Xuerui Yang, Yuqi Zhou, Junkun Zhou, Xuan Huang, Xin Ao, Guangni Ding, Xiaowei Huang, Naigen Zhou, Guanglei Cui, Yong Yang
The practical development of rechargeable magnesium batteries is fundamentally limited by anode passivation, electrolyte-induced corrosion, and sluggish interfacial Mg2+ transport. Herein, we develop a universal electrolyte design strategy that exploits the synergy between halides and phosphate esters to address these long-standing challenges. Typically, the incorporation of SiBr4 and tris(trimethylsilyl) phosphate (TMSP) extends the electrochemical stability window of the electrolyte from 2.75 to 3.94 V and reconstructs the solvation environment toward bis(trifluoromethanesulfonyl)imide (TFSI-) and TMSP-dominated coordination, significantly lowering the Mg2+ desolvation barrier. Preferential reduction of SiBr4 and TMSP yields a cross-linked, inorganic-rich interphase comprising Mg3(PO4)2, MgSiO3, and MgBr2, which enables fast Mg2+ transport and effectively suppresses parasitic reactions. Meanwhile, Mg3(PO4)2 and MgSiO3 within the interphase serve as robust scaffolds that immobilize soluble MgBr2, further reinforcing interfacial stability. Besides, the electron-rich P=O groups in TMSP further stabilize reactive SiBr3+ intermediates, thereby preventing electrolyte acidification and corrosion. Consequently, MgǁMg symmetric cells cycle stably for 1800 h with a low 0.14 V overpotential. MgǁMo cells reach a peak Coulombic efficiency of 99.97% at 3.4 V after the activation process. Full cells with Mo6S8 cathode deliver a capacity of 80 mAh g-1 with only 0.08% fading over 500 cycles, and Mgǁpolyaniline-intercalated V2O5 (PANI-V2O5) cells achieve 160 mAh g-1 at a cut-off voltage of 2.6 V. This synergistic regulation concept is generalizable to other halides and phosphate esters, providing new mechanistic insights and a general framework for designing stable electrolytes for multivalent batteries.
可充电镁电池的实际发展从根本上受到阳极钝化、电解质诱导腐蚀和界面Mg2+传输缓慢的限制。在此，我们开发了一种通用的电解质设计策略，利用卤化物和磷酸酯之间的协同作用来解决这些长期存在的挑战。典型地，SiBr4和三甲基硅基磷酸酯（TMSP）的加入将电解液的电化学稳定性窗口从2.75 V扩展到3.94 V，并重建了双（三氟甲磺酰）亚胺（TFSI-）和TMSP主导的配位的溶剂化环境，显著降低了Mg2+的脱溶势垒。SiBr4和TMSP优先还原生成交联的富无机间相，由Mg3(PO4)2、MgSiO3和MgBr2组成，可实现Mg2+的快速运输并有效抑制寄生反应。同时，界面内的Mg3(PO4)2和MgSiO3作为坚固的支架固定可溶MgBr2，进一步增强界面稳定性。此外，TMSP中富含电子的P=O基团进一步稳定了活性SiBr3+中间体，从而防止了电解质酸化和腐蚀。因此，MgǁMg对称电池稳定循环1800小时，过电位低0.14 V。MgǁMo电池在3.4 V时库仑效率达到99.97%的峰值。Mo6S8阴极的全电池在500次循环中提供80 mAh g-1的容量，只有0.08%的衰落，Mgǁpolyaniline-intercalated V2O5 （PANI-V2O5）电池在2.6 V的截止电压下实现160 mAh g-1。这种协同调节概念可推广到其他卤化物和磷酸酯，为多价电池稳定电解质的设计提供了新的机制见解和总体框架。
{"title":"Synergistic Halide and Phosphate Ester Electrolytes for Overcoming Corrosion and Interfacial Challenges in Magnesium Batteries","authors":"Xuerui Yang, Yuqi Zhou, Junkun Zhou, Xuan Huang, Xin Ao, Guangni Ding, Xiaowei Huang, Naigen Zhou, Guanglei Cui, Yong Yang","doi":"10.1039/d6sc00095a","DOIUrl":"https://doi.org/10.1039/d6sc00095a","url":null,"abstract":"The practical development of rechargeable magnesium batteries is fundamentally limited by anode passivation, electrolyte-induced corrosion, and sluggish interfacial Mg2+ transport. Herein, we develop a universal electrolyte design strategy that exploits the synergy between halides and phosphate esters to address these long-standing challenges. Typically, the incorporation of SiBr4 and tris(trimethylsilyl) phosphate (TMSP) extends the electrochemical stability window of the electrolyte from 2.75 to 3.94 V and reconstructs the solvation environment toward bis(trifluoromethanesulfonyl)imide (TFSI-) and TMSP-dominated coordination, significantly lowering the Mg2+ desolvation barrier. Preferential reduction of SiBr4 and TMSP yields a cross-linked, inorganic-rich interphase comprising Mg3(PO4)2, MgSiO3, and MgBr2, which enables fast Mg2+ transport and effectively suppresses parasitic reactions. Meanwhile, Mg3(PO4)2 and MgSiO3 within the interphase serve as robust scaffolds that immobilize soluble MgBr2, further reinforcing interfacial stability. Besides, the electron-rich P=O groups in TMSP further stabilize reactive SiBr3+ intermediates, thereby preventing electrolyte acidification and corrosion. Consequently, MgǁMg symmetric cells cycle stably for 1800 h with a low 0.14 V overpotential. MgǁMo cells reach a peak Coulombic efficiency of 99.97% at 3.4 V after the activation process. Full cells with Mo6S8 cathode deliver a capacity of 80 mAh g-1 with only 0.08% fading over 500 cycles, and Mgǁpolyaniline-intercalated V2O5 (PANI-V2O5) cells achieve 160 mAh g-1 at a cut-off voltage of 2.6 V. This synergistic regulation concept is generalizable to other halides and phosphate esters, providing new mechanistic insights and a general framework for designing stable electrolytes for multivalent batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138757","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}
Mahendiran Dharmasivam, Sadia Faiz, Busra Kaya, Tharushi P. Wijesinghe, Mediha Suleymanoglu, Mahan Gholam Azad, Vera Richardson, Ameer Fawad Zahoor, Danuta Kalinowski, William Lewis, Paul V. Bernhardt, Rukhsana Anjum, Des R. Richardson
Designing ligands for cancer has traditionally overlooked complex dissociation and transmetalation in enhancing efficacy. Another neglected criterion is the ligands' ability to intercept the labile Fe(II) pool released after transferrin endocytosis and reduction of transferrin-bound Fe(III). Given iron's essential role in cancer proliferation, disrupting metal homeostasis offers a promising therapeutic strategy. Herein, we introduce a new class of Fe(II)-selective ligands and their Ga(III) complexes for cancer therapy, guided by insights into their dissociative dynamics and transmetalation behavior. Unlike prior approaches focused on static metal coordination, this work integrates dissociation and transmetalation as design features, enabling selective interception of intracellular Fe(II) trafficking. Relative to the ligand, Ga(III) complexation led to a pronounced (p < 0.001–0.0001) enhancement in anti-proliferative activity, with up to a 70-fold increase in potency. This result was in contrast to the modest increase in potency (up to 2.4-fold) observed for the Cu(II) or Zn(II) complexes. Mechanistic dissection demonstrated that, unlike the complete dissociation of the Ga(III) complexes, the relative Zn(II) and Cu(II) complexes underwent only partial dissociation. This difference facilitates complete ligand and Ga(III) release from the complex and may account for the superior cytotoxicity of the Ga(III) complexes versus their Zn(II) and Cu(II) counterparts. Furthermore, their potency was linked to Fe(II) ligation rather than Fe(III), despite electronic similarity to Ga(III). This study introduces three underexplored design principles for anti-cancer ligand engineering: (i) dynamic complex dissociation; (ii) selective intracellular transmetalation using NNO-containing ligands; and (iii) interception of labile Fe(II) generated after endosomal Fe(III) reduction.
{"title":"Implementing the design cues of dissociation dynamics and transmetalation in gallium(III) complexes to promote the anti-proliferative activity of ligands targeting intracellular iron(II) trafficking","authors":"Mahendiran Dharmasivam, Sadia Faiz, Busra Kaya, Tharushi P. Wijesinghe, Mediha Suleymanoglu, Mahan Gholam Azad, Vera Richardson, Ameer Fawad Zahoor, Danuta Kalinowski, William Lewis, Paul V. Bernhardt, Rukhsana Anjum, Des R. Richardson","doi":"10.1039/d5sc06084b","DOIUrl":"https://doi.org/10.1039/d5sc06084b","url":null,"abstract":"Designing ligands for cancer has traditionally overlooked complex dissociation and transmetalation in enhancing efficacy. Another neglected criterion is the ligands' ability to intercept the labile Fe(<small>II</small>) pool released after transferrin endocytosis and reduction of transferrin-bound Fe(<small>III</small>). Given iron's essential role in cancer proliferation, disrupting metal homeostasis offers a promising therapeutic strategy. Herein, we introduce a new class of Fe(<small>II</small>)-selective ligands and their Ga(<small>III</small>) complexes for cancer therapy, guided by insights into their dissociative dynamics and transmetalation behavior. Unlike prior approaches focused on static metal coordination, this work integrates dissociation and transmetalation as design features, enabling selective interception of intracellular Fe(<small>II</small>) trafficking. Relative to the ligand, Ga(<small>III</small>) complexation led to a pronounced (<em>p</em> < 0.001–0.0001) enhancement in anti-proliferative activity, with up to a 70-fold increase in potency. This result was in contrast to the modest increase in potency (up to 2.4-fold) observed for the Cu(<small>II</small>) or Zn(<small>II</small>) complexes. Mechanistic dissection demonstrated that, unlike the complete dissociation of the Ga(<small>III</small>) complexes, the relative Zn(<small>II</small>) and Cu(<small>II</small>) complexes underwent only partial dissociation. This difference facilitates complete ligand and Ga(<small>III</small>) release from the complex and may account for the superior cytotoxicity of the Ga(<small>III</small>) complexes <em>versus</em> their Zn(<small>II</small>) and Cu(<small>II</small>) counterparts. Furthermore, their potency was linked to Fe(<small>II</small>) ligation rather than Fe(<small>III</small>), despite electronic similarity to Ga(<small>III</small>). This study introduces three underexplored design principles for anti-cancer ligand engineering: (i) dynamic complex dissociation; (ii) selective intracellular transmetalation using NNO-containing ligands; and (iii) interception of labile Fe(<small>II</small>) generated after endosomal Fe(<small>III</small>) reduction.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138751","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}
Perovskite nanocrystals (PNCs) have emerged as a versatile platform for next-generation optoelectronics owing to high photoluminescence quantum yields, tunable bandgaps, and superior charge transport. Yet, the intrinsic disorder of colloidal systems and limitations of scalable processing severely restrict their performance. The structurally ordered PNCs, called herein as OPNCs, has emerged as a promising strategy to overcome the intrinsic limitations of disordered colloidal systems. Controllable self-assembly enables the formation of ordered superlattices, where collective effects such as enhanced carrier mobility, improved photoluminescence, and miniband formation can be realized. In this perspective, we highlight recent advances in solvent engineering, functionalized ligand design, and external-field modulation that provide new levers for achieving structural control. We further discuss how ordered architectures open pathways toward device applications such as pixelated light-emitting devices, low-threshold lasers, and polarization-sensitive photodetectors. By reframing self-assembly as a controllable and designable process, we propose that OPNC superlattices hold transformative potential for stable and high-performance optoelectronic applications.
{"title":"Ordered Perovskite Nanocrystals: a Transformative Platform for Optoelectronic Applications","authors":"Lujun Zhai, Huifeng Li, Tom Wu, Jianyu Yuan","doi":"10.1039/d5sc08666c","DOIUrl":"https://doi.org/10.1039/d5sc08666c","url":null,"abstract":"Perovskite nanocrystals (PNCs) have emerged as a versatile platform for next-generation optoelectronics owing to high photoluminescence quantum yields, tunable bandgaps, and superior charge transport. Yet, the intrinsic disorder of colloidal systems and limitations of scalable processing severely restrict their performance. The structurally ordered PNCs, called herein as OPNCs, has emerged as a promising strategy to overcome the intrinsic limitations of disordered colloidal systems. Controllable self-assembly enables the formation of ordered superlattices, where collective effects such as enhanced carrier mobility, improved photoluminescence, and miniband formation can be realized. In this perspective, we highlight recent advances in solvent engineering, functionalized ligand design, and external-field modulation that provide new levers for achieving structural control. We further discuss how ordered architectures open pathways toward device applications such as pixelated light-emitting devices, low-threshold lasers, and polarization-sensitive photodetectors. By reframing self-assembly as a controllable and designable process, we propose that OPNC superlattices hold transformative potential for stable and high-performance optoelectronic applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"161 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138753","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}
Hengxuan Qi, Huaxin Li, Zujin Zhao, Hao Liu, Lin Wu, Deli Li, jiasen zhang, Ziru Xin, Chao Xia, Ruixiang Peng, Wenjun Wang, wei Li, Ziyi Ge
We implemented a "terminal engineering" strategy to address the challenges of low efficiency and the difficulty of effectively narrowing the emission spectra within the single boron-nitrogen (BN) multi-resonance thermally activated delayed fluorescence (MR-TADF) emitter system. By adding flexible diphenylamino groups and insulating tert-butyl (t-Bu) groups, respectively, into the structurally simple CzBN and the polycyclic aromatic hydrocarbon (PAH)-based Indo-CzBN, two novel proof-of-concept MR-TADF emitters, DPA-CzBN and Indo-tCzBN, were successfully developed. Notably, the incorporation of t-butyl units into polycyclic aromatic hydrocarbon (PAH)-structured indolocarbazole derivatives not only markedly suppresses the vibration relaxation of the excited state, enabling Indo-tCzBN to achieve an exceptionally narrow full width at half maximum (FWHM) of 19 nm and a high photoluminescence quantum yield (PLQY) of up to 97.5%, but also significantly enhances the horizontal dipole orientation factor (Θ//) of Indo-tCzBN to 85.3%, compared to approximately 73.6% for Indo-CzBN.Accordingly, benefiting from the synergistic effect of a high Θ// factor and a high PLQY, both the non-sensitized and sensitized organic light-emitting diodes (OLEDs) based on Indo-tCzBN achieved maximum external quantum efficiencies (EQEmax) of 37.4% and 39.0%, respectively. These values rank among the highest reported for MR-TADF emitters constructed on a single BN molecular architecture.
{"title":"Single-B/N MR-TADF Emitters Enhancing Electroluminescence Efficiency via 'Terminal Engineering' Strategy","authors":"Hengxuan Qi, Huaxin Li, Zujin Zhao, Hao Liu, Lin Wu, Deli Li, jiasen zhang, Ziru Xin, Chao Xia, Ruixiang Peng, Wenjun Wang, wei Li, Ziyi Ge","doi":"10.1039/d5sc10069k","DOIUrl":"https://doi.org/10.1039/d5sc10069k","url":null,"abstract":"We implemented a \"terminal engineering\" strategy to address the challenges of low efficiency and the difficulty of effectively narrowing the emission spectra within the single boron-nitrogen (BN) multi-resonance thermally activated delayed fluorescence (MR-TADF) emitter system. By adding flexible diphenylamino groups and insulating tert-butyl (t-Bu) groups, respectively, into the structurally simple CzBN and the polycyclic aromatic hydrocarbon (PAH)-based Indo-CzBN, two novel proof-of-concept MR-TADF emitters, DPA-CzBN and Indo-tCzBN, were successfully developed. Notably, the incorporation of t-butyl units into polycyclic aromatic hydrocarbon (PAH)-structured indolocarbazole derivatives not only markedly suppresses the vibration relaxation of the excited state, enabling Indo-tCzBN to achieve an exceptionally narrow full width at half maximum (FWHM) of 19 nm and a high photoluminescence quantum yield (PLQY) of up to 97.5%, but also significantly enhances the horizontal dipole orientation factor (Θ//) of Indo-tCzBN to 85.3%, compared to approximately 73.6% for Indo-CzBN.Accordingly, benefiting from the synergistic effect of a high Θ// factor and a high PLQY, both the non-sensitized and sensitized organic light-emitting diodes (OLEDs) based on Indo-tCzBN achieved maximum external quantum efficiencies (EQEmax) of 37.4% and 39.0%, respectively. These values rank among the highest reported for MR-TADF emitters constructed on a single BN molecular architecture.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"387 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138754","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}
Yan Guo, Menglan Luo, Wenbo Zhang, Peidong Liu, Jin Liu, Shudong Huang, Jiancheng Lv, Bowen Ke, Xianggen Liu
Large Language Models (LLMs) have revolutionized machine learning with their few-shot learning and reasoning capabilities, demonstrating impressive results in fields like natural language processing and computer vision. However, when applied to the domains of biology and chemistry, current LLMs face substantial limitations, particularly in capturing the nuanced relationships between molecular structure and pharmacochemical properties. This challenge has constrained the application of few-shot learning for small-molecule generation and optimization in drug discovery. Here, we introduce DrugLLM, a novel LLM tailored specifically for molecular optimization. DrugLLM leverages Functional Group Tokenization (FGT), which effectively tokenizes molecules for LLM learning, achieving over 53% token compression compared to SMILES. Besides, we propose a new pre-training strategy that enables DrugLLM to iteratively predict and modify molecular structures based on a few prior modifications, aligning each modification toward optimizing a specified pharmacological property. In multiple computational experiments, DrugLLM achieved state-of-the-art performance in few-shot molecular generation, surpassing all the mainstream LLMs including GPT-4. Furthermore, by applying DrugLLM to optimize HCN2 inhibitors, two bioactive compounds were obtained and successfully validated through wet-lab experiments. These results highlight the robust potential of DrugLLM in accelerating the optimization of molecules and AI-driven drug discovery.
{"title":"Few-shot molecular property optimization via a domain-specialized large language model","authors":"Yan Guo, Menglan Luo, Wenbo Zhang, Peidong Liu, Jin Liu, Shudong Huang, Jiancheng Lv, Bowen Ke, Xianggen Liu","doi":"10.1039/d5sc08859c","DOIUrl":"https://doi.org/10.1039/d5sc08859c","url":null,"abstract":"Large Language Models (LLMs) have revolutionized machine learning with their few-shot learning and reasoning capabilities, demonstrating impressive results in fields like natural language processing and computer vision. However, when applied to the domains of biology and chemistry, current LLMs face substantial limitations, particularly in capturing the nuanced relationships between molecular structure and pharmacochemical properties. This challenge has constrained the application of few-shot learning for small-molecule generation and optimization in drug discovery. Here, we introduce DrugLLM, a novel LLM tailored specifically for molecular optimization. DrugLLM leverages Functional Group Tokenization (FGT), which effectively tokenizes molecules for LLM learning, achieving over 53% token compression compared to SMILES. Besides, we propose a new pre-training strategy that enables DrugLLM to iteratively predict and modify molecular structures based on a few prior modifications, aligning each modification toward optimizing a specified pharmacological property. In multiple computational experiments, DrugLLM achieved state-of-the-art performance in few-shot molecular generation, surpassing all the mainstream LLMs including GPT-4. Furthermore, by applying DrugLLM to optimize HCN2 inhibitors, two bioactive compounds were obtained and successfully validated through wet-lab experiments. These results highlight the robust potential of DrugLLM in accelerating the optimization of molecules and AI-driven drug discovery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"176 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138759","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}
Oxetanes have recently garnered large amounts of interest from synthetic chemists due to their unique structural and chemical properties. Despite substantial advances for the formation of 3,3-disubstituted oxetanes, its 2-functionalized counterparts remain a challenging synthetic motif. Furthermore, methods to form alkyl oxetanes remain underdeveloped. Herein, we disclose a novel protocol for the synthesis of various alkyl and aryl 2-oxetanes leveraging a Giese addition to α-oxy radicals, furnishing the desired products in up to 95% yield.
{"title":"Visible-light-mediated synthesis of 2-oxetanes via Giese addition to α-oxy radicals","authors":"Matthew Liu, Elvis C. McFee, Corinna S. Schindler","doi":"10.1039/d5sc07764h","DOIUrl":"https://doi.org/10.1039/d5sc07764h","url":null,"abstract":"Oxetanes have recently garnered large amounts of interest from synthetic chemists due to their unique structural and chemical properties. Despite substantial advances for the formation of 3,3-disubstituted oxetanes, its 2-functionalized counterparts remain a challenging synthetic motif. Furthermore, methods to form alkyl oxetanes remain underdeveloped. Herein, we disclose a novel protocol for the synthesis of various alkyl and aryl 2-oxetanes leveraging a Giese addition to α-oxy radicals, furnishing the desired products in up to 95% yield.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138758","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}
With the progressive development of DNA nanotechnology and synthetic biology, the applications of DNA have expanded from traditional genetics study to materials science. By employing DNA as a structural framework or cross-linking agent, DNA hydrogels retain a hydrophilic three-dimensional (3D) network structure similar to biological tissues, exhibiting high biocompatibility, programmable responsiveness, and specific recognition functions. In this perspective, we summarize the preparation strategies of DNA hydrogels, analyze their application advantages, and highlight recent advances in areas such as cell culture, drug delivery, and tissue engineering. Finally, we discuss the current challenges in DNA hydrogel development and offer insights into future research directions.
{"title":"Preparation strategies and biomedical applications of DNA hydrogels.","authors":"Miaomiao Qiu, Jing Wang, Xinchang Pang, Dongsheng Liu, Yuanchen Dong","doi":"10.1039/d5sc08190d","DOIUrl":"https://doi.org/10.1039/d5sc08190d","url":null,"abstract":"<p><p>With the progressive development of DNA nanotechnology and synthetic biology, the applications of DNA have expanded from traditional genetics study to materials science. By employing DNA as a structural framework or cross-linking agent, DNA hydrogels retain a hydrophilic three-dimensional (3D) network structure similar to biological tissues, exhibiting high biocompatibility, programmable responsiveness, and specific recognition functions. In this perspective, we summarize the preparation strategies of DNA hydrogels, analyze their application advantages, and highlight recent advances in areas such as cell culture, drug delivery, and tissue engineering. Finally, we discuss the current challenges in DNA hydrogel development and offer insights into future research directions.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.4,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879038/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146141225","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}
Modulating the intrinsic leaving-group tendency of halides remains a long-standing challenge in synthetic chemistry. Herein, we reported dynamic anion recognition and demonstrated its application in nucleophilic substitution reactions, enabling an apparent reversal of halide leaving-group tendency sequence. A bidentate Lewis acid-based platform was developed to selectively bind halide ions, forming host–guest complexes that were characterized by NMR spectroscopy and X-ray crystallography. Competitive experiments with the host molecule have revealed tunable binding affinities for the halides based on the cavity size of the bisboron center. Moreover, anion exchange experiments have demonstrated that the dynamic binding of halides is primarily influenced by their nucleophilicity and ion radius. The recognition of organohalides by diborane hosts induced a reversal of the leaving ability of Br⁻ and Cl⁻ in diborane-catalyzed transformations, which deviated from the conventional sequence.
{"title":"Modulating Halide Leaving-Group Trends through Recognition by Bisboranes","authors":"Tong-Tong Liu, Xiao-Wen Li, Yun-Shu Cui, Zi-Hao Deng, Feng Liu, Dan-Dan Zhai, Zhang-Jie Shi","doi":"10.1039/d5sc10013e","DOIUrl":"https://doi.org/10.1039/d5sc10013e","url":null,"abstract":"Modulating the intrinsic leaving-group tendency of halides remains a long-standing challenge in synthetic chemistry. Herein, we reported dynamic anion recognition and demonstrated its application in nucleophilic substitution reactions, enabling an apparent reversal of halide leaving-group tendency sequence. A bidentate Lewis acid-based platform was developed to selectively bind halide ions, forming host–guest complexes that were characterized by NMR spectroscopy and X-ray crystallography. Competitive experiments with the host molecule have revealed tunable binding affinities for the halides based on the cavity size of the bisboron center. Moreover, anion exchange experiments have demonstrated that the dynamic binding of halides is primarily influenced by their nucleophilicity and ion radius. The recognition of organohalides by diborane hosts induced a reversal of the leaving ability of Br⁻ and Cl⁻ in diborane-catalyzed transformations, which deviated from the conventional sequence.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"48 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129472","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}
Jie Zhou, Yuwei Sha, Ling'ou Qin, Fengying Yuan, Yu Ouyang, Yaqin Chai, Pu Zhang, Ruo Yuan
Profiling cell cycle phase progression and determining how cells respond to external stimuli through miRNA quantification will enable substantial improvements in therapeutic assessment. However, miRNA evaluation is challenging due to its transient nature and the complex cellular environment. Here, we report “cShot” (cell cycle shot), a method for spatial dynamic imaging of miRNA across different cell cycles via dynamic DNA sequences that integrate a pair of competitive probes into a set of static target-binding probes. Compared to traditional irreversible binding probes, cShot enables dynamic binding and dissociation of miRNA through constitutional exchange between two probe sets. Typically, cShot relies on multiple signal outputs, ensuring an accurate signal output through adaptive regulation of the probes. The dynamic behavior of cShot is accompanied by kinetic models, providing a systematic self-checking ability for c-Shot. By tethering DNA tetrahedra to the cShot system and utilizing a hybridization chain reaction, cShot enables real-time monitoring of cell cycle-dependent heterogeneity in synchronized MCF-7 cells under radiomimetic drug stimulation.
{"title":"cShot: spatial dynamic imaging of cell cycle-dependent miRNA heterogeneity using dynamic DNA patterns","authors":"Jie Zhou, Yuwei Sha, Ling'ou Qin, Fengying Yuan, Yu Ouyang, Yaqin Chai, Pu Zhang, Ruo Yuan","doi":"10.1039/d5sc09638c","DOIUrl":"https://doi.org/10.1039/d5sc09638c","url":null,"abstract":"Profiling cell cycle phase progression and determining how cells respond to external stimuli through miRNA quantification will enable substantial improvements in therapeutic assessment. However, miRNA evaluation is challenging due to its transient nature and the complex cellular environment. Here, we report “cShot” (cell cycle shot), a method for spatial dynamic imaging of miRNA across different cell cycles <em>via</em> dynamic DNA sequences that integrate a pair of competitive probes into a set of static target-binding probes. Compared to traditional irreversible binding probes, cShot enables dynamic binding and dissociation of miRNA through constitutional exchange between two probe sets. Typically, cShot relies on multiple signal outputs, ensuring an accurate signal output through adaptive regulation of the probes. The dynamic behavior of cShot is accompanied by kinetic models, providing a systematic self-checking ability for c-Shot. By tethering DNA tetrahedra to the cShot system and utilizing a hybridization chain reaction, cShot enables real-time monitoring of cell cycle-dependent heterogeneity in synchronized MCF-7 cells under radiomimetic drug stimulation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"45 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146007","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}
Aqueous zinc–iodine batteries (ZIBs) are a promising energy storage technology due to the abundance of iodine, environmental friendliness, and low cost. This study introduces a multifunctional additive, L-lysine hydrochloride (LLH), designed to activate the four-electron transfer chemistry between I+ and I− species, significantly boosting energy density. LLH stabilizes I+via dual coordination from the amino groups and chloride ion, effectively suppressing hydrolysis and enabling reversible 2I−/I02/2I+ conversion. The preferential adsorption of the carboxyl group of protonated L-lysine at the zinc anode promotes uniform zinc deposition while inhibiting the hydrogen evolution reaction. Additionally, the incorporation of LLH effectively suppresses the shuttle effect by interacting with iodine species through its carboxyl and amino groups. LLH-modified Zn‖Zn symmetric batteries demonstrate extended cycling stability, operating beyond 4000 hours, while Zn‖I2 full batteries deliver a high specific capacity of 502 mAh g−1 at 1 A g−1. This additive strategy renders a facile and efficient approach to realizing high-capacity and durable ZIBs.
水相锌-碘电池具有丰富的碘含量、环保、低成本等优点，是一种很有前途的储能技术。本研究引入了一种多功能添加剂，l -赖氨酸盐酸盐（LLH），旨在激活I+和I -物种之间的四电子转移化学，显著提高能量密度。LLH通过氨基和氯离子的双重配位稳定I+，有效抑制水解并实现可逆的2I−/I02/2I+转化。质子化l -赖氨酸羧基在锌阳极上的优先吸附促进了均匀的锌沉积，同时抑制了析氢反应。此外，LLH的掺入通过其羧基和氨基与碘物质相互作用，有效地抑制了穿梭效应。llh改性Zn‖Zn对称电池表现出延长的循环稳定性，运行超过4000小时，而Zn‖I2全电池在1 a g−1时提供502 mAh g−1的高比容量。这种添加策略为实现高容量和持久的zib提供了一种简单有效的方法。
{"title":"A dual-function molecule enables stable four-electron conversion and Zn deposition for high-capacity aqueous Zn–I2 batteries","authors":"Huiquan Zhang, Xueying Zhang, Dongmin Ma, Xinxin Cai, Mochi Lv, Hongting Yan, Junbo Niu, Weixing Song","doi":"10.1039/d6sc00182c","DOIUrl":"https://doi.org/10.1039/d6sc00182c","url":null,"abstract":"Aqueous zinc–iodine batteries (ZIBs) are a promising energy storage technology due to the abundance of iodine, environmental friendliness, and low cost. This study introduces a multifunctional additive, <small>L</small>-lysine hydrochloride (LLH), designed to activate the four-electron transfer chemistry between I<small><sup>+</sup></small> and I<small><sup>−</sup></small> species, significantly boosting energy density. LLH stabilizes I<small><sup>+</sup></small> <em>via</em> dual coordination from the amino groups and chloride ion, effectively suppressing hydrolysis and enabling reversible 2I<small><sup>−</sup></small>/I<small><sup>0</sup></small><small><sub>2</sub></small>/2I<small><sup>+</sup></small> conversion. The preferential adsorption of the carboxyl group of protonated <small>L</small>-lysine at the zinc anode promotes uniform zinc deposition while inhibiting the hydrogen evolution reaction. Additionally, the incorporation of LLH effectively suppresses the shuttle effect by interacting with iodine species through its carboxyl and amino groups. LLH-modified Zn‖Zn symmetric batteries demonstrate extended cycling stability, operating beyond 4000 hours, while Zn‖I<small><sub>2</sub></small> full batteries deliver a high specific capacity of 502 mAh g<small><sup>−1</sup></small> at 1 A g<small><sup>−1</sup></small>. This additive strategy renders a facile and efficient approach to realizing high-capacity and durable ZIBs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146008","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}
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