Here we demonstrate the prediction of the isotropization temperatures of nanostructured ionic liquid crystals (ILCs) by a machine learning method. ILCs, which self-assemble into dynamic and well-ordered nanostructures, have been extensively studied, because they can be used as various functional materials including electrolytes, water treatment membranes, and stimuli-responsive materials. In general, machine learning is not easily applied to predict dynamic functions of such self-assembled materials because of the complex structural-function relationship and small data size. Our approach is to use the machine learning method combined with our experimental experiences and chemical insights as researchers. Training data of order-disorder transition (isotropic) temperatures consisting of 116 wedge-shaped ILCs reported by our groups or other groups has been analyzed by this method, leading to successful construction of the prediction model with the root mean squared error value of 23.7 °C. The model is straightforward, interpretable and reasonable from a viewpoint of chemistry. Moreover, the constructed model predicted the transition temperatures of 45 wedge-shaped ILCs in test data. The model has sufficient accuracy to predict the transition temperatures of certain kinds of ILCs, which help the molecular designs of ILCs. The transition temperature of the isotropization, which is the transition from an ordered liquid-crystalline state to a random isotropic state, is the key properties for the ILCs to achieve their excellent properties. It is important to predict the transition temperatures before starting experiments, while it has been challenging because the complex factors determine the transition temperatures. The model constructed in the present study may accelerate the development of functional ILCs.
{"title":"Prediction of the phase transition temperatures of functional nanostructured liquid crystals: machine learning method based on small data for the design of self-assembled materials","authors":"Shingo Takegawa, Haruka Tobita, Yasuhiko Igarashi, Yuya Oaki, Takashi Kato","doi":"10.1039/d5nr04714e","DOIUrl":"https://doi.org/10.1039/d5nr04714e","url":null,"abstract":"Here we demonstrate the prediction of the isotropization temperatures of nanostructured ionic liquid crystals (ILCs) by a machine learning method. ILCs, which self-assemble into dynamic and well-ordered nanostructures, have been extensively studied, because they can be used as various functional materials including electrolytes, water treatment membranes, and stimuli-responsive materials. In general, machine learning is not easily applied to predict dynamic functions of such self-assembled materials because of the complex structural-function relationship and small data size. Our approach is to use the machine learning method combined with our experimental experiences and chemical insights as researchers. Training data of order-disorder transition (isotropic) temperatures consisting of 116 wedge-shaped ILCs reported by our groups or other groups has been analyzed by this method, leading to successful construction of the prediction model with the root mean squared error value of 23.7 °C. The model is straightforward, interpretable and reasonable from a viewpoint of chemistry. Moreover, the constructed model predicted the transition temperatures of 45 wedge-shaped ILCs in test data. The model has sufficient accuracy to predict the transition temperatures of certain kinds of ILCs, which help the molecular designs of ILCs. The transition temperature of the isotropization, which is the transition from an ordered liquid-crystalline state to a random isotropic state, is the key properties for the ILCs to achieve their excellent properties. It is important to predict the transition temperatures before starting experiments, while it has been challenging because the complex factors determine the transition temperatures. The model constructed in the present study may accelerate the development of functional ILCs.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"146 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yulong Wu, Luyao Wen, Shiqiang Wei, Jialin Shi, Quan Zhou, Qian Zhou, Wei Jiang, Xiaojun Wu, Chimtali Joseph Peter, Qiang Chi, Changda Wang, Li Song
Uncontrolled side reactions and dendrite growth on Zn anodes present significant challenges to the commercial application of aqueous zinc-ion batteries (AZIBs). Electrolyte additive is recognized as an effective approach with operational convenience and multifunctionality for achieving stable AZIBs. Herein, 1-Ethyl-3-methylimidazolium iodide (EMImI) ionic liquid was introduced into the electrolyte to stabilize the Zn anode. The characterizations revealed that EMIm + and I -could be selectively adsorbed on the Zn surface to generate a water-deficient electric double layer and promote the formation of a ZnS/ZnI 2 -riched gradient solid electrolyte interface (SEI). The water decomposition-induced side reactions were subsequently suppressed with enhanced zinc deposition kinetics. Notably, the selective adsorption of cations and anions on different crystal planes induced preferentially (002) oriented dendrite-free zinc deposition behavior, and ultimately achieved high performance in AZIBs. Experimental results confirmed that the EMImI-modulated interfacial chemistry significantly improved the stability and reversibility of the Zn anode, resulting in Zn//Zn symmetric cells with an ultra-long lifespan exceeding 7100 hours at 1 mA cm -2 and 1 mAh cm -2 . The Zn//PANI full cells containing EMImI also exhibited outstanding cycling stability, i.e., 68.7% capacity retention after 2700 cycles at 0.5 A g -1 and over 10000 stable cycles at 5 A g -1 and 10 A g -1 . This work provides an ionbased electrolyte-engineering strategy for achieving highly stable and reversible Zn anodes.
锌阳极上不受控制的副反应和枝晶生长对水锌离子电池（AZIBs）的商业应用提出了重大挑战。电解质添加剂被认为是实现稳定azib的有效方法，具有操作方便和多功能性。在电解液中引入1-乙基-3-甲基咪唑碘化（EMImI）离子液体来稳定Zn阳极。表征结果表明，EMIm +和I -可选择性吸附在Zn表面形成缺水双电层，促进富ZnS/ZnI 2梯度固体电解质界面（SEI）的形成。随着锌沉积动力学的增强，水分解引起的副反应随后被抑制。值得注意的是，阳离子和阴离子在不同晶体平面上的选择性吸附诱导了优先（002）取向的无枝晶锌沉积行为，并最终实现了azib的高性能。实验结果证实，emimi调制的界面化学显著提高了Zn阳极的稳定性和可逆性，导致Zn/ Zn对称电池在1 mA cm -2和1 mAh cm -2下的超长寿命超过7100小时。含有EMImI的Zn//PANI全电池也表现出了出色的循环稳定性，即在0.5 A g -1下循环2700次后容量保持率为68.7%，在5 A g -1和10 A g -1下稳定循环超过10000次。这项工作为实现高度稳定和可逆的锌阳极提供了一种基于离子的电解质工程策略。
{"title":"Interfacial Chemistry Modulation of Zn Anode via EMImI Ionic Liquid Additive for Stable Aqueous Zinc-Ion Batteries","authors":"Yulong Wu, Luyao Wen, Shiqiang Wei, Jialin Shi, Quan Zhou, Qian Zhou, Wei Jiang, Xiaojun Wu, Chimtali Joseph Peter, Qiang Chi, Changda Wang, Li Song","doi":"10.1039/d5nr04306a","DOIUrl":"https://doi.org/10.1039/d5nr04306a","url":null,"abstract":"Uncontrolled side reactions and dendrite growth on Zn anodes present significant challenges to the commercial application of aqueous zinc-ion batteries (AZIBs). Electrolyte additive is recognized as an effective approach with operational convenience and multifunctionality for achieving stable AZIBs. Herein, 1-Ethyl-3-methylimidazolium iodide (EMImI) ionic liquid was introduced into the electrolyte to stabilize the Zn anode. The characterizations revealed that EMIm + and I -could be selectively adsorbed on the Zn surface to generate a water-deficient electric double layer and promote the formation of a ZnS/ZnI 2 -riched gradient solid electrolyte interface (SEI). The water decomposition-induced side reactions were subsequently suppressed with enhanced zinc deposition kinetics. Notably, the selective adsorption of cations and anions on different crystal planes induced preferentially (002) oriented dendrite-free zinc deposition behavior, and ultimately achieved high performance in AZIBs. Experimental results confirmed that the EMImI-modulated interfacial chemistry significantly improved the stability and reversibility of the Zn anode, resulting in Zn//Zn symmetric cells with an ultra-long lifespan exceeding 7100 hours at 1 mA cm -2 and 1 mAh cm -2 . The Zn//PANI full cells containing EMImI also exhibited outstanding cycling stability, i.e., 68.7% capacity retention after 2700 cycles at 0.5 A g -1 and over 10000 stable cycles at 5 A g -1 and 10 A g -1 . This work provides an ionbased electrolyte-engineering strategy for achieving highly stable and reversible Zn anodes.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"26 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704821","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Janus membranes with hydrophilic surfaces have been developed to mitigate natural organic fouling during membrane distillation (MD) seawater desalination. Nevertheless, most Janus membranes remain susceptible to fouling and pore wetting during prolonged operation, primarily attributed to the penetration of negatively charged humic acid (HA) through hydrophilic layers and lack of bulk hydrophobicity across the membrane. Herein, we develop a Janus membrane featuring a negatively charged hydrophilic polyelectrolyte complex (PEC) layer and tailored hydrophobicity of pore surfaces for stable MD seawater desalination. The PEC layers with negatively charged surface are fabricated via a rapid droplet superspreading strategy with aqueous phase separation. The robust hydrophobicity is achieved by constructing nanostructures on pore surfaces using hydrophobic silica (F-SiO2) nanoparticles. The resulting PEC-based Janus membranes exhibit stable MD flux (29.0 kg m-2 h-1) and high salt rejection (>99.9%) during cyclic desalination of simulated seawater. Our strategy demonstrates promising potential for developing high-performance MD membranes in seawater desalination.
具有亲水性表面的Janus膜用于膜蒸馏（MD）海水淡化过程中的天然有机污染。然而，在长时间的操作过程中，大多数Janus膜仍然容易受到污染和孔隙润湿，这主要是由于带负电荷的腐植酸（HA）通过亲水性层渗透，以及膜上缺乏整体疏水性。在此，我们开发了一种Janus膜，该膜具有带负电的亲水聚电解质复合物（PEC）层和定制的孔表面疏水性，用于稳定的MD海水淡化。采用水相分离的快速液滴超扩散策略制备了表面带负电荷的PEC层。利用疏水性二氧化硅（F-SiO2）纳米颗粒在孔表面构建纳米结构，实现了良好的疏水性。所得的pec基Janus膜在模拟海水循环脱盐过程中表现出稳定的MD通量（29.0 kg m-2 h-1）和高的除盐率（>99.9%）。我们的策略显示了在海水淡化中开发高性能MD膜的潜力。
{"title":"Negatively charged Janus membrane with robust pore anti-wettability for stable membrane distillation of seawater","authors":"Yuxiang Zhu, Yuxin Zhang, Yiting Liang, Wenbiao Zhou, Xiao Chen, Pengchao Zhang","doi":"10.1039/d5nr04151a","DOIUrl":"https://doi.org/10.1039/d5nr04151a","url":null,"abstract":"Janus membranes with hydrophilic surfaces have been developed to mitigate natural organic fouling during membrane distillation (MD) seawater desalination. Nevertheless, most Janus membranes remain susceptible to fouling and pore wetting during prolonged operation, primarily attributed to the penetration of negatively charged humic acid (HA) through hydrophilic layers and lack of bulk hydrophobicity across the membrane. Herein, we develop a Janus membrane featuring a negatively charged hydrophilic polyelectrolyte complex (PEC) layer and tailored hydrophobicity of pore surfaces for stable MD seawater desalination. The PEC layers with negatively charged surface are fabricated via a rapid droplet superspreading strategy with aqueous phase separation. The robust hydrophobicity is achieved by constructing nanostructures on pore surfaces using hydrophobic silica (F-SiO2) nanoparticles. The resulting PEC-based Janus membranes exhibit stable MD flux (29.0 kg m-2 h-1) and high salt rejection (>99.9%) during cyclic desalination of simulated seawater. Our strategy demonstrates promising potential for developing high-performance MD membranes in seawater desalination.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"35 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The variation in electronic, magnetic, and nonlinear optoelectronic properties due to interstitial doping on group-12 based single-atom thick ternary metal-phosphorus-chalcogenide quantum dots (MPC QDs) have been studied with density functional theory computations. This novel doping strategy intended to examine the impacts of P3–TM hybridizations in surface-bound region and how it systematically regulates multifunctional behavior of these nanoflakes. It is found that the placement of a transition metal (TM) atom at a hollow site, in proximity to the substituted phosphorus, leads to localized magnetic moments in these honeycomb-shaped nanoflakes. Moreover, a few configurations retain their nonmagnetic character despite the interstitial coordination (spin compensation), while nonlocal chalcogen coordination within the host framework modulates the overall magneto-electronic response. The spin-polarization can be tuned to achieve specific magnetic ordering with S = 1, 3/2, 2, and 3, confirming constrained spatial extent of stable spin density around the dopant. Pristine MPCQDshaveenergy gaps of 2.7–7.37 eV, which increase for Zn/Cd and decrease for Hg with chalcogens, while Co-, Ni-, Mn-, or V-doped cases range from 4.53 to 9.10 eV (E↑ g) and from 3.89 to 7.13 eV (E↓ g). Moreover, linear polarizability increases with chalcogens (S to Te) for pristine and ternary cases, while interstitial cases show enhanced static first-hyperpolarizability due to co-doping-induced charge asymmetry. Overall, understanding doping-induced local hybridization in wide-gap nanoflakes, which gives rise to proximal magnetic moments with controllable HOMO-LUMO distributions and enhanced hyper(polarizability), enables the effort to engineer spin-filtering devices, spin-based quantum computation, second-harmonic generation (SHG), and electro-optic modulation.
利用密度泛函理论计算研究了12基单原子厚三元金属磷硫系量子点（MPC QDs）的电子、磁性和非线性光电性能的变化。这种新颖的掺杂策略旨在研究P3-TM杂化在表面结合区域的影响，以及它如何系统地调节这些纳米片的多功能行为。研究发现，过渡金属（TM）原子放置在靠近取代磷的空心位置，导致这些蜂窝状纳米片中的局部磁矩。此外，尽管存在间隙配位（自旋补偿），但一些构型仍保持其非磁性，而宿主框架内的非局域硫配位调节了整体磁电子响应。在S = 1、3/2、2和3时，可调谐自旋极化以实现特定的磁有序，从而确定了掺杂剂周围稳定自旋密度的受限空间范围。纯净mpcqd的能隙在2.7 ~ 7.37 eV之间，其中Zn/Cd的能隙增大，Hg的能隙减小，而Co、Ni、Mn、v掺杂的能隙在4.53 ~ 9.10 eV （E↑g）和3.89 ~ 7.13 eV （E↓g）之间。此外，对于原始态和三元态，线性极化率随着硫元（S到Te）的增加而增加，而间隙态由于共掺杂引起的电荷不对称而表现出静态第一超极化率的增强。总的来说，了解宽间隙纳米片中掺杂诱导的局部杂化，可以产生具有可控HOMO-LUMO分布和增强超极化率的近端磁矩，从而使设计自旋滤波器件、基于自旋的量子计算、二次谐波产生（SHG）和电光调制成为可能。
{"title":"Interstitial TM–P Pairing in P3-Coordinated Wide-Gap Quantum Dots: Spin-Selective Insulating States and Enhanced Hyperpolarizability","authors":"Saraf Mohaimen Chowdhury, Ishmam Hossain, Mahdy Rahman Chowdhury","doi":"10.1039/d5nr02041g","DOIUrl":"https://doi.org/10.1039/d5nr02041g","url":null,"abstract":"The variation in electronic, magnetic, and nonlinear optoelectronic properties due to interstitial doping on group-12 based single-atom thick ternary metal-phosphorus-chalcogenide quantum dots (MPC QDs) have been studied with density functional theory computations. This novel doping strategy intended to examine the impacts of P3–TM hybridizations in surface-bound region and how it systematically regulates multifunctional behavior of these nanoflakes. It is found that the placement of a transition metal (TM) atom at a hollow site, in proximity to the substituted phosphorus, leads to localized magnetic moments in these honeycomb-shaped nanoflakes. Moreover, a few configurations retain their nonmagnetic character despite the interstitial coordination (spin compensation), while nonlocal chalcogen coordination within the host framework modulates the overall magneto-electronic response. The spin-polarization can be tuned to achieve specific magnetic ordering with S = 1, 3/2, 2, and 3, confirming constrained spatial extent of stable spin density around the dopant. Pristine MPCQDshaveenergy gaps of 2.7–7.37 eV, which increase for Zn/Cd and decrease for Hg with chalcogens, while Co-, Ni-, Mn-, or V-doped cases range from 4.53 to 9.10 eV (E↑ g) and from 3.89 to 7.13 eV (E↓ g). Moreover, linear polarizability increases with chalcogens (S to Te) for pristine and ternary cases, while interstitial cases show enhanced static first-hyperpolarizability due to co-doping-induced charge asymmetry. Overall, understanding doping-induced local hybridization in wide-gap nanoflakes, which gives rise to proximal magnetic moments with controllable HOMO-LUMO distributions and enhanced hyper(polarizability), enables the effort to engineer spin-filtering devices, spin-based quantum computation, second-harmonic generation (SHG), and electro-optic modulation.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"239 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaoyi Meng, Fang Wang, Huijuan Duan, Wenfei Xu, Wenjing Liu, Hong Sun, Jun Ye, Yin Xiao, Zhaogang Sun, Hongqian Chu
Photodynamic therapy (PDT) represents a promising noninvasive modality for clinical cancer treatment. However, its efficacy is constrained by the limited penetration depth of excitation light for most photosensitizers and the therapy-induced hypoxia within the tumor microenvironment (TME). To overcome these limitations, we rationally designed a composite upconversion nanoparticle, UCNPs@MSN-Ce6/TPZ (UMCT), integrating the photosensitizer chlorin e6 (Ce6) and the hypoxia-activated prodrug tirapazamine (TPZ) for synergistic PDT and chemotherapy. Utilizing the unique properties of upconversion nanoparticles, UMCT generates singlet oxygen (1O2) via Ce6 activation upon 980 nm near-infrared (NIR) light irradiation, thereby initiating PDT. Concurrently, TPZ exploits both the PDT-aggravated hypoxia and the intrinsically hypoxic TME to exert its tumoricidal effects. Significantly, UMCT demonstrates effective accumulation at the tumor site, achieving a potent and synergistic tumor-suppressing effect both in vitro and in vivo. This work provides a promising strategy for designing more efficient PDT nanoplatforms and advancing their biomedical applications.
{"title":"NIR-Light Triggered Photodynamic Therapy Combined with Hypoxia Activated Chemotherapy for Anti-Tumor Effect","authors":"Xiaoyi Meng, Fang Wang, Huijuan Duan, Wenfei Xu, Wenjing Liu, Hong Sun, Jun Ye, Yin Xiao, Zhaogang Sun, Hongqian Chu","doi":"10.1039/d5nr04208a","DOIUrl":"https://doi.org/10.1039/d5nr04208a","url":null,"abstract":"Photodynamic therapy (PDT) represents a promising noninvasive modality for clinical cancer treatment. However, its efficacy is constrained by the limited penetration depth of excitation light for most photosensitizers and the therapy-induced hypoxia within the tumor microenvironment (TME). To overcome these limitations, we rationally designed a composite upconversion nanoparticle, UCNPs@MSN-Ce6/TPZ (UMCT), integrating the photosensitizer chlorin e6 (Ce6) and the hypoxia-activated prodrug tirapazamine (TPZ) for synergistic PDT and chemotherapy. Utilizing the unique properties of upconversion nanoparticles, UMCT generates singlet oxygen (1O2) via Ce6 activation upon 980 nm near-infrared (NIR) light irradiation, thereby initiating PDT. Concurrently, TPZ exploits both the PDT-aggravated hypoxia and the intrinsically hypoxic TME to exert its tumoricidal effects. Significantly, UMCT demonstrates effective accumulation at the tumor site, achieving a potent and synergistic tumor-suppressing effect both in vitro and in vivo. This work provides a promising strategy for designing more efficient PDT nanoplatforms and advancing their biomedical applications.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"69 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Transforming a rigid photoresponsive molecular crystal composed of anisotropic molecular packing structures into a highly disordered and soft gel using low-intensity visible light illumination is intriguing but remains a challenge. Here, we demonstrated that the slender molecular crystal microrods of an anthracene derivative (APA) rapidly (≤1 min) transform into amorphous gels, accompanied by vigorous mechanical motions, including bending, twisting, expansion, and curling, under relatively low-intensity visible light (450 nm, 20 mW/cm²) illumination. APA molecules in a highly crystalline microrod can undergo effective Z-to-E photoisomerization when exposed to visible light, causing significant molecular configuration changes to destroy the rigid crystal lattice and drive the microrod to move and deform drastically. When placed in an aqueous environment, an APA microrod rapidly (~30 s) transforms into a gel and expands by incorporating surrounding water molecules. The resulting photoproduct gels can also engulf and gather microscopic particles, such as polystyrene microspheres, silica nanoparticles, and silver (Ag) and gold (Au) nanoparticles, due to the extensively inflated volume after gelation. As a result, the dynamic Z-to-E isomerization in the APA microrods can be in situ characterized using a microscope equipped with laser Raman spectroscopy measurements by incorporating Ag nanoparticles to amplify signals. Our research provides a facile method for achieving a rapid phase transition from a stiff material to a highly flexible state and also offers a new approach for instantaneously monitoring the dynamic photochemistry of responsive materials.
{"title":"Photoinduced Dynamic Gelation and Deformations Based on Molecular Crystal Microrods Stimulated by Z-to-E Photoisomerization","authors":"Yu-Hao Li, Jiang-Tao Liu, Ya-Bing Sun, Yun-Peng Huang, Jia-Wang Hou, Yikai Xu, Chen-Chen Zhang, Tian-Yi Xu, Fei Tong","doi":"10.1039/d5nr03308j","DOIUrl":"https://doi.org/10.1039/d5nr03308j","url":null,"abstract":"Transforming a rigid photoresponsive molecular crystal composed of anisotropic molecular packing structures into a highly disordered and soft gel using low-intensity visible light illumination is intriguing but remains a challenge. Here, we demonstrated that the slender molecular crystal microrods of an anthracene derivative (APA) rapidly (≤1 min) transform into amorphous gels, accompanied by vigorous mechanical motions, including bending, twisting, expansion, and curling, under relatively low-intensity visible light (450 nm, 20 mW/cm²) illumination. APA molecules in a highly crystalline microrod can undergo effective Z-to-E photoisomerization when exposed to visible light, causing significant molecular configuration changes to destroy the rigid crystal lattice and drive the microrod to move and deform drastically. When placed in an aqueous environment, an APA microrod rapidly (~30 s) transforms into a gel and expands by incorporating surrounding water molecules. The resulting photoproduct gels can also engulf and gather microscopic particles, such as polystyrene microspheres, silica nanoparticles, and silver (Ag) and gold (Au) nanoparticles, due to the extensively inflated volume after gelation. As a result, the dynamic Z-to-E isomerization in the APA microrods can be in situ characterized using a microscope equipped with laser Raman spectroscopy measurements by incorporating Ag nanoparticles to amplify signals. Our research provides a facile method for achieving a rapid phase transition from a stiff material to a highly flexible state and also offers a new approach for instantaneously monitoring the dynamic photochemistry of responsive materials.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"11 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718479","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xutao Chen, Yue Wang, Kunkun Wei, Yunxin Bao, Jifeng Ouyang, Chengyuan Liu, Yang Pan, Shihui Zou, Jie Fan
The development of efficient CH3Cl-to-C2H3Cl catalysts remains challenging due to the poor dispersion of Na2WO4 at high loadings, which limits catalytic performance. This study addresses this issue by employing silicon carbide (SiC) as a support, which undergoes an in-situ phase transformation to α-cristobalite during calcination, effectively enhancing Na2WO4 dispersion even at 35 wt% loading. The resulting catalyst achieved a vinyl chloride selectivity of 35.1% and a yield of 31.4% at 700 °C, significantly outperforming conventional Na2WO4/SiO2 catalysts synthesized with α-cristobalite. These findings highlight the importance of support-mediated phase transformations in designing high-performance MCTV catalysts, offering a sustainable pathway for VCM production.
{"title":"Phase transition of SiC support induces dispersed Na2WO4 catalysts for CH3Cl-to-C2H3Cl conversion","authors":"Xutao Chen, Yue Wang, Kunkun Wei, Yunxin Bao, Jifeng Ouyang, Chengyuan Liu, Yang Pan, Shihui Zou, Jie Fan","doi":"10.1039/d5nr03574k","DOIUrl":"https://doi.org/10.1039/d5nr03574k","url":null,"abstract":"The development of efficient CH3Cl-to-C2H3Cl catalysts remains challenging due to the poor dispersion of Na2WO4 at high loadings, which limits catalytic performance. This study addresses this issue by employing silicon carbide (SiC) as a support, which undergoes an in-situ phase transformation to α-cristobalite during calcination, effectively enhancing Na2WO4 dispersion even at 35 wt% loading. The resulting catalyst achieved a vinyl chloride selectivity of 35.1% and a yield of 31.4% at 700 °C, significantly outperforming conventional Na2WO4/SiO2 catalysts synthesized with α-cristobalite. These findings highlight the importance of support-mediated phase transformations in designing high-performance MCTV catalysts, offering a sustainable pathway for VCM production.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"6 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704822","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We report the magneto-optic response of “puckered” graphene quantum sheets (GQSs) decorated by graphene quantum dots (GQDs) of ~5 nm in size. The magneto-optic coupling helps in improving the response of the photodetectors. The enhancement ratio (ROFF /RON) of the commercial bare and coated light dependent resistors (LDRs) are analyzed in the absence and presence of magnetic field and UV light. The magnetic coupling is exhibiting due to the availability of unpaired electrons in GQSs. The Raman study supports the presence of defect sites leading to spin polarization of the delocalized electrons in the influence of a transverse magnetic field. The magnetic field increases the conductivity by allowing charge carriers to travel in curved trajectory experiencing Lorentz force. The measured response and decay times are 5.56 and 93.28 ms, respectively which are comparable to the commercial LDRs. The cumulative contribution of higher sp2 % (87 %), enhanced I2D/ID (~25) and lower ID/IG (0.02) ratios enhanced the magneto-optic response ~15 % at 300 K with the variation of magnetic field from 0 to 0.7 T. The synthesized unique puckered graphene quantum materials showing reasonably improved magneto-optic characteristics may find its application in various quantum technologies.
{"title":"Development of magneto-optic sensors in ultra-violet region employing graphene quantum architectures","authors":"Rajib Mahato, Maruthi Mala, Anagh Bhaumik","doi":"10.1039/d5nr04296h","DOIUrl":"https://doi.org/10.1039/d5nr04296h","url":null,"abstract":"We report the magneto-optic response of “puckered” graphene quantum sheets (GQSs) decorated by graphene quantum dots (GQDs) of ~5 nm in size. The magneto-optic coupling helps in improving the response of the photodetectors. The enhancement ratio (ROFF /RON) of the commercial bare and coated light dependent resistors (LDRs) are analyzed in the absence and presence of magnetic field and UV light. The magnetic coupling is exhibiting due to the availability of unpaired electrons in GQSs. The Raman study supports the presence of defect sites leading to spin polarization of the delocalized electrons in the influence of a transverse magnetic field. The magnetic field increases the conductivity by allowing charge carriers to travel in curved trajectory experiencing Lorentz force. The measured response and decay times are 5.56 and 93.28 ms, respectively which are comparable to the commercial LDRs. The cumulative contribution of higher sp2 % (87 %), enhanced I2D/ID (~25) and lower ID/IG (0.02) ratios enhanced the magneto-optic response ~15 % at 300 K with the variation of magnetic field from 0 to 0.7 T. The synthesized unique puckered graphene quantum materials showing reasonably improved magneto-optic characteristics may find its application in various quantum technologies.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"5 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Plinio Daniel Rosales, Amartya Viravalli, Anna Schneider, Natalie Boehnke
Understanding how lipids integrate and self-assemble into nanoparticles is needed to design functional lipid-based drug delivery systems. While lipid-based nanoparticles offer a modular and chemically diverse design space, tools to quantitatively assess the assembly and distribution of diverse lipids within nanoparticles remain limited. Here, we present a Förster Resonance Energy Transfer (FRET)-based approach to quantify lipid incorporation within liposomes and lipid nanoparticles (LNPs). This approach is modular and adaptable, compatible with a broad range of lipids with chemically modifiable moieties. To guide experimental design and optimal labeling, we developed a theoretical model describing the distribution of labeled lipids within a nanoparticle and experimentally validated it using established liposomal formulations. We applied our FRET-based approach to monitor lipid post-insertion into liposomes and quantify incorporation of a range of phospholipids. This includes an understudied but therapeutically relevant class of lipids known as plasmalogens, which have self-assembly properties that are difficult to predict. We further extended our toolkit to study lipid incorporation in LNPs and found that lipid incorporated uniformly without disrupting Fluorescence nanoparticle tracking analysis (F-NTA) confirmed our findings. Overall, by enabling quantitative analysis of individual lipid components within complex formulations, this toolkit fills a critical gap in nanoparticle characterization and can accelerate the rational design of next-generation lipid-based therapeutics.
{"title":"A FRET-based toolkit for quantifying lipid incorporation into nanoparticles","authors":"Plinio Daniel Rosales, Amartya Viravalli, Anna Schneider, Natalie Boehnke","doi":"10.1039/d5nr03734d","DOIUrl":"https://doi.org/10.1039/d5nr03734d","url":null,"abstract":"Understanding how lipids integrate and self-assemble into nanoparticles is needed to design functional lipid-based drug delivery systems. While lipid-based nanoparticles offer a modular and chemically diverse design space, tools to quantitatively assess the assembly and distribution of diverse lipids within nanoparticles remain limited. Here, we present a Förster Resonance Energy Transfer (FRET)-based approach to quantify lipid incorporation within liposomes and lipid nanoparticles (LNPs). This approach is modular and adaptable, compatible with a broad range of lipids with chemically modifiable moieties. To guide experimental design and optimal labeling, we developed a theoretical model describing the distribution of labeled lipids within a nanoparticle and experimentally validated it using established liposomal formulations. We applied our FRET-based approach to monitor lipid post-insertion into liposomes and quantify incorporation of a range of phospholipids. This includes an understudied but therapeutically relevant class of lipids known as plasmalogens, which have self-assembly properties that are difficult to predict. We further extended our toolkit to study lipid incorporation in LNPs and found that lipid incorporated uniformly without disrupting Fluorescence nanoparticle tracking analysis (F-NTA) confirmed our findings. Overall, by enabling quantitative analysis of individual lipid components within complex formulations, this toolkit fills a critical gap in nanoparticle characterization and can accelerate the rational design of next-generation lipid-based therapeutics.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"27 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Houting Wang,Yongjie Wang,Zeyang Liu,Yuanli Zhu,Cheng Wang,Leyi Wang,Rui Liu,Guohua Liu,Chunxia Tan
Overcoming mass transport limitations imposed by stagnant boundary layers is critical for advancing heterogeneous catalysis. Building upon strategies utilizing deformable metal-organic nanosheets (MONs) to enhance diffusion, we report the synthesis of well-defined core-shell microspheres that integrate flexible and functional two-dimensional MONs. Nonporous carboxyl-terminated SiO2 nanoparticle cores are seamlessly enveloped by ultrathin Zr-MON shells through a facile bottom-up approach. The resulting MON@SiO2 architecture exposes abundant coordinatively unsaturated Zr(IV) Lewis acid sites on its deformable nanosheets. Further introduction of the triethylenediamine (DABCO) moieties into the MON produces MON-DABCO@SiO2, enabling the co-existence of isolated Lewis acid and base sites amenable to promoting challenging reactions that are unachievable by homogeneous systems. These dynamic core-shell structures significantly enhance molecular diffusion to the active sites, as evidenced by ultra-efficient catalysis (>99% yield) in the one-pot hydrolysis-Knoevenagel tandem reactions across broad-scope substrates. Importantly, the SiO2 core confers exceptional structural durability, enabling great catalytic recyclability for at least 5 consecutive cycles without any degradation of the performances, which is in stark contrast to the unsupported MONs. This work therefore establishes core-shell engineering of deformable MONs as a versatile approach for architecting high-performance and durable heterogeneous catalysts by synergistically combining enhanced mass transport with nanoconfinement effects.
{"title":"Deformable metal-organic nanosheets@SiO2 core-shell for heterogeneous tandem catalytic transformations.","authors":"Houting Wang,Yongjie Wang,Zeyang Liu,Yuanli Zhu,Cheng Wang,Leyi Wang,Rui Liu,Guohua Liu,Chunxia Tan","doi":"10.1039/d5nr04441c","DOIUrl":"https://doi.org/10.1039/d5nr04441c","url":null,"abstract":"Overcoming mass transport limitations imposed by stagnant boundary layers is critical for advancing heterogeneous catalysis. Building upon strategies utilizing deformable metal-organic nanosheets (MONs) to enhance diffusion, we report the synthesis of well-defined core-shell microspheres that integrate flexible and functional two-dimensional MONs. Nonporous carboxyl-terminated SiO2 nanoparticle cores are seamlessly enveloped by ultrathin Zr-MON shells through a facile bottom-up approach. The resulting MON@SiO2 architecture exposes abundant coordinatively unsaturated Zr(IV) Lewis acid sites on its deformable nanosheets. Further introduction of the triethylenediamine (DABCO) moieties into the MON produces MON-DABCO@SiO2, enabling the co-existence of isolated Lewis acid and base sites amenable to promoting challenging reactions that are unachievable by homogeneous systems. These dynamic core-shell structures significantly enhance molecular diffusion to the active sites, as evidenced by ultra-efficient catalysis (>99% yield) in the one-pot hydrolysis-Knoevenagel tandem reactions across broad-scope substrates. Importantly, the SiO2 core confers exceptional structural durability, enabling great catalytic recyclability for at least 5 consecutive cycles without any degradation of the performances, which is in stark contrast to the unsupported MONs. This work therefore establishes core-shell engineering of deformable MONs as a versatile approach for architecting high-performance and durable heterogeneous catalysts by synergistically combining enhanced mass transport with nanoconfinement effects.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"30 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704429","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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