rCol III contributed to restore transepidermal water loss (TEWL) values of UV-damaged skin to normal levels. Histological analysis further confirmed that rCol III substantially accelerated skin repair by enhancing collagen regeneration. Additionally, rCol III facilitated the regeneration of zebrafish tail fin tissue and alleviated shrinkage caused by excessive UV exposure. The biocompatible and bioactive rCol III offers a novel strategy for treating UV-induced skin damage, holding immense potential for applications in skin tissue engineering.</p>","PeriodicalId":65,"journal":{"name":"Biomaterials Science","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453563","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Fundamental basis of mechanochemical reactivity.","authors":"Adam A L Michalchuk, Francesco Delogu","doi":"10.1039/d4cp90153c","DOIUrl":"https://doi.org/10.1039/d4cp90153c","url":null,"abstract":"","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shiai Zeng, Lan Gao, Kai Wang, Xuwei Liu, Zhuoyan Hu, Lei Zhao
Although it has been established that polysaccharides have an effect on bone marrow haematopoiesis, it remains unclear how polysaccharides regulate bone marrow haematopoiesis during absorption and metabolism in vivo. In this study, the effect of a longan polysaccharide of large molecular weight (TLPL) on the gut microbiota of mice and its implications for the haematopoietic process in bone marrow was discussed. Here, the results show that after 21 days of TLPL consumption, the respective quantities of white blood cells, platelets, hemoglobin and bone marrow nucleated cells were determined to be 3.18 ± 1.71 (109 L-1), 1238.10 ± 164.41 (109 L-1), 135.10 ± 4.95 (g L-1), and 1.70 × 107, which reached 56.98%, 117.28%, and 47.74%, respectively, of the results for NC. TLPL both increased the thymus and spleen indexes by up to 2.08 ± 0.64 (mg g-1) and 6.49 ± 2.45 (mg g-1), respectively. Additionally, TLPL remodeled the gut microbiota with a significant increase in Lactobacillus in particular, and a significant increase in the level of the potential intestinal metabolite lactate was detected in the serum. Most importantly, a similarly significant up-regulation of the gene expression of the lactate receptor, Gpr81, in the myeloid cells was observed. These changes contributed to the activation of the secretion of various cytokines associated with haematopoiesis, with the levels of G-CSF, EPO, SCF and PF4 increased by 2.44 times, 1.14 times, 1.56 times and 1.13 times, respectively, compared to the MC group, which subsequently accelerated production of bone marrow cells and blood cells. The findings of this study reveal the unique mechanism of dried longan polysaccharides in ameliorating myelosuppression and provide a feasible strategy for the treatment of chemotherapy-induced myelosuppression with bioactive polysaccharides.
{"title":"Along the gut-bone marrow signaling pathway: use of longan polysaccharides to regenerate blood cells after chemotherapy-induced myelosuppression.","authors":"Shiai Zeng, Lan Gao, Kai Wang, Xuwei Liu, Zhuoyan Hu, Lei Zhao","doi":"10.1039/d4fo03758h","DOIUrl":"https://doi.org/10.1039/d4fo03758h","url":null,"abstract":"<p><p>Although it has been established that polysaccharides have an effect on bone marrow haematopoiesis, it remains unclear how polysaccharides regulate bone marrow haematopoiesis during absorption and metabolism <i>in vivo</i>. In this study, the effect of a longan polysaccharide of large molecular weight (TLPL) on the gut microbiota of mice and its implications for the haematopoietic process in bone marrow was discussed. Here, the results show that after 21 days of TLPL consumption, the respective quantities of white blood cells, platelets, hemoglobin and bone marrow nucleated cells were determined to be 3.18 ± 1.71 (10<sup>9</sup> L<sup>-1</sup>), 1238.10 ± 164.41 (10<sup>9</sup> L<sup>-1</sup>), 135.10 ± 4.95 (g L<sup>-1</sup>), and 1.70 × 10<sup>7</sup>, which reached 56.98%, 117.28%, and 47.74%, respectively, of the results for NC. TLPL both increased the thymus and spleen indexes by up to 2.08 ± 0.64 (mg g<sup>-1</sup>) and 6.49 ± 2.45 (mg g<sup>-1</sup>), respectively. Additionally, TLPL remodeled the gut microbiota with a significant increase in <i>Lactobacillus</i> in particular, and a significant increase in the level of the potential intestinal metabolite lactate was detected in the serum. Most importantly, a similarly significant up-regulation of the gene expression of the lactate receptor, Gpr81, in the myeloid cells was observed. These changes contributed to the activation of the secretion of various cytokines associated with haematopoiesis, with the levels of G-CSF, EPO, SCF and PF4 increased by 2.44 times, 1.14 times, 1.56 times and 1.13 times, respectively, compared to the MC group, which subsequently accelerated production of bone marrow cells and blood cells. The findings of this study reveal the unique mechanism of dried longan polysaccharides in ameliorating myelosuppression and provide a feasible strategy for the treatment of chemotherapy-induced myelosuppression with bioactive polysaccharides.</p>","PeriodicalId":77,"journal":{"name":"Food & Function","volume":null,"pages":null},"PeriodicalIF":5.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"农林科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nikki McArthur, Jay D Squire, Ogechukwu J Onyeachonam, Nemil N Bhatt, Cynthia Jerez, Abigail L Holberton, Peter M Tessier, Levi B Wood, Rakez Kayed, Ravi S Kane
Tauopathies are neurodegenerative diseases that involve tau misfolding and aggregation in the brain. These diseases, including Alzheimer's disease (AD), are some of the least understood and most difficult to treat neurodegenerative disorders. Antibodies and antibody fragments that target tau oligomers, which are especially toxic forms of tau, are promising options for immunotherapies and diagnostic tools for tauopathies. In this study, we have developed conformational, tau oligomer-specific nanobodies, or single-domain antibodies. We demonstrate that these nanobodies, OT2.4 and OT2.6, are highly specific for tau oligomers relative to tau monomers and fibrils. We used epitope mapping to verify that these nanobodies bind to discontinuous epitopes on tau and to support the idea that they interact with a conformation present in the oligomeric, and not monomeric or fibrillar, forms of tau. We show that these nanobodies interact with tau oligomers in brain samples from AD patients and from healthy older adults with primary age-related tauopathy. Our results demonstrate the potential of these nanobodies as tau oligomer-specific binding reagents and future tauopathy therapeutics and diagnostics.
Tauopathies 是一种神经退行性疾病,涉及大脑中 tau 的错误折叠和聚集。包括阿尔茨海默病(AD)在内的这些疾病是人们最不了解和最难治疗的神经退行性疾病。针对tau寡聚体(毒性特别强的tau形式)的抗体和抗体片段是免疫疗法和tau病诊断工具的理想选择。在这项研究中,我们开发出了构象、tau寡聚体特异性纳米抗体或单域抗体。我们证明了这些纳米抗体(OT2.4和OT2.6)对tau少聚体(相对于tau单体和纤维)具有高度特异性。我们利用表位图谱验证了这些纳米抗体与 tau 上不连续的表位结合,并支持了它们与 tau 的低聚物而非单体或纤维形式中存在的构象相互作用的观点。我们的研究表明,这些纳米抗体能与AD患者和患有原发性年龄相关性tau蛋白病的健康老年人脑样本中的tau低聚体相互作用。我们的研究结果证明了这些纳米抗体作为tau寡聚体特异性结合试剂以及未来的tau病治疗和诊断方法的潜力。
{"title":"Generation of nanobodies with conformational specificity for tau oligomers that recognize tau aggregates from human Alzheimer's disease samples.","authors":"Nikki McArthur, Jay D Squire, Ogechukwu J Onyeachonam, Nemil N Bhatt, Cynthia Jerez, Abigail L Holberton, Peter M Tessier, Levi B Wood, Rakez Kayed, Ravi S Kane","doi":"10.1039/d4bm00707g","DOIUrl":"https://doi.org/10.1039/d4bm00707g","url":null,"abstract":"<p><p>Tauopathies are neurodegenerative diseases that involve tau misfolding and aggregation in the brain. These diseases, including Alzheimer's disease (AD), are some of the least understood and most difficult to treat neurodegenerative disorders. Antibodies and antibody fragments that target tau oligomers, which are especially toxic forms of tau, are promising options for immunotherapies and diagnostic tools for tauopathies. In this study, we have developed conformational, tau oligomer-specific nanobodies, or single-domain antibodies. We demonstrate that these nanobodies, OT2.4 and OT2.6, are highly specific for tau oligomers relative to tau monomers and fibrils. We used epitope mapping to verify that these nanobodies bind to discontinuous epitopes on tau and to support the idea that they interact with a conformation present in the oligomeric, and not monomeric or fibrillar, forms of tau. We show that these nanobodies interact with tau oligomers in brain samples from AD patients and from healthy older adults with primary age-related tauopathy. Our results demonstrate the potential of these nanobodies as tau oligomer-specific binding reagents and future tauopathy therapeutics and diagnostics.</p>","PeriodicalId":65,"journal":{"name":"Biomaterials Science","volume":null,"pages":null},"PeriodicalIF":5.8,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ella F Clark, Estelle Dunstan, Gabriele Kociok-Köhn, Antoine Buchard
The Kirsanov reaction has been used to synthesise air stable, efficient and selective bifunctional aminophosphonium catalysts for the alternating ring-opening copolymerisation of cyclohexene oxide and phthalic anhydride without the need for a co-initiator.
{"title":"Aminophosphonium organocatalysts for the ring-opening copolymerisation of epoxide and cyclic anhydride.","authors":"Ella F Clark, Estelle Dunstan, Gabriele Kociok-Köhn, Antoine Buchard","doi":"10.1039/d4cc03947e","DOIUrl":"https://doi.org/10.1039/d4cc03947e","url":null,"abstract":"<p><p>The Kirsanov reaction has been used to synthesise air stable, efficient and selective bifunctional aminophosphonium catalysts for the alternating ring-opening copolymerisation of cyclohexene oxide and phthalic anhydride without the need for a co-initiator.</p>","PeriodicalId":67,"journal":{"name":"Chemical Communications","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453597","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We herein describe an alkylation reaction of indoles with NHC salts to access bis(indolyl)methanes as product. The NHC salt (or free NHC) serves as a C1 precursor due to decomposition of its N-heterocyclic ring. Although the exact roles of zinc powder and acetic/formic acid remain elusive, both of them are indispensable for this reaction. Two possible reaction pathways are proposed based on the results of mechanistic experiments.
{"title":"Synthesis of bis(indolyl)methanes using N-heterocyclic carbene salt as a C1 precursor.","authors":"Bingwei Zhou, Zhao Gao, Yanhao Yang, Yuanyuan Hu","doi":"10.1039/d4ob01568a","DOIUrl":"https://doi.org/10.1039/d4ob01568a","url":null,"abstract":"<p><p>We herein describe an alkylation reaction of indoles with NHC salts to access bis(indolyl)methanes as product. The NHC salt (or free NHC) serves as a C1 precursor due to decomposition of its N-heterocyclic ring. Although the exact roles of zinc powder and acetic/formic acid remain elusive, both of them are indispensable for this reaction. Two possible reaction pathways are proposed based on the results of mechanistic experiments.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453702","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
<p >This article derives theoretical foundations of force field functional theory (FFFT). FFFT studies topics related to the functional representation of nonreactive forcefields to achieve various desirable properties such as: (a) formal exactness of the forcefield's energy functional under certain conditions, (b) a formally exact ansatz separating the bonded potential energy from the nonbonded potential energy within a bonded cluster in a way that enables bonded parameters to be optimized using linear regression instead of requiring nonlinear regression, (c) the potential energy's continuous differentiability to various orders with respect to energetically accessible internal coordinate displacements within a subdomain defined by one electronic ground state, (d) forcefield design that guarantees the reference ground-state geometry is exactly reproduced as an equilibrium structure on the forcefield's potential energy landscape, (e) reasonably accurate and broadly applicable frugal model potentials, (f) computationally efficient embedded feature selection that identifies and removes unimportant forcefield terms, (g) well-designed methods to parameterize the forcefield from quantum-mechanically-computed and (optionally) experimental reference data, and (h) forcefields that approximately reproduce experimentally-measured properties. This article also introduces: (1) an angle-bending model potential that more accurately describes physical dynamics and is continuously differentiable to all orders with respect to internal coordinate displacements even when the bond angle is linear (<em>i.e.</em>, <em>θ</em> = π (180°)) and (2) a first-principles-derived stretch potential that accurately describes short-range Pauli repulsion and the long-range bond dissociation energy. This new angle-bending potential gave good agreement to CCSD quantum-chemistry calculations for CaH<small><sub>2</sub></small>, CO<small><sub>2</sub></small>, H<small><sub>2</sub></small>O, HNO, Li<small><sub>2</sub></small>O, NO<small><sub>2</sub></small>, NS<small><sub>2</sub></small>, SF<small><sub>2</sub></small>, SiH<small><sub>2</sub></small>, and SO<small><sub>2</sub></small> molecules. This new bond-stretch potential reproduced the first 12+ and 30+ vibrational energy levels of H<small><sub>2</sub></small> and O<small><sub>2</sub></small> molecules, respectively, within a few percent of experimental values. Studying the C–F bond stretch in C<small><sub>6</sub></small>F<small><sub>6</sub></small> as an example, the new ansatz (item (b) above) reduced sensitivity of the optimized force constant's value to choice of nonbonded interaction parameters by an order of magnitude compared to the old ansatz. Normal mode analysis of optimized flexibility models for CO<small><sub>2</sub></small>, H<small><sub>2</sub></small>O, HNO, and SO<small><sub>2</sub></small> molecules yielded vibrational transition frequencies within a few percent of experimental values. These results demonstrate advant
{"title":"A formally exact theory to construct nonreactive forcefields using linear regression to optimize bonded parameters†","authors":"Thomas A. Manz","doi":"10.1039/D4RA01861C","DOIUrl":"https://doi.org/10.1039/D4RA01861C","url":null,"abstract":"<p >This article derives theoretical foundations of force field functional theory (FFFT). FFFT studies topics related to the functional representation of nonreactive forcefields to achieve various desirable properties such as: (a) formal exactness of the forcefield's energy functional under certain conditions, (b) a formally exact ansatz separating the bonded potential energy from the nonbonded potential energy within a bonded cluster in a way that enables bonded parameters to be optimized using linear regression instead of requiring nonlinear regression, (c) the potential energy's continuous differentiability to various orders with respect to energetically accessible internal coordinate displacements within a subdomain defined by one electronic ground state, (d) forcefield design that guarantees the reference ground-state geometry is exactly reproduced as an equilibrium structure on the forcefield's potential energy landscape, (e) reasonably accurate and broadly applicable frugal model potentials, (f) computationally efficient embedded feature selection that identifies and removes unimportant forcefield terms, (g) well-designed methods to parameterize the forcefield from quantum-mechanically-computed and (optionally) experimental reference data, and (h) forcefields that approximately reproduce experimentally-measured properties. This article also introduces: (1) an angle-bending model potential that more accurately describes physical dynamics and is continuously differentiable to all orders with respect to internal coordinate displacements even when the bond angle is linear (<em>i.e.</em>, <em>θ</em> = π (180°)) and (2) a first-principles-derived stretch potential that accurately describes short-range Pauli repulsion and the long-range bond dissociation energy. This new angle-bending potential gave good agreement to CCSD quantum-chemistry calculations for CaH<small><sub>2</sub></small>, CO<small><sub>2</sub></small>, H<small><sub>2</sub></small>O, HNO, Li<small><sub>2</sub></small>O, NO<small><sub>2</sub></small>, NS<small><sub>2</sub></small>, SF<small><sub>2</sub></small>, SiH<small><sub>2</sub></small>, and SO<small><sub>2</sub></small> molecules. This new bond-stretch potential reproduced the first 12+ and 30+ vibrational energy levels of H<small><sub>2</sub></small> and O<small><sub>2</sub></small> molecules, respectively, within a few percent of experimental values. Studying the C–F bond stretch in C<small><sub>6</sub></small>F<small><sub>6</sub></small> as an example, the new ansatz (item (b) above) reduced sensitivity of the optimized force constant's value to choice of nonbonded interaction parameters by an order of magnitude compared to the old ansatz. Normal mode analysis of optimized flexibility models for CO<small><sub>2</sub></small>, H<small><sub>2</sub></small>O, HNO, and SO<small><sub>2</sub></small> molecules yielded vibrational transition frequencies within a few percent of experimental values. These results demonstrate advant","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra01861c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452867","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rong Fu, Di Lei, Zhenlu Li, Hangjian Zhang, Xiaofei Zhao, Shuo Tao
Here, we report that black photothermal materials elevate solar heating temperatures across high solar absorption and low infrared radiation. Fe3O4 nanostructure films can be heated to 350 °C under light irradiation, and this system shows effective visible-light-driven ammonia synthesis production of 3677 μg g-1 h-1 under gas-solid phase catalysis without noble metals.
{"title":"Fe<sub>3</sub>O<sub>4</sub> nanostructure films as solar-thermal conversion materials for ammonia synthesis.","authors":"Rong Fu, Di Lei, Zhenlu Li, Hangjian Zhang, Xiaofei Zhao, Shuo Tao","doi":"10.1039/d4cc04112g","DOIUrl":"https://doi.org/10.1039/d4cc04112g","url":null,"abstract":"<p><p>Here, we report that black photothermal materials elevate solar heating temperatures across high solar absorption and low infrared radiation. Fe<sub>3</sub>O<sub>4</sub> nanostructure films can be heated to 350 °C under light irradiation, and this system shows effective visible-light-driven ammonia synthesis production of 3677 μg g<sup>-1</sup> h<sup>-1</sup> under gas-solid phase catalysis without noble metals.</p>","PeriodicalId":67,"journal":{"name":"Chemical Communications","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453601","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}