Faraday Discussions最新文献_第2页

Silica biomineralization in plants alters the structure of lignin. 植物中二氧化硅生物矿化改变了木质素的结构。

IF 3.3 3区化学

Faraday Discussions Pub Date : 2025-05-29 DOI: 10.1039/d5fd00011d

Srinath Palakurthy, Michael Elbaum, Rivka Elbaum

{"title":"Silica biomineralization in plants alters the structure of lignin.","authors":"Srinath Palakurthy, Michael Elbaum, Rivka Elbaum","doi":"10.1039/d5fd00011d","DOIUrl":"https://doi.org/10.1039/d5fd00011d","url":null,"abstract":"Biomineralization of silica is a major process in plants, which may contribute 3-10% of tissue dry weight. For reasons that remain unclear, plants containing silica are less sensitive to abiotic and biotic stress. In particular, the mechanisms of silica deposition and stress amelioration are still not fully understood. Silica resides mostly in the extracellular volume (the apoplast) which is made of the lignocellulosic cell wall. In a previous work we showed that synthetic lignin catalyses the formation of silica nanoparticles at RC-OSi(OH)3 positions. Since the phenolic O-4 position is the most reactive during lignin polymerization, the binding sites form at the expense of β-O-4 lignin backbone bonds. Therefore, synthetic lignin becomes more branched when polymerized in the presence of silicic acid, as compared to lignin polymerized without silicic acid. To study lignin-silica relationships in the plant, we extracted lignin from stems of wild type sorghum and compared it to lignin extracted from mutants exhibiting high and low silica contents. The thermal stability of both non-extracted biomass and extracted lignin was measured using thermogravimetric analysis (TGA). High-silica biomass was thermally less stable than low-silica biomass, suggesting lower content of ether (β-O-4) linkages. This interpretation was supported by gas chromatography-mass spectroscopy (GC-MS). Fourier transform infrared (FTIR) and X-ray photoelectron spectra (XPS) indicated lignin with C-O-Si modifications in all genotypes and further showed silicic acid binding to lignin phenolics and carbonyl moieties. Our results show that lignin extracted from genotypes with native-silicon levels have higher affinity to silicic acid, catalysing silica deposition through Si-O-4 (Si-phenoxyl) bonds, and suggest that the presence of silicic acid during in vivo lignin polymerization reduces β-O-4 ether linkages.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144172067","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}

引用次数: 0

Aerosol, clouds and particles: general discussion. 气溶胶、云和粒子：一般性讨论。

IF 3.3 3区化学

Faraday Discussions Pub Date : 2025-05-29 DOI: 10.1039/d5fd90012c

Sarah Albertin, Markus Ammann, Thorsten Bartels-Rausch, James Brean, Lucy J Carpenter, Rohit Chikkaraddy, Martyn P Chipperfield, Giancarlo Ciarelli, Hugh Coe, Jenée D Cyran, Barbara D'Anna, Bruno Delille, Valerio Ferracci, Markus M Frey, Natasha Garner, Dwayne Heard, Zamin A Kanji, Saewung Kim, Julia Kojoj, Alexis Lamothe, Kathy S Law, Sönke Maus, Claudia Mohr, Jennifer G Murphy, Christian Pfrang, Kerri Pratt, Tjarda Roberts, Jochen Stutz, Thomas Whale, Megan Willis, Xin Yang, Paul Zieger

引用次数: 0

Bone mineralization and the effects of elevated osteopontin: from symmetry-breaking foci to 3D space-filling tessellation. 骨矿化和骨桥蛋白升高的影响：从对称性破坏病灶到三维空间填充镶嵌。

IF 3.3 3区化学

Faraday Discussions Pub Date : 2025-05-29 DOI: 10.1039/d5fd00013k

Joseph Deering, Daniel J Buss, Roland Kröger, Hojatollah Vali, Maureen J Lagos, Natalie Reznikov, Marc D McKee

{"title":"Bone mineralization and the effects of elevated osteopontin: from symmetry-breaking foci to 3D space-filling tessellation.","authors":"Joseph Deering, Daniel J Buss, Roland Kröger, Hojatollah Vali, Maureen J Lagos, Natalie Reznikov, Marc D McKee","doi":"10.1039/d5fd00013k","DOIUrl":"10.1039/d5fd00013k","url":null,"abstract":"At the nanoscale, lamellar bone tissue mineralization ensues via heteronucleation of small mineral foci within the osteoid. The foci grow to produce a mature, volume-filling tessellation pattern at the micrometer-scale. Mineralization-inhibiting osteopontin (OPN) mediates this bone mineralization pathway and, eventually, the microscale properties of bone tissue. Using 2D and 3D electron microscopy, here we have assessed how the abundance of OPN can affect nanoscale mineralization, mineral ripening, and microscale patterning of mineral in normal wild-type mouse bone, and we compare that to mutant mouse models having elevated OPN (Fgf23-/- and Hyp mice). When OPN is elevated, volume-filling mineral tessellation was incomplete (showing a four-fold increase in mineral surface area in the vicinity of the mineralization front in Hyp bone). Immunogold labeling showed excessive OPN in the foci, suggesting an arrest of their growth and an interruption of the pathway towards microscale tessellation. In Fgf23-/- mice, electron tomography and 3D focused ion beam-scanning electron microscopy (FIB-SEM) imaging of mineral foci show instances of core-shell morphology with crystalline mineral confined to the focus interior, and an amorphous nanogranular texture persisting in the outer shell. Electron energy-loss spectroscopy, which is sensitive to nanoscale elemental composition, showed a lower Ca/P ratio at the periphery of Hyp foci, consistent with a more amorphous mineral character, suggesting that OPN may play a role in delaying the amorphous-to-crystalline transition. These aspects of nanoscale mineral maturation in mutant mice having elevated OPN implicate this protein as a fine-tuning regulator of mineralization kinetics, mineral composition, and mechanical properties of bone.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144172063","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}

引用次数: 0

Investigating temperature influences on shell growth and microstructural variations in bay scallops: insights from multiscale microscopy. 研究温度对海湾扇贝壳生长和微观结构变化的影响：来自多尺度显微镜的见解。

IF 3.3 3区化学

Faraday Discussions Pub Date : 2025-05-27 DOI: 10.1039/d5fd00023h

Benazir Khurshid, Arnaud Benchetrite, Lise Guichaoua, Nicolas Brodusch, Bryce D Stewart, Roland Kröger, Raynald Gauvin, Martin Mallet, Réjean Tremblay, Natalie Reznikov

{"title":"Investigating temperature influences on shell growth and microstructural variations in bay scallops: insights from multiscale microscopy.","authors":"Benazir Khurshid, Arnaud Benchetrite, Lise Guichaoua, Nicolas Brodusch, Bryce D Stewart, Roland Kröger, Raynald Gauvin, Martin Mallet, Réjean Tremblay, Natalie Reznikov","doi":"10.1039/d5fd00023h","DOIUrl":"https://doi.org/10.1039/d5fd00023h","url":null,"abstract":"Scallops (order Pectinida) are well-known for their robust and beautiful calcitic shells that protect them from external impacts and predators. Scallops respond to environmental conditions, including water temperature, salinity, and food supply, which are reflected in the shell growth rates and patterning. The bay scallop (Argopecten irradians) is a species of high ecological and aquacultural value in North America, and its habitat may expand towards higher latitudes with inevitable global warming. To investigate the effect of water temperature on the accretion rate and the polycrystalline microstructure of the Bay scallop shell, we conducted a controlled growth experiment on juveniles, 4 weeks following their larval metamorphosis. Approximately 400 individuals, collected from a hatchery 4 weeks after metamorphosis, were then reared in reconstituted seawater for 9 weeks at 23 °C and 26 °C. At 7-, 9-, 11-, and 13-weeks post-metamorphosis, calcein was added to the water for 7 hours for fluorescent staining, and then equal batches of scallops were collected and fixed. Morphologic characterization of bay scallop shells included micro-computed X-ray tomography for 3D measurements to measure shell thickness, and fluorescence light microscopy for accretion rate assessment. We used mechanical testing of complete shells in compression to assess their stiffness, strength and toughness. Microstructural analysis of the shells included scanning electron microscopy and crystallographic analysis by electron backscattered diffraction. The scallops reared in warmer water exhibited a faster growth rate with shells showing higher calcite grain misorientation, no difference in relative shell thickness, and inconclusive difference in the shell mechanical properties. This study may help us to understand the multifarious implications of climate change.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148705","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}

引用次数: 0

Three-dimensional imaging of vasculature and forming quail femur using cryo-correlative light and electron microscopy (cryo-CLEM). 用低温相关光电子显微镜（cryo-CLEM）观察鹌鹑股骨血管和成形的三维成像。

IF 3.3 3区化学

Faraday Discussions Pub Date : 2025-05-27 DOI: 10.1039/d5fd00022j

Anne Seewald, Jingxiao Zhong, Macarena Siri, Peter Fratzl, Emeline Raguin

{"title":"Three-dimensional imaging of vasculature and forming quail femur using cryo-correlative light and electron microscopy (cryo-CLEM).","authors":"Anne Seewald, Jingxiao Zhong, Macarena Siri, Peter Fratzl, Emeline Raguin","doi":"10.1039/d5fd00022j","DOIUrl":"https://doi.org/10.1039/d5fd00022j","url":null,"abstract":"Bone mineralization during embryonic development requires the transport and deposition of an enormous amount of mineral precursors. In avian embryos, blood vessels play a dual role in this context: facilitating the demineralization of the eggshell to supply calcium and other minerals on the one hand, and mediating their deposition into the developing skeleton on the other. Understanding the interface between blood vessels and the surrounding tissues is therefore crucial for unraveling the mechanisms underlying biomineralization. However, visualizing this interface poses significant challenges and requires imaging methods that preserve the ultrastructure in a close-to-native state. Here we present a detailed methodology for a cryogenic correlative light and electron microscopy (cryo-CLEM) workflow to investigate the transport of mineral precursors in blood vessels of the femur of quail embryos during bone development. To achieve this, we use a fluorophore-conjugated antibody to label endothelial cells, which form the inner lining of blood vessels and which mediate exchanges between the bloodstream and developing tissues. This approach enables precise localization of blood vessels through fluorescence microscopy, which is subsequently correlated with 3D high-resolution electron microscopy using Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM). This methodology allows imaging of a sufficient volume to observe both the lumen of the blood vessels and the surrounding matrix, providing deeper insights into calcium transport and bone mineralization during quail embryogenesis.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148707","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}

引用次数: 0

Fiber formation seen through the high-resolution computational microscope. 通过高分辨率计算机显微镜观察到的纤维形成。

IF 3.3 3区化学

Faraday Discussions Pub Date : 2025-05-23 DOI: 10.1039/d4fd00188e

Tomasz K Piskorz, Vasudevan Lakshminarayanan, Alex H de Vries, Jan H van Esch

{"title":"Fiber formation seen through the high-resolution computational microscope.","authors":"Tomasz K Piskorz, Vasudevan Lakshminarayanan, Alex H de Vries, Jan H van Esch","doi":"10.1039/d4fd00188e","DOIUrl":"https://doi.org/10.1039/d4fd00188e","url":null,"abstract":"Supramolecular fibers draw widespread attention due to their role in biological systems and ability to form complex materials exhibiting rich and dynamic behavior. Although the information about the supramolecular structure is encoded in their molecular blocks, a complete understanding of how this information translates into the final structure requires detailed insights into the energy landscape of the process and the possible routes across this landscape. Here, we study the formation of 1,3,5-cyclohexanetricarboxamide fibers by a Markov state model of molecular dynamics simulations with the polarizable CHARMM Drude force-field. We provide insights into all stages of supramolecular fiber formation up to microsecond timescales, starting from primary nucleation, through fiber elongation and secondary nucleation, and finally, the assembly of single fibers into bundles. Our results show that nucleation involves a rapid collapse of dissolved monomers into disordered assemblies, which gradually transform into nuclei and then grow into elongated fibers. Moreover, elongation and secondary nucleation appeared to be competing processes, depending on the density of the monomers adsorbed at the fiber-liquid interface. Finally, bundling involves the initial association of fibers by interactions between surface-exposed groups, followed by stabilization of the bundle by surface reorganization, which allows for favorable interactions between aromatic groups.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144126252","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}

引用次数: 0

Revealing enameloid shark chemistry at the nanoscale. 在纳米尺度上揭示类搪瓷鲨鱼的化学性质。

IF 3.3 3区化学

Faraday Discussions Pub Date : 2025-05-23 DOI: 10.1039/d5fd00019j

Alberto Perez-Huerta, Eshita Samajpati, Gabriela A Farfan

{"title":"Revealing enameloid shark chemistry at the nanoscale.","authors":"Alberto Perez-Huerta, Eshita Samajpati, Gabriela A Farfan","doi":"10.1039/d5fd00019j","DOIUrl":"https://doi.org/10.1039/d5fd00019j","url":null,"abstract":"Shark teeth are considered excellent bio-archives because of their high abundance and preservation potential. Chemical proxies recorded by the teeth enameloid layers are used to interpret ecological and environmental parameters throughout the geological record. The use of these proxies relies on the assumption that biomineralization processes for enameloid formation have remained constant during shark evolution. Here, we test such an assumption by comparing the chemical composition at the nanoscale, using the technique of atom probe tomography (APT), of enameloid in modern and fossil shark teeth. Results indicate that there are clear differences in the chemistry at the core and inter-crystalline grain boundaries of fluorapatite crystals. These boundaries are enriched in strontium in all shark teeth, whereas there are differences in the distribution of magnesium, sodium, and iron. Teeth of the modern shark Isurus oxyrinchus have magnesium and sodium distributed at the inter-crystalline grain boundaries. Teeth of Eocene fossil sharks, Striatolamia macrota and Macrorhizodus praecursor, have a unique distribution of iron, at the inter-crystalline boundaries, and sodium, at the core of the crystals. This observation may indicate that biomineralization processes resulting in enameloid formation are not constant across the phylogeny of sharks. Overall, our findings strongly suggest that the enameloid content and distribution of magnesium, iron, strontium, and sodium are highly controlled by biomineralization processes. The role of magnesium and sodium seems to be similar in mammalian enamel and shark enameloid formation. Yet, nanoscale chemical differences, such as the presence of strontium in tooth enameloid, are likely associated to functional morphology.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144126253","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}

引用次数: 0

Multiphase chemistry: general discussion. 多相化学：一般讨论。

IF 3.3 3区化学

Faraday Discussions Pub Date : 2025-05-22 DOI: 10.1039/d5fd90014j

Sarah Albertin, Markus Ammann, Patrick Ayotte, Thorsten Bartels-Rausch, Hendrik Bluhm, James Brean, Natalie Brett, Lucy V Brown, Tillmann Buttersack, Lucy J Carpenter, Rohit Chikkaraddy, Hugh Coe, Jenée D Cyran, Natasha Garner, Dwayne Heard, Deanna Huff, Saewung Kim, Jingqiu Mao, Jennifer G Murphy, Christian Pfrang, Kerri A Pratt, Matti Rissanen, Joel Savarino, Céline Toubin, Thomas Whale, Megan Willis

引用次数: 0

Unveiling the structure of protein-based hydrogels by overcoming cryo-SEM sample preparation challenges. 通过克服低温扫描电镜样品制备挑战揭示蛋白质基水凝胶的结构。

IF 3.3 3区化学

Faraday Discussions Pub Date : 2025-05-22 DOI: 10.1039/d4fd00204k

Dimitra Katrantzi, Stuart Micklethwaite, Nicole Hondow, Andy Brown, Lorna Dougan

{"title":"Unveiling the structure of protein-based hydrogels by overcoming cryo-SEM sample preparation challenges.","authors":"Dimitra Katrantzi, Stuart Micklethwaite, Nicole Hondow, Andy Brown, Lorna Dougan","doi":"10.1039/d4fd00204k","DOIUrl":"https://doi.org/10.1039/d4fd00204k","url":null,"abstract":"Protein-based hydrogels have gained significant attention for their potential use in applications such as drug delivery and tissue engineering. Their internal structure is complex, spans across multiple length scales and affects their functionality, yet is not well understood because of folded proteins' sensitivity to physical and chemical perturbations and the high water content of hydrogels. Cryo-scanning electron microscopy (cryo-SEM) has the potential to reveal such hierarchical structure when hydrated hydrogels are prepared with appropriate cryofixation. We show for photochemically cross-linked, folded globular bovine serum albumin (BSA) protein hydrogels that preparation artefacts are reduced by in situ gelation, high pressure freezing (HPF), plasma focused ion beam (pFIB) milling, sublimation, and low dose secondary electron imaging. Cryo-SEM of folded BSA protein hydrogels prepared in this way reveals a heterogeneous network with nanoscale porosity (∼60 nm pores) surrounded by high secondary electron emission regions (∼30 nm diameter) interconnected by narrower, lower emission regions (∼20 nm length). This heterogeneous network structure is consistent with small angle scattering studies of folded protein hydrogels, with fractal-like clusters connected by intercluster regions. We further test the potential of cryo-SEM to detect the impact of protein unfolding on hydrogel network formation and reveal nanoscale differences in cluster sizes consistent with those derived from scattering data. Importantly, cryo-SEM directly images pores for sizing in both systems, with initial results on BSA suggesting protein unfolding induces an increase of ∼10 nm in pore sizes. Our findings on cryo-SEM sample preparation challenges and solutions provide new opportunities to link hydrogel structure to function.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118371","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}

引用次数: 0

Co-assembled supramolecular hydrogels: nano-IR sheds light on tripeptide assemblies. 共组装的超分子水凝胶：纳米红外揭示了三肽组装。

IF 3.3 3区化学

Faraday Discussions Pub Date : 2025-05-21 DOI: 10.1039/d4fd00193a

Paola Alletto, Ana M Garcia, Federica Piccirilli, Silvia Marchesan

引用次数: 0