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Boosting narrow-band near-infrared-emitting efficiency of thulium by lattice modulation for reflective absorption bioimaging 通过晶格调制提高铥的窄带近红外发射效率,实现反射吸收生物成像
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2024.09.024
Kaina Wang , Jipeng Fu , Sibo Zhan , Hongliang Dong , Chenjie Lou , Tianyi Sun , Jinru Liu , Bingyu Huang , Long Tian , Lihong Jiang , Ran Pang , Su Zhang , Huajie Luo , Mathieu Allix , Xiaojun Kuang , Shiqing Xu , Hongjie Zhang , Mingxue Tang
Near-infrared (NIR) luminescence materials with narrow-band emissions are essential for brain and muscle activity imaging based on the absorption difference of oxygenated proteins. However, most known NIR-emitting materials are limited by low external quantum efficiency (EQE) and broadband properties. This work presents the careful design of Tm, Na-doped strontium sulfide (SrS: Tm3+, Na+) phosphor for NIR light-emitting diode (LED), which shows a narrow emitting band of 27 nm. The successful incorporation of Na+ into SrS: Tm3+ contributes to the suppression of lattice phonons, resulting in significant improvement in EQE from 33.6% to 53.7% and an increase in thermal stability. The efficient host absorption and energy transfer are facilitated by the crystallographic Sr defects and the distortion in the symmetric crystal, disclosed by solid-state NMR, electron paramagnetic resonance (EPR), transient spectra, and X-ray total scattering analysis. Subsequently, efficient identification of vascular patterns based on the differential absorption of hemoglobin enables the potential application of rare-earth luminescent materials in NIR phosphor-converted light-emitting diodes (pc-LEDs) and bioimaging.
基于含氧蛋白质的吸收差异,具有窄带发射的近红外(NIR)发光材料对于大脑和肌肉活动成像至关重要。然而,大多数已知的近红外发光材料都受限于较低的外部量子效率(EQE)和宽带特性。本研究精心设计了掺 Tm、Na 的硫化锶(SrS:Tm3+、Na+)荧光粉,用于近红外发光二极管(LED)。将 Na+ 成功加入 SrS:Tm3+ 中成功掺入 Na+ 有助于抑制晶格声子,从而将 EQE 从 33.6% 显著提高到 53.7%,并增强了热稳定性。固态核磁共振(NMR)、电子顺磁共振(EPR)、瞬态光谱和 X 射线全散射分析表明,晶体学上的 Sr 缺陷和对称晶体的畸变促进了高效的宿主吸收和能量转移。随后,根据血红蛋白的差异吸收有效识别血管模式,使稀土发光材料有望应用于近红外荧光粉转换发光二极管(pc-LED)和生物成像。
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引用次数: 0
Remote optical chirality transfer via helical polyaromatic capsules upon encapsulation 通过螺旋多芳香族胶囊封装实现远程光学手性转移
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2024.09.031
Hayate Sasafuchi , Mayuko Ueda , Natsuki Kishida , Tomohisa Sawada , Seika Suzuki , Yoshitane Imai , Michito Yoshizawa
Helical molecular assemblies have been widely created so far, taking inspiration from helical bioconstructs (e.g., DNAs and proteins). However, the host utilities of such synthetic helices remain largely underdeveloped, particularly as chiroptical nanotools. Here, we report the preparation of new polyaromatic capsules with right- or left-handed quadruple helicity, regulated by chiral saccharide-based side chains attached at the outer surface. The capsule quantitatively encapsulates achiral fluorescent dyes in the cavity. The resultant host-guest complexes display excellent circularly polarized luminescence properties (up to |glum| = 1.6 × 10−2) derived from the bound dyes, through efficient optical chirality transfer from the outer biochiral groups to the inner achiral dyes via the quadruple helical shell, which represents an unprecedented chiroptical strategy. This nanotool can be applied to spherical fullerene to induce its chirality with high efficiency in solution (up to |gabs| = 1.0 × 10−2) and in the solid state.
迄今为止,人们从螺旋状生物结构(如 DNA 和蛋白质)中汲取灵感,广泛创造出螺旋状分子组装体。然而,这种合成螺旋的宿主效用在很大程度上仍未得到充分开发,尤其是在作为光电纳米工具方面。在此,我们报告了新型多芳香族胶囊的制备过程,这种胶囊具有右手或左手四重螺旋,由连接在外表面的手性糖基侧链调节。这种胶囊可在空腔中定量封装非手性荧光染料。通过外层生物手性基团经由四重螺旋壳向内层非手性染料的高效光学手性转移,由此产生的主-客复合物显示出源自结合染料的优异圆偏振发光特性(高达 |glum| = 1.6 × 10-2),这是一种前所未有的手性策略。这种纳米工具可用于球形富勒烯,在溶液中(高达 |gabs| = 1.0 × 10-2)和固态下高效诱导其手性。
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引用次数: 0
Site-selective C(sp3)–H oxidation of alkyl substrates devoid of functional handles
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2025.102442
Yiheng Lu , Melina Knezevic , Alessandro Prescimone , Bernd Goldfuss , Konrad Tiefenbacher
Although the field of C(sp3)–H oxidation has progressed tremendously over the last decades, the selective oxidation of non-activated positions on hydrocarbon skeletons is still highly challenging. It usually requires the presence of a suitable functional handle in proximity to the desired oxidation site. Here, we present a novel approach to catalyst-directed C–H oxidation that relies on substrate binding via the solvophobic effect in fluorinated alcohols and thus is independent of specific functional groups on the substrate. The supramolecular catalyst Mn(mcp)-RS2 enables the preferential oxidation at the fifth position from the less-hindered side on aliphatic substrates.
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引用次数: 0
Soft microrobots for long-span precise stem cell delivery and restoration of neural connections
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2025.102492
Engui Zhao , Ting Ma
Precisely navigating stem cells is crucial for enhancing the therapeutic outcomes in treating spinal cord injury (SCI). In a recent study published in Matter, Shen et al. introduced a breakthrough strategy that uses computed tomography (CT)-guided magnetic-driven soft microrobots for long-distance, precise stem cell delivery. This innovative approach offers great potential to accelerate the clinical translation of stem cell therapy for SCI.
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引用次数: 0
Recycling homocarbon backbone polymers toward a circular materials economy
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2024.102406
Jie Zheng , Zhuang Mao Png , Xin Yi Oh , Huanning Zuo , Zibiao Li
Global plastic waste has reached a critical level, posing serious hazards to ecosystems and human health because of its persistent presence in landfills, oceans, and natural environments. Unlike heteroatom-backbone polymers, which feature a heterochain structure, homocarbon backbone polymers with nonpolar C–C backbones exhibit unprecedented durability and resistance to environmental factors, making them less prone to degradation. Consequently, the conversion of such plastic waste into valuable chemicals via chemical recycling presents a crucial solution to address the issues stemming from plastic waste. This review aims to summarize the latest developments in the closed-loop recycling and upcycling of homocarbon backbone polymers with a specific focus on the conversion of waste plastics into their original monomers and/or value-added chemicals through bio-, thermo-, and photocatalysis, which promotes a circular economy. Notably, the development of highly active catalysts and related depolymerization systems accelerates the evolution of plastic degradation and enhances product controllability, rendering the recycling of plastic waste feasible and affordable.
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引用次数: 0
Excited-state protonation and reduction enable the umpolung Birch reduction of naphthalenes 激发态质子化和还原使萘的umpolung Birch 还原成为可能
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2024.10.009
Javier Corpas , Eva Rivera-Chao , Enrique M. Arpa , Miguel Gomez-Mendoza , Yuri Katayama , Victor A. de la Peña O’Shea , Céline Bouchel , Clément Jacob , Pierre-Georges Echeverria , Alessandro Ruffoni , Daniele Leonori
The Birch reaction is a classical process used for the partial reduction of aromatics into non-conjugated cyclohexadienes that can be further functionalized. This strategy and its more modern variants are all based on an initial single-electron transfer event converting the arene into the corresponding radical anion for either protonation or hydrogen-atom transfer. Herein, we demonstrate an umpolung approach where the aromatic is first protonated to its corresponding carbocation and then reduced using the Lewis acid-base complex Et3N−BH3. This strategy requires aromatic photoexcitation so that protonation is favored by charge-transfer and driven by excited-state antiaromaticity relief. This means that aromatic excited-state basicity rather than ground-state redox potential needs to be considered when approaching reaction development. The mild conditions and the avoidance of strong reductants have enabled tolerance of functionalities generally not compatible under standard Birch conditions.
桦木反应是将芳烃部分还原成可进一步官能化的非共轭环己二烯的经典工艺。这种策略及其更现代的变体都是基于最初的单电子转移事件,将炔转化为相应的自由基阴离子,进行质子化或氢原子转移。在这里,我们展示了一种umpolung 方法,即首先将芳香族质子化为其相应的碳位,然后使用路易斯酸碱复合物 Et3N-BH3 还原。这种策略需要芳香族的光激发,从而通过电荷转移促进质子化,并通过激发态反芳香性缓解来驱动质子化。这意味着在进行反应发展时,需要考虑芳香激发态碱性,而不是基态氧化还原电位。由于条件温和,且避免使用强还原剂,因此可以容许在标准桦木条件下通常不兼容的官能团。
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引用次数: 0
Cluster-based redox-responsive super-atomic MRI contrast agents 基于簇的氧化还原反应超原子核磁共振成像造影剂
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2024.09.029
Alexandros A. Kitos , Raúl Castañeda , Zachary J. Comeau , Niki Mavragani , Nicholas D. Calvert , Alexia Kirby , Francisco M. Martinez-Santiesteban , Peter J. Pallister , Timothy J. Scholl , Muralee Murugesu , Adam J. Shuhendler , Jaclyn L. Brusso
Transition metal molecular clusters hold great promise as magnetic resonance imaging (MRI) probes, where careful chemical design can afford control over the size, shape, and total spin state of the contrast agent (CA). Although such clusters can act as a single entity, exhibiting advanced in situ reactivity to key diagnostic biomolecules, their dissociation/speciation in biological media hinders their potential as MRI CAs. To resolve this, the N-2-pyrimidylimidoyl-2-pyrimidylamidine chelate was employed to selectively bind 3d metal ions, forming highly stable mixed-metal clusters. Through spectroscopic, electrochemical, and magnetic analysis, along with in vitro and in vivo studies, the application of iron and manganese homo- and heterometallic complexes as MRI CAs capable of mapping tumor redox status through a simple T1w/T2w ratiometric approach was demonstrated. The use of heteropolynuclear 3d super-atomic complexes suitable for semi-quantitative in vivo MRI of tissue redox status opens new avenues for non-invasive characterization of biochemical microenvironments by MRI.
过渡金属分子团簇很有希望成为磁共振成像(MRI)探针,精心的化学设计可以控制造影剂(CA)的大小、形状和总自旋状态。虽然此类团簇可以作为单一实体发挥作用,对关键的诊断生物分子表现出先进的原位反应性,但它们在生物介质中的解离/分化阻碍了它们作为磁共振成像造影剂的潜力。为了解决这个问题,我们采用了 N-2-嘧啶亚氨酰基-2-嘧啶脒螯合物来选择性地结合 3d 金属离子,形成高度稳定的混合金属团簇。通过光谱、电化学和磁性分析,以及体外和体内研究,证明了铁和锰同金属和异金属复合物作为磁共振成像 CAs 的应用,能够通过简单的 T1w/T2w 比率测量法绘制肿瘤氧化还原状态图。使用适用于组织氧化还原状态半定量活体磁共振成像的异多核 3d 超原子复合物,为通过磁共振成像无创描述生化微环境开辟了新途径。
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引用次数: 0
Interfacial solvation-structure effects of molecularly dispersed CoPc catalysts on CO2 electrochemical conversion
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2025.102458
Ning Han , Xianqiang Xiong , Mohamed Noufal , Bo Weng , Alain R. Puente-Santiago
Heterogenized molecular electrocatalysts offer the potential to convert waste into valuable products, but the effect of molecular dispersion states on catalytic processes is poorly understood. Reporting recently in Nature Catalysis, Baker and co-workers investigate how molecular solvation structure and cation coordination affect the activity and selectivity of electrocatalytic CO2 reduction.
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引用次数: 0
Next-generation de novo luciferases: How artificial intelligence is improving its own designs at light speed
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2025.102491
Yosta de Stigter , Maarten Merkx
Advances in artificial intelligence are revolutionizing protein design, and new methods are emerging rapidly. In this issue of Chem, Yeh and co-workers leverage recent deep-learning-based tools to create a series of improved de novo luciferases and color variants that successfully address the limitations of native luciferases.
{"title":"Next-generation de novo luciferases: How artificial intelligence is improving its own designs at light speed","authors":"Yosta de Stigter ,&nbsp;Maarten Merkx","doi":"10.1016/j.chempr.2025.102491","DOIUrl":"10.1016/j.chempr.2025.102491","url":null,"abstract":"<div><div>Advances in artificial intelligence are revolutionizing protein design, and new methods are emerging rapidly. In this issue of <em>Chem</em>, Yeh and co-workers leverage recent deep-learning-based tools to create a series of improved <em>de novo</em> luciferases and color variants that successfully address the limitations of native luciferases.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102491"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143507488","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
Structural stability of a bent tetra(amino)tetraborane ring across four charge states
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-03-13 DOI: 10.1016/j.chempr.2024.10.005
Eva Beck , Ivo Krummenacher , Thomas Kupfer , Maximilian Dietz , Maximilian Michel , Kai Hammond , Holger Braunschweig
Boron rings with electron-precise (i.e., non-cluster) bonds represent a largely untapped area in boron chemistry, and investigating their properties could potentially open up exciting new research avenues. In this work, we present an efficient method for synthesizing the cyclic tetraborane B4(NCy2)4 by reduction of the amino(dihalo)borane (Cy2N)BCl2 (Cy, cyclohexyl). This puckered, covalently bonded compound features unprecedented stability across four charge states, highlighting the capacity of the B4 ring to adapt to varying σ- and π-electron counts. Density functional theory (DFT) calculations elucidate the electronic structure of all species, revealing how electron delocalization is modulated.
{"title":"Structural stability of a bent tetra(amino)tetraborane ring across four charge states","authors":"Eva Beck ,&nbsp;Ivo Krummenacher ,&nbsp;Thomas Kupfer ,&nbsp;Maximilian Dietz ,&nbsp;Maximilian Michel ,&nbsp;Kai Hammond ,&nbsp;Holger Braunschweig","doi":"10.1016/j.chempr.2024.10.005","DOIUrl":"10.1016/j.chempr.2024.10.005","url":null,"abstract":"<div><div>Boron rings with electron-precise (i.e., non-cluster) bonds represent a largely untapped area in boron chemistry, and investigating their properties could potentially open up exciting new research avenues. In this work, we present an efficient method for synthesizing the cyclic tetraborane B<sub>4</sub>(NCy<sub>2</sub>)<sub>4</sub> by reduction of the amino(dihalo)borane (Cy<sub>2</sub>N)BCl<sub>2</sub> (Cy, cyclohexyl). This puckered, covalently bonded compound features unprecedented stability across four charge states, highlighting the capacity of the B<sub>4</sub> ring to adapt to varying <em>σ</em>- and <em>π</em>-electron counts. Density functional theory (DFT) calculations elucidate the electronic structure of all species, revealing how electron delocalization is modulated.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102338"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143610937","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
期刊
Chem
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