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Porosity dominates over microgel stiffness for promoting chondrogenesis in zwitterionic granular hydrogels. 在促进齐聚物颗粒水凝胶中的软骨生成方面,孔隙率比微凝胶硬度更重要。
IF 5.8 3区 医学 Q1 MATERIALS SCIENCE, BIOMATERIALS Pub Date : 2024-10-22 DOI: 10.1039/d4bm00233d
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.

由交联微凝胶组成的颗粒状水凝胶作为基于细胞的疗法(包括软骨组织再生)的生物材料支架具有巨大的潜力。由于水凝胶的硬度和孔隙率会影响包裹细胞的表型和组织再生的程度,因此设计可调颗粒水凝胶来控制和优化这些参数是非常有必要的。我们假设,可以使用一种基于生物相容性、具有独立的微凝胶内和微凝胶间交联机制的齐聚物材料的颗粒水凝胶平台来调节软骨生成。微凝胶是通过机械破碎光交联的齐聚物羧基甜菜碱丙烯酰胺(CBAA)和甲基丙烯酸磺基甜菜碱(SBMA)水凝胶制成的,并在细胞存在的情况下使用过氧化辣根(HRP)进行二次交联,以产生含有细胞的颗粒状水凝胶。我们改变了微凝胶内部的交联密度,生产出了具有不同硬度(1-3 kPa)和膨胀特性的微凝胶。当这些微凝胶以相同的重量分数重新悬浮并进行二次交联时,由于不同的膨胀特性,会产生具有不同孔隙率(5-40%)的颗粒状水凝胶。具有最高微凝胶硬度和最高孔隙率的支架可实现最大程度的软骨生成。然而,当支架孔隙率保持不变而仅微凝胶硬度发生变化时,不同支架的细胞表型和软骨生成情况相似。这些结果表明,颗粒状支架孔隙率对软骨形成起主导作用,而微凝胶硬度的作用相对较小。这些观察结果与包裹在传统块状水凝胶中的细胞形成了鲜明对比,在传统块状水凝胶中,硬度会显著影响软骨细胞的反应。总之,我们引入了化学定义的齐聚物生物材料来制造多功能颗粒水凝胶,使支架孔隙率和微凝胶硬度可调,从而研究和影响软骨形成。
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引用次数: 0
Retraction: Glycolipid nanotube templates for the production of hydrophilic/hydrophobic and left/right-handed helical polydiacetylene nanotubes.
IF 4.3 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.1039/d4cc90368d
Naohiro Kameta, Wuxiao Ding, Mitsutoshi Masuda

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.

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引用次数: 0
Biocompatible recombinant type III collagen enhancing skin repair and anti-wrinkle effects. 生物相容性重组 III 型胶原蛋白可增强皮肤修复和抗皱效果。
IF 5.8 3区 医学 Q1 MATERIALS SCIENCE, BIOMATERIALS Pub Date : 2024-10-22 DOI: 10.1039/d4bm01284d
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。
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引用次数: 0
Fundamental basis of mechanochemical reactivity. 机械化学反应的基本原理。
IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-22 DOI: 10.1039/d4cp90153c
Adam A L Michalchuk, Francesco Delogu
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引用次数: 0
Along the gut-bone marrow signaling pathway: use of longan polysaccharides to regenerate blood cells after chemotherapy-induced myelosuppression.
IF 5.1 1区 农林科学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2024-10-22 DOI: 10.1039/d4fo03758h
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.

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引用次数: 0
Generation of nanobodies with conformational specificity for tau oligomers that recognize tau aggregates from human Alzheimer's disease samples.
IF 5.8 3区 医学 Q1 MATERIALS SCIENCE, BIOMATERIALS Pub Date : 2024-10-22 DOI: 10.1039/d4bm00707g
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。
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引用次数: 0
Aminophosphonium organocatalysts for the ring-opening copolymerisation of epoxide and cyclic anhydride.
IF 4.3 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.1039/d4cc03947e
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.

利用基尔萨诺夫反应合成了空气稳定、高效和选择性双功能氨基膦催化剂,用于环己烯氧化物和邻苯二甲酸酐的交替开环共聚,而无需助引发剂。
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引用次数: 0
Synthesis of bis(indolyl)methanes using N-heterocyclic carbene salt as a C1 precursor. 使用 N-杂环碳烯盐作为 C1 前体合成双(吲哚基)甲烷。
IF 2.9 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-10-22 DOI: 10.1039/d4ob01568a
Bingwei Zhou, Zhao Gao, Yanhao Yang, Yuanyuan Hu

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.

我们在此介绍吲哚与 NHC 盐的烷基化反应,以获得双(吲哚基)甲烷作为产物。NHC 盐(或游离 NHC)因其 N-杂环的分解而成为 C1 前体。虽然锌粉和乙酸/甲酸的确切作用仍难以确定,但它们在该反应中都是不可或缺的。根据机理实验的结果,提出了两种可能的反应途径。
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引用次数: 0
A formally exact theory to construct nonreactive forcefields using linear regression to optimize bonded parameters† 利用线性回归优化键合参数,构建非反应力场的正式精确理论†。
IF 3.9 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.1039/D4RA01861C
Thomas A. Manz
<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
本文推导了力场函数论(FFFT)的理论基础。FFFT 研究与非反应力场函数表示相关的课题,以实现各种理想特性,如(a) 力场的能量函数在某些条件下具有形式上的精确性,(b) 具有形式上精确的反演,可将键合簇内的键合势能与非键合势能分开,从而使键合参数可通过线性回归进行优化,而无需非线性回归,(c) 在由一个电子基态定义的子域内,相对于能量上可获得的内部坐标位移,势能具有各种阶次的连续可微分性、(d) 力场设计能保证参考基态几何结构作为平衡结构在力场势能图上精确再现;(e) 合理准确且广泛适用的节俭模型势能;(f) 计算效率高的嵌入式特征选择,能识别并去除不重要的力场项;(g) 设计合理的方法,根据量子力学计算和(可选)实验参考数据对力场进行参数化;以及 (h) 近似再现实验测量特性的力场。本文还介绍了:(1) 一种角度弯曲模型势能,它能更准确地描述物理动力学,即使在键角是线性的情况下(即 θ = π (180°)),也能对内部坐标位移进行所有阶的连续微分;(2) 一种第一原理衍生的拉伸势能,它能准确地描述短程保利斥力和长程键解离能。这种新的角度弯曲势与 CaH2、CO2、H2O、HNO、Li2O、NO2、NS2、SF2、SiH2 和 SO2 分子的 CCSD 量子化学计算结果非常吻合。这种新的键伸展势分别再现了 H2 和 O2 分子的前 12+ 和 30+ 个振动能级,与实验值相差无几。以研究 C6F6 中的 C-F 键伸展为例,与旧公式相比,新公式(上述(b)项)将优化力常数值对非键相互作用参数选择的敏感性降低了一个数量级。对 CO2、H2O、HNO 和 SO2 分子的优化柔性模型进行法向模态分析,得出的振动转变频率与实验值相差无几。这些结果证明了这种新方法的优势。
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引用次数: 0
Fe3O4 nanostructure films as solar-thermal conversion materials for ammonia synthesis.
IF 4.3 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.1039/d4cc04112g
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.

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引用次数: 0
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