Accounts of Chemical Research最新文献

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Rational Design and Controlled Synthesis of High-Performance Inorganic Short-Wave UV Nonlinear Optical Materials.
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-12-12 DOI: 10.1021/acs.accounts.4c00704
Xuehua Dong, Ling Huang, Guohong Zou
{"title":"Rational Design and Controlled Synthesis of High-Performance Inorganic Short-Wave UV Nonlinear Optical Materials.","authors":"Xuehua Dong, Ling Huang, Guohong Zou","doi":"10.1021/acs.accounts.4c00704","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00704","url":null,"abstract":"<p><p>ConspectusThe invention of the laser marked a milestone in modern science and technology. Inorganic second-order nonlinear optical (NLO) crystals, with their unique frequency conversion capabilities, play a critical role in extending laser wavelength ranges. These materials are indispensable in laser science, information transmission, and other fields such as the industrial Internet. As Moore's Law drives the demand for shorter wavelengths and higher-precision laser sources, the development of high-performance short-wave ultraviolet (UV) (<300 nm) NLO materials for UV solid-state lasers has become increasingly important. While researchers have synthesized a variety of NLO crystals, their discovery has largely relied on trial-and-error approaches, which are not only time-consuming but also serendipitous rather than based on rational design principles. Moreover, the complexity of designing these materials is compounded by the need to meet several strict functional criteria, including a short UV cutoff edge, a strong second-harmonic generation (SHG) effect, and moderate birefringence, all of which hinder efficient synthesis. The rational design and controlled synthesis of high-performance short-wave UV NLO crystals, therefore, remains a significant scientific challenge.In this Account, we propose a three-step strategy to address this challenge: (1) Rational screening of highly polar functional groups, particularly new NLO-active groups with novel bonding characteristics (π-localized distorted [O<sub>2</sub>]<sup>2-</sup> anions, highly polarizable <i>d</i><sup>10</sup> cations such as Zn<sup>2+</sup>, Cd<sup>2+</sup>, and Hg<sup>2+</sup>, and cations containing stereochemically active lone pairs (SCALP) including Ge<sup>2+</sup>, Sn<sup>2+</sup>, Sb<sup>3+</sup>, and Pb<sup>2+</sup>) that exhibit significantly enhanced polarization anisotropy and hyperpolarizability, to replace traditional anionic groups (planar π-conjugated groups such as [BO<sub>3</sub>]<sup>3-</sup>, [CO<sub>3</sub>]<sup>2-</sup>, and [NO<sub>3</sub>]<sup>-</sup>, and non-π-conjugated tetrahedral anions, such as [SO<sub>4</sub>]<sup>2-</sup> and [PO<sub>4</sub>]<sup>3-</sup>). (2) Precise regulation of crystal structures to sequentially construct functional groups using two methods: (a) a template-oriented synthesis strategy, which is a method that guides the formation of desired materials through crystal engineering, based on ideal structural models, and (b) a multifunctional primitive module assembly strategy, by identifying and designing multifunctional modules with specific structural configurations to achieve ordered arrangement, which facilitates the creation of high-performance materials. (3) Controlled synthesis of target compounds through synthesis method innovation. These strategies have successfully guided the discovery of several high-performance short-wave UV NLO crystals, including GeHPO<sub>3</sub>, ASbX<sub>2</sub>SO<sub>4</sub> (A = K, Rb, Cs, NH<sub>4</sub","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816631","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
Photoresponsive Chemistries for User-Directed Hydrogel Network Modulation to Investigate Cell-Matrix Interactions.
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-12-12 DOI: 10.1021/acs.accounts.4c00548
Monica L Ohnsorg, Ella A Hushka, Kristi S Anseth
{"title":"Photoresponsive Chemistries for User-Directed Hydrogel Network Modulation to Investigate Cell-Matrix Interactions.","authors":"Monica L Ohnsorg, Ella A Hushka, Kristi S Anseth","doi":"10.1021/acs.accounts.4c00548","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00548","url":null,"abstract":"<p><p>ConspectusSynthetic extracellular matrix (ECM) engineering is a highly interdisciplinary field integrating materials and polymer science and engineering, chemistry, cell biology, and medicine to develop innovative strategies to investigate and control cell-matrix interactions. Cellular microenvironments are complex and highly dynamic, changing in response to injury and disease. To capture some of these critical dynamics <i>in vitro</i>, biomaterial matrices have been developed with tailorable properties that can be modulated <i>in situ</i> in the presence of cells. While numerous macromolecules can serve as a basis in the design of a synthetic ECM, our group has exploited multi-arm poly(ethylene glycol) (PEG) macromolecules because of the ease of functionalization, many complementary bio-click reactions to conjugate biological signals, and ultimately, the ability to create well-defined systems to investigate cell-matrix interactions. To date, significant strides have been made in developing bio-responsive and transient synthetic ECM materials that degrade, relax stress, or strain-stiffen in response to cell-mediated stimuli through ECM-cleaving enzymes or integrin-mediated ECM adhesions. However, our group has also designed hydrogels incorporating different photoresponsive moieties, and these moieties facilitate user-defined spatiotemporal modulation of the extracellular microenvironment <i>in vitro</i>. The application of light allows one to break, form, and rearrange network bonds in the presence of cells to alter the biomechanical and biochemical microenvironment to investigate cell-matrix interactions in real-time. Such photoresponsive materials have facilitated fundamental discoveries in the biological pathways related to outside-in signaling, which guide important processes related to tissue development, homeostasis, disease progression, and regeneration.This review focuses on the phototunable chemical toolbox that has been used by Anseth and co-workers to modulate hydrogel properties post-network formation through: bond-breaking chemistries, such as <i>o</i>-nitrobenzyl and coumarin methyl ester photolysis; bond-forming chemistries, such as azadibenzocyclooctyne photo-oligomerization and anthracene dimerization; and bond-rearranging chemistries, such as allyl sulfide addition-fragmentation chain transfer and reversible ring opening polymerization of 1,2-dithiolanes. By using light to modulate the cellular microenvironment (in 2D, 3D, and even 4D), innovative experiments can be designed to study mechanosensing of single cells or multicellular constructs, pattern adhesive ligands to spatially control cell-integrin binding or modulate on-demand the surrounding cell niche to alter outside-in signaling in a temporally controlled manner. To date, these photochemically defined materials have been used for the culture, differentiation, and directed morphogenesis of primary cells and stem cells, co-cultured cells, and even multicellular const","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142811395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
N-Acyl-N-alkyl/aryl Sulfonamide Chemistry Assisted by Proximity for Modification and Covalent Inhibition of Endogenous Proteins in Living Systems.
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-12-11 DOI: 10.1021/acs.accounts.4c00628
Tomonori Tamura, Itaru Hamachi
{"title":"<i>N</i>-Acyl-<i>N</i>-alkyl/aryl Sulfonamide Chemistry Assisted by Proximity for Modification and Covalent Inhibition of Endogenous Proteins in Living Systems.","authors":"Tomonori Tamura, Itaru Hamachi","doi":"10.1021/acs.accounts.4c00628","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00628","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusSelective chemical modification of endogenous proteins in living systems with synthetic small molecular probes is a central challenge in chemical biology. Such modification has a variety of applications important for biological and pharmaceutical research, including protein visualization, protein functionalization, proteome-wide profiling of enzyme activity, and irreversible inhibition of protein activity. Traditional chemistry for selective protein modification in cells largely relies on the high nucleophilicity of cysteine residues to ensure target-selectivity and site-specificity of modification. More recently, lysine residues, which are more abundant on protein surfaces, have attracted attention for the covalent modification of proteins. However, it has been difficult to efficiently modify the ε-amino groups of lysine side-chains, which are mostly (∼99.9%) protonated and thus exhibit low nucleophilicity at physiological pH. Our group revealed that &lt;i&gt;N&lt;/i&gt;-acyl-&lt;i&gt;N&lt;/i&gt;-alkyl sulfonamide (NASA) moieties can rapidly and efficiently acylate noncatalytic (i.e., less reactive) lysine residues in proteins by leveraging a reaction acceleration effect via proximity. The excellent reaction kinetics and selectivity for lysine of the NASA chemistry enable covalent modification of natural intracellular and cell-surface proteins, which is intractable using conventional chemistries. Moreover, recently developed &lt;i&gt;N&lt;/i&gt;-acyl-&lt;i&gt;N&lt;/i&gt;-aryl sulfonamide (ArNASA) scaffolds overcome some problems faced by the first-generation NASA compounds. In this Account, we summarize our recent works in the development of NASA/ArNASA chemistry and several applications reported by ourselves and other groups. First, we characterize the basic properties of NASA/ArNASA chemistry, including the labeling kinetics, amino acid preference, and biocompatibility, and compare this approach with other ligand-directed chemistries. This section also describes the principles of nucleophilic organocatalyst-mediated protein acylation, another important protein labeling strategy using the NASA reactive group, and its application to neurotransmitter receptor labeling in brain slices. Second, we highlight various recent examples of protein functionalization using NASA/ArNASA chemistry, such as visualization of membrane proteins including therapeutically important G-protein coupled receptors, gel-based ligand screening assays, photochemical control of protein activity, and targeted protein degradation. Third, we survey covalent inhibition of proteins by NASA/ArNASA-based lysine-targeting. The unprecedented reactivity of NASA/ArNASA toward lysine allows highly potent, irreversible inhibition of several drug targets for the treatment of cancer, including HSP90, HDM2-p53 protein-protein interaction, and a Bruton's tyrosine kinase mutant that has developed resistance to cysteine-targeted covalent-binding drugs. Finally, current limitations of, and future perspectives on, this resear","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
Physics and Chemistry of Two-Dimensional Triangulene-Based Lattices. 基于二维三角菱形晶格的物理和化学。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-12-10 DOI: 10.1021/acs.accounts.4c00557
Hongde Yu, Yu Jing, Thomas Heine
{"title":"Physics and Chemistry of Two-Dimensional Triangulene-Based Lattices.","authors":"Hongde Yu, Yu Jing, Thomas Heine","doi":"10.1021/acs.accounts.4c00557","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00557","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusTriangulene (TRI) and its heterotriangulene (HT) derivatives are planar, triangle-shaped molecules that, via suitable coupling reactions, can form extended organic two-dimensional (2D) crystal (O2DC) structures. While TRI is a diradical, HTs are either closed-shell molecules or monoradicals which can be stabilized in their cationic form.Triangulene-based O2DCs have a characteristic honeycomb-kagome lattice. This structure gives rise to four characteristic electronic bands: two of them form Dirac points, while the other two are flat and sandwich the Dirac bands. Functionalization and heteroatoms are suitable means to engineer this band structure. Heteroatoms like boron and nitrogen shift the Fermi level upward and downward, respectively, while bridging groups and functionalized triangulene edges can introduce a dispersion to the flat bands.The stable backbone architecture makes 2D HT-polymers ideal for photoelectrochemical applications: (i) bridge functionalization can tune the band gap and maximize absorption, (ii) the choice of the center atom (B or N) controls the band occupation and shifts the Fermi level with respect to vacuum, allowing in some cases for overpotential-free photon-driven surface reactions, and (iii) the large surface area allows for a high flux of educts and products.The spin polarization in TRI and in open-shell HTs is maintained when linking them to dimers or extended frameworks with direct coupling or more elaborate bridging groups (acetylene, diacetylene, and phenyl). The dimers have a high spin-polarization energy and some of them are strongly magnetically coupled, resulting in stable high-spin or broken-symmetry (BS) low-spin systems. As O2DCs, some systems become antiferromagnetic Mott insulators with large band gaps, while others show Stoner ferromagnetism, maintaining the characteristic honeycomb-kagome bands but shifting the opposite spin-polarized bands to different energies. For O2DCs based on aza- and boratriangulene (monoradicals as building blocks), the Fermi level is shifted to a spin-polarized Dirac point, and the systems have a Curie temperature of about 250 K. For half-filled (all-carbon) systems, the Ovchinnikov rule or, equivalently, Lieb's theorem, is sufficient to predict the magnetic ordering of the systems, while the non-half-filled systems (i.e., those with heteroatoms) obey the more involved Goodenough-Kanamori rule to interpret the magnetism on the grounds of fundamental electronic interactions.There remain challenges in experiment and in theory to advance the field of triangulene-based O2DCs: Coupling reactions beyond surface chemistry have to be developed to allow for highly ordered, extended crystals. Multilayer structures, which are unexplored to date, will be inevitable in alternative synthesis approaches. The predictive power of density-functional theory (DFT) within state-of-the-art functionals is limited for the description of magnetic couplings in these systems due to the ap","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142826513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
Emergence of Low-Cost and High-Performance Nonfused Ring Electron Acceptors. 低成本高性能非熔环电子受体的出现。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-12-03 Epub Date: 2024-11-20 DOI: 10.1021/acs.accounts.4c00592
Pengcheng Jiang, Yahui Liu, Jinsheng Song, Zhishan Bo
{"title":"Emergence of Low-Cost and High-Performance Nonfused Ring Electron Acceptors.","authors":"Pengcheng Jiang, Yahui Liu, Jinsheng Song, Zhishan Bo","doi":"10.1021/acs.accounts.4c00592","DOIUrl":"10.1021/acs.accounts.4c00592","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusOrganic solar cells (OSCs) have garnered significant attention in academic and industrial circles due to their advantages such as lightweight, excellent bending performance, and the ability to be fabricated into semitransparent devices. Since the proposal of the bulk heterojunction concept by Heeger et al. in 1995, conjugated polymer/fullerene pairs have gradually emerged as the optimal choice for active layer materials in OSCs. Fullerene derivatives were preferred as electron acceptors in OSCs because of their high electron mobility. However, due to limitations such as insufficient light absorption, limited derivative potential, and poor energy level tunability, the power conversion efficiency (PCE) of OSCs based on fullerene derivatives has encountered a bottleneck of approximately 12%, despite the continuous updates in polymer donor materials over nearly two decades of development, leading to a gradual decline in their importance. By contrast, nonfullerene electron acceptors (NFAs) have gradually gained dominance in this field since first appearing in 2015, thanks to their advantages of tunable absorption spectrum, adjustable energy levels, and modifiable chemical structure. Among nonfullerene acceptors, fused-ring electron acceptors (FREAs) such as ITIC and Y6 have achieved significant progress, boosting the PCE of OSCs to 20%. This milestone achievement indicates the potential of their commercial applications. However, the synthesis process of FREA is complex and often constrained by low-yield ring-closure reactions, resulting in high costs.The molecular backbone of nonfused ring electron acceptors (NFREAs) is composed of single bonds, which enables the adoption of modular synthesis mainly via Stille (based on organotin reactant) and/or Suzuki (based on organoboron reactant) coupling or C-H activation (without prefunctionalization) and avoids low-yield ring-closing reactions, thus making them a potential alternative to fused-ring acceptors. To achieve a planar molecular backbone and minimize energy loss due to conformational rotation, our team innovatively used intramolecular noncovalent interactions as a replacement for traditional covalent bonds. Furthermore, to address the issues of poor solubility and excessive aggregation during film formation for NFREAs, we strategically introduced sterically hindered side groups, such as 2,6-bis(alkyloxy)phenyl and diphenylamino, into the molecular design, effectively mitigating these problems. These innovative design concepts have significantly advanced the development of high-performance NFREAs and have garnered increasing attention from the research community. The PCEs of OSCs based on NFREAs have significantly improved from less than 10% to close to 20% since their initial discovery. By optimizing the device fabrication process, we have achieved a PCE of over 19%, which is comparable to that of FREAs. This article will delve into the evolution and latest research progress of NFREAs","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"3419-3432"},"PeriodicalIF":16.4,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142680017","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
The Emerging Roles of Multimolecular G-Quadruplexes in Transcriptional Regulation and Chromatin Organization. 多分子 G-四联体在转录调控和染色质组织中的新作用
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-12-03 Epub Date: 2024-11-18 DOI: 10.1021/acs.accounts.4c00574
Naura Fakhira Antariksa, Marco Di Antonio
{"title":"The Emerging Roles of Multimolecular G-Quadruplexes in Transcriptional Regulation and Chromatin Organization.","authors":"Naura Fakhira Antariksa, Marco Di Antonio","doi":"10.1021/acs.accounts.4c00574","DOIUrl":"10.1021/acs.accounts.4c00574","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusThe ability of genomic DNA to adopt non-canonical secondary structures known as G-quadruplexes (G4s) under physiological conditions has been recognized for its potential regulatory function of various biological processes. Among those, transcription has recently emerged as a key process that can be heavily affected by G4 formation, particularly when these structures form at gene promoters. While the presence of G4s within gene promoters has been traditionally associated with transcriptional inhibition, in a model whereby G4s act as roadblocks to polymerase elongation, recent genomics experiments have revealed that the regulatory role of G4s in transcription is more complex than initially anticipated. Indeed, earlier studies linking G4-formation and transcription mainly relied on small-molecule ligands to stabilize and promote G4s, which might lead to disruption of protein-DNA interactions and local environments and, therefore, does not necessarily reflect the endogenous function of G4s at gene promoters. There is now strong evidence pointing toward G4s being associated with transcriptional enhancement, rather than repression, through multifaceted mechanisms such as recruitment of key transcriptional proteins, molding of chromatin architecture, and mode of phase separation.In this Account, we explore pivotal findings from our research on a particular subset of G4s, namely, those formed through interactions between distant genomic locations or independent nucleic acid strands, referred to as multimolecular G4s (mG4s), and discuss their active role in transcriptional regulation. We present our recent studies suggesting that the formation of mG4s may positively regulate transcription by inducing phase-separation and selectively recruiting chromatin-remodeling proteins. Our work highlighted how mG4-forming DNA and RNA sequences can lead to liquid-liquid phase separation (LLPS) in the absence of any protein. This discovery provided new insights into a potential mechanism by which mG4 can positively regulate active gene expression, namely, by establishing DNA networks based on distal guanine-guanine base pairing that creates liquid droplets at the interface of DNA loops. This is particularly relevant in light of the increasing evidence suggesting that G4 structures formed at enhancers can drive elevated expression of the associated genes. Given the complex three-dimensional nature of enhancers, our findings underscore how mG4 formation at enhancers would be particularly beneficial for promoting transcription. Moreover, we will elaborate on our recent discovery of a DNA repair and chromatin remodeling protein named Cockayne Syndrome B (CSB) that displays astonishing binding selectivity to mG4s over the more canonical unimolecular counterparts, suggesting another role of mG4s for molding chromatin architecture at DNA loops sites.Altogether, the studies presented in this Account suggest that mG4 formation in a chromatin context could be a c","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"3397-3406"},"PeriodicalIF":16.4,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11618987/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646167","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Renewable Fuels and Chemical Recycling of Plastics via Hydrothermal Liquefaction. 通过水热液化实现塑料的可再生燃料和化学回收。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-12-03 Epub Date: 2024-11-20 DOI: 10.1021/acs.accounts.4c00524
Phillip E Savage
{"title":"Renewable Fuels and Chemical Recycling of Plastics via Hydrothermal Liquefaction.","authors":"Phillip E Savage","doi":"10.1021/acs.accounts.4c00524","DOIUrl":"10.1021/acs.accounts.4c00524","url":null,"abstract":"<p><p>ConspectusHydrothermal liquefaction (HTL) converts a wide range of biomass feedstocks into a renewable bio-oil via reactions in hot, compressed water. Other products that form partition into the gas, aqueous, or solid phases. The reactions taking place during HTL include hydrolysis, decarboxylation, condensations, additions, deamination, and dehydration. Bio-oil production from HTL has been demonstrated for many renewable materials including microalgae, macroalgae, sludge from water treatment, food waste, agricultural residues, bacteria, yeast, and a wide variety of lignocellulosic materials. HTL of whole biomass is an energy densification process as it generally recovers about 70-80% of chemical energy in an oil product that is just 20-50 wt % of the mass of the original feedstock. The oil is typically rich in oxygen (10 -20 wt %) and also in nitrogen (about 5 wt %), if the biomass contains protein. The oil also contains metals such as iron. Therefore, an upgrading and/or refining process would be required to convert the crude bio-oil to a finished fuel. Each biochemical component in biomass (e.g., polysaccharides, protein, lipids, lignin) contributes different proportions of its initial mass to biocrude. Lipids provide the highest biocrude yields whereas polysaccharides and lignin provide the lowest. Kinetics models have been developed that incorporate different reactivities for the different biochemical components. These models, which are effective in correlating and predicting the yields of biocrude and other product fractions from HTL, can be used in technoeconomic analysis and life-cycle assessments to advance commercial adoption of the technology.HTL is also effective in producing an oil product from decomposition of many different plastics. Thus, it can be used for chemical recycling or valorization of post-consumer waste plastics. Polyolefins and polycarbonates can give oil yields exceeding 90 wt %. Polyethylene terephthalate (PET) gives very low oil yields. The major product from PET hydrolysis, terephthalic acid, is a solid at room temperature and not soluble in the organic solvents typically used to recover oil.Hydrothermal decomposition of isolated biochemical components of biomass and individual synthetic polymers provides insights into the governing chemical reaction pathways. Results from such experiments also enable development of component additivity models that can predict oil yields and other outcomes from HTL of biomass, plastics, and their mixtures.Research needs in this field include more detailed, molecular-level kinetics models, experimental work on HTL and hydrolysis of the many synthetic plastics that have not yet been adequately explored, and experiments and modeling for mixtures of different plastics and mixtures of plastics with biomass.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"3386-3396"},"PeriodicalIF":16.4,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142680024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
Children's Perspectives on Food Allergy in Schools: A Qualitative Study. 儿童对学校食物过敏的看法:定性研究。
IF 1.5 1区 化学
Accounts of Chemical Research Pub Date : 2024-12-01 Epub Date: 2022-10-11 DOI: 10.1177/10598405221130694
Laura Y Feldman, Kaitlyn Merrill, Michael A Golding, Tessa Memauri, S Michelle Driedger, Nancy L Ross, Jennifer L P Protudjer
{"title":"Children's Perspectives on Food Allergy in Schools: A Qualitative Study.","authors":"Laura Y Feldman, Kaitlyn Merrill, Michael A Golding, Tessa Memauri, S Michelle Driedger, Nancy L Ross, Jennifer L P Protudjer","doi":"10.1177/10598405221130694","DOIUrl":"10.1177/10598405221130694","url":null,"abstract":"<p><p>Approximately 7% of children live with food allergy, a condition that requires dietary avoidance to prevent an allergic reaction. In this qualitative study, we aimed to understand food allergy-related experiences, beliefs and learning preferences among children with and without food allergies, to inform a school-based, food allergy education program. Data were analysed thematically. We virtually interviewed children in Kindergarten-Grade 8 in Manitoba, Canada, with (n = 7) and without (n = 9) parent-reported, physician-diagnosed food allergies. We identified three themes: Naive reliance on peers and school staff to assist with food allergy management; Limited food allergy knowledge; and, Recommended food allergy curricula: complementary perspective. Our findings will help inform the development of a school-based, food allergy education program, with a long-term goal of minimizing food allergy-related worries and optimizing safety for children with food allergy. Ongoing, school-based food allergy education is needed.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"653-661"},"PeriodicalIF":1.5,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11558932/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"33498109","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Endoscopic excision of an aqueduct of Sylvius cavernoma causing obstructive hydrocephalus: technical note. 导致梗阻性脑积水的西尔维斯海绵瘤导水管内窥镜切除术:技术说明。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-12-01 Epub Date: 2022-01-10 DOI: 10.1080/02688697.2021.2024501
Daniel De-Liang Loh, Min Wei Chen, Jia Xu Lim, Nicole Chwee Har Keong, Ramez Wadie Kirollos
{"title":"Endoscopic excision of an aqueduct of Sylvius cavernoma causing obstructive hydrocephalus: technical note.","authors":"Daniel De-Liang Loh, Min Wei Chen, Jia Xu Lim, Nicole Chwee Har Keong, Ramez Wadie Kirollos","doi":"10.1080/02688697.2021.2024501","DOIUrl":"10.1080/02688697.2021.2024501","url":null,"abstract":"<p><strong>Background and importance: </strong>Acquired lesions within the aqueduct of Sylvius are rare and their surgical management is challenging. Open transcranial approaches require dissection and manipulation of surrounding eloquent structures. Use of an endoscope can avoid potential morbidity from traversing and handling eloquent structures during open approaches whilst providing better visualisation of an intraventricular lesion.</p><p><strong>Clinical presentation: </strong>A 62-year-old female presented with insidious onset short-term memory loss, unsteady gait, urinary incontinence and left-sided dysaesthesia. Magnetic resonance imaging (MRI) revealed hydrocephalus from an obstructive haemorrhagic lesion consistent with a cavernoma at the central midbrain within the aqueduct of Sylvius. An endoscopic approach was selected to provide optimal visualisation of the lesion. As only a single instrument could be accommodated, rotational movements were employed to tease out the lesion. Gross total resection was achieved. Her symptoms improved immediately postoperatively and she made a complete recovery by 2 months. Post-operative MRI showed resolution of hydrocephalus and no evidence of residual/recurrence of the lesion. Unfortunately, she developed hydrocephalus 3 months post-op and required placement of a ventriculoperitoneal shunt.</p><p><strong>Conclusions: </strong>Endoscopic resection is safe and feasible for selected periaqueductal lesions as it provides direct access while minimising disruption of the surrounding anatomical structures. The limitation of only having a single instrument can be overcome by employing rotational movements.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"1475-1478"},"PeriodicalIF":16.4,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"39801369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
A complex anterior communicating artery aneurysm projecting into the sella turcica. 一个复杂的前交通动脉瘤突入蝶鞍。
IF 16.4 1区 化学
Accounts of Chemical Research Pub Date : 2024-12-01 Epub Date: 2022-11-29 DOI: 10.1080/02688697.2022.2151562
Austin J Borja, Awinita Barpujari, Omar A Choudhri
{"title":"A complex anterior communicating artery aneurysm projecting into the sella turcica.","authors":"Austin J Borja, Awinita Barpujari, Omar A Choudhri","doi":"10.1080/02688697.2022.2151562","DOIUrl":"10.1080/02688697.2022.2151562","url":null,"abstract":"<p><p>Intrasellar aneurysms are rare vascular lesions that typically present with symptoms of mass effect upon the pituitary gland and optic apparatus. Most arise from the internal carotid artery, while only a handful of case reports describe intrasellar aneurysms originating from the anterior communicating artery. The appropriate recognition and management of these lesions are critical to prevent irreversible neurological deficits and catastrophic hemorrhage. Here, we highlight a patient with an anterior communicating artery aneurysm projecting into the sella turcica, leading to hyponatremia, pituitary dysfunction, and chiasmal compression.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":"1302-1303"},"PeriodicalIF":16.4,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"40722961","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
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