Science Advances
·
2024
·Vol. 10
·期 42
·
IF 11.7
Jun Zhang,Kai Wu,Xiaoqing Gao,Min Zhang,Xin Zhou,Florian Bertram,Chen Shen,Yunlong Zhou
Chiral structures and functions are essential natural components in biominerals and biological crystals. Chiral molecules direct inorganics through chiral growth of facets or screw dislocation of crystal clusters. As chirality promoters, they initiate an asymmetric hierarchical self-assembly in a quasi-thermodynamic steady state. However, achieving chiral assembly requires a delicate balance between intricate interactions. This complexity causes the roles of achiral-chiral and inorganic components in crystallization to remain ambiguous. Here, we elucidate a definitive mechanism using an achiral-chiral ligand strategy to assemble inorganics into hierarchical, self-organized superstructures. Achiral ligands cluster inorganic building blocks, while chiral ligands impart chiral rotation. Achiral and chiral ligands can flexibly modulate the chirality of superstructures by fully using their competition in coordination chemistry. This dual-ligand strategy offers a versatile framework for engineering chiroptical nanomaterials tailored to optical devices and metamaterials with optical activities across a broad wavelength range, with applications in imaging, detection, catalysis, and sensing.
研究领域:
材料科学
·
纳米技术
·
化学
·
光学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Nano
·
2020
·
IF 14.588
Jiaqi Liang,Peipei Guo,Xujin Qin,Xiaohui Gao,Kai Ma,Xuefeng Zhu,Xue Jin,Weiwei Xu,Lingxiang Jiang,Pengfei Duan
Biomaterials in nature often exhibit hierarchical chiral structures with an intriguing mechanism involving hierarchical chirality transfer from molecular to supramolecular and the nano- or microscale level. To mimic the cross-level chirality transfer, we present here one kind of host–guest complex system built of β-cyclodextrin (β-CD), sodium dodecyl sulfate (SDS), and fluorescent dyes, which show multilevel chirality, including molecular chirality of β-CD, induced supramolecular chirality of β-CD/SDS host–guest complexes, a chiral lattice self-assembled nanosheet, mesoscopic chirality of an assembled helical tube, induced chirality of a dye-doped chiral tube. The hierarchical chirality involved a chiral lattice self-assembly process, which can be identified by small-angle X-ray scattering, optical studies, circular dichroism, and circularly polarized luminescence spectral measurements. Benefiting from the chiral lattice self-assembly, intense circularly polarized luminescence was observed from the achiral dye-doped complexes with a large dissymmetry factor up to +0.1. This work thus provides a feasible insight for developing hierarchical chiroptical materials based on the lattice self-assembly.
研究领域:
材料科学
·
化学
·
生物仿生学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Physical Chemistry Letters
·
2022
·
IF 6.888
Xudong Li,Peixian Chen,Yong Xia,Ji Weng,Meijuan Chen,Tingchao He,Yiwen Li,Jiaji Cheng,Lei Zhang
Chiral tellurium nanoparticles have recently garnered tremendous attention as emerging inorganic nanomaterials with intrinsically chiral space groups owing to their potential in next-generation stereosynthesis, spintronics, and optoelectronics. Inspired by the chiral ligand-mediated synthetic strategy, we herein present hydrothermal-assisted synthesis of chiral polyhedral tellurium nanoparticles that provides differed chirogenesis than that of particles fabricated by wet chemistry in recent studies; the thiolated cysteine molecules change the morphology of tellurium nanoparticles from fundamental two-dimensional shapes to chiral three-dimensional polyhedra owing to the screw dislocation effects observed only during nanoparticle growth. However, the nanoparticles do not exhibit chiral behaviors at the nucleation stage. Further investigation indicates that the growth of chiral polyhedral tellurium nanoparticles is overwhelmingly affected by parameters such as the hydrothermal reaction time, amount of polyvinylpyrrolidone, and species of chiral molecules. We believe that these findings can provide new insights into the fundamental relationships among structural chirality, chiral ligands, screw dislocations, and chiral space groups in principle.
研究领域:
纳米材料
·
无机化学
·
材料科学
·
物理化学
·
手性
✓ 已验证
DOI
高影响因子
ANALYTICAL CHEMISTRY
·
2020
·
IF 6.785
Chengyi Xie,Liancheng Gu,Qidi Wu,Lei Li,Chenlu Wang,Jiancheng Yu,Keqi Tang
Chiral analysis is critical to many research fields due to different biological functions of enantiomers in living systems. Although the use of ion mobility spectrometry (IMS) has become an alternative technology in the area of chiral measurements, there is still a lack of a general chiral selector for IMS-based chiral recognition, especially for small chiral molecules. Here, a new method using oligosaccharides as the chiral selector has been developed to discriminate chiral amino acids (AAs) by trapped ion mobility spectrometry-mass spectrometry (TIMS-MS). We analyzed 21 chiral amino acids, including small molecules (e.g., alanine and cysteine). Our data showed that the use of nonreducing tetrasaccharides was effective for the separation of chiral AAs, which differentiated 21 chiral AAs without using metal ions. By further incorporating a copper ion, the separation resolution could be improved to 1.64 on average, which accounts for an additional 52% improvement on top of the already achieved separation in metal-free analysis. These results indicate that the use of tetrasaccharides is an effective strategy for the separation of AA enantiomers by TIMS. The method developed in this study may open up a new strategy for effective IMS-based chiral analysis.
研究领域:
分析化学
·
质谱
·
手性
·
生物化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ANALYTICAL SCIENCES
·
2022
·Vol. 38
·期 7
·989-1002
·
IF 1.967
Zeng Qingli,Zhong Hui,Zhang Tianci,Huang Zhiqin,Li Laisheng
A large π-conjugated perylenediimide bridged bis (β-cyclodextrin)-bonded stationary phase (PBCDP) was first prepared and characterized. The chiral HPLC performance was systematically evaluated using a series of chiral probes. The results showed that PBCDP could resolve 36 kinds of chiral compounds in reversed-phase and polar organic modes with high resolutions ( R s) 1.48–3.28 for profens, 1.25–2.85 for triazoles, 1.34–5.29 for flavanones, 1.66–4.58 for amino acids and 1.22–1.97 for β-blockers. Especially, PBCDP could completely resolve acidic non-steroidal chiral drugs (profens) and simultaneously resolve basic five triazole pesticides, which were difficult to separate by ordinary CDCSP. Compared with CDCSP (15 kinds), the new stationary phase has a wider resolution range (36 kinds). Obviously, the synergistic inclusion of the two cavities of bridged cyclodextrin, as well as the large π–π stacking, hydrogen bond, dipole–dipole and basic primary amine site (–NH–) provided by the perylenediimide bridging group contributed together to the improvement of the above chiral separations. PBCDP was a new type of versatile chiral separation material without port derivatization. Graphical abstract
研究领域:
分析化学
·
色谱技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SCIENCE
·
2025
·Vol. 389
·期 6761
·
IF 45.8
Minju Kim,Mingyue Zhang,You-Liang Zhu,Yan Yan,Xin Pu,Woosung Choi,Sein Chung,Kilwon Cho,Jeongwon Kim,Vladimir Tsukruk,Zhenzhong Yang,Nicholas A. Kotov,Zhong-Yuan Lu,Dong Ha Kim,Zhiqun Lin
Supramolecular assemblies hold great promise for advanced chiral materials because of their structural diversity and dynamic features, but their low chiroptical activity limits practical applications. We report hierarchical supramolecular assemblies with giant chiroptical activity and mechanical attributes achieved through coassembly of achiral amphiphilic unimolecular micelles and chiral additives. Chiral fibrillar assemblies emerge from the nanostructured environment imposed by the micelles, driven by progressive chirality transfer through multiple hydrogen bonds between components. Integrating multifarious achiral luminescent molecules and nanocrystals into these assemblies leads to full-color circularly polarized luminescence–active materials with dissymmetry factors of ~10 −1 . A concentration-dependent chirality inversion is accessed through tailoring the coassembly kinetics. This strategy enables efficient red CPL, crucial for quantum and optical technologies.
研究领域:
超分子化学
·
材料科学
·
手性光学
·
纳米技术
·
发光材料
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Polymer Chemistry
·
2015
·Vol. 6
·期 39
·7045-7052
·
IF 5.52
Lu Yin,Yin Zhao,Shunqin Jiang,Laibing Wang,Zhengbiao Zhang,Jian Zhu,Wei Zhang,Xiulin Zhu
A series of star-shaped azobenzene (Azo)-containing side chain polymers with 3, 4 and 6 arms were synthesized by the atom transfer radical polymerization technique initiated by multifunctional initiators. The intense bisignated circular dichroism (CD) signals in the UV–vis region were observed when these star polymers aggregated in a dichloroethane/limonene mixed solvent, indicating the successful chirality transfer from limonene molecules to these star Azo polymers. The chirality originates from the preferential supramolecular chirality of well-organized optically inactive side-chain Azo units. The supramolecular chirality is closely related to the volume fraction of cosolvents, the enantiopurity (ee) of limonene, molecular weight and arm numbers of star Azo polymers. Interestingly, the maximum values of CD and gCD of the polymer aggregates increase with molecular weight in the case of 3-armed Azo polymers, and increase simultaneously with arm numbers of the polymers having similar repeating units under each optimized experimental condition. Surprisingly, the first chiral amplification behaviours were observed in the 4- and 6-armed Azo polymers, but absent in linear and 3-armed counterparts. The supramolecular chirality can be destroyed by trans–cis photoisomerization and recovered by thermal cis–trans isomerization of Azo units. The current research will provide further insight into the mechanism study and production of effective chiroptical materials in chiral solvation induced supramolecular chirality of the achiral polymers.
研究领域:
高分子化学
·
超分子化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
COLLOIDS AND SURFACES B-BIOINTERFACES
·
2018
·
IF 3.997
Na Fan,Rongzheng Liu,Pingping Ma,Xin Wang,Chang Li,Jing Li
In the current stage, the On-Off mechanism of chiral mesoporous silica nanoparticles (CMSN) for delivering achiral drug in chiral environment has rarely been reported. Herein, On-Off chiral mesoporous silica nanoparticles (On-Off-D-CMSN and On-Off-L-CMSN) were successfully synthesized and its particular contribution in delivering achiral drug indometacin (IMC) in chiral environment was mainly studied. The as-synthesized On-Off-D-CMSN and On-Off-L-CMSN were verified by fourier transform infrared spectrometer and circular dichroism. The transmission electron microscope test and nitrogen adsorption/desorption analysis showed that On-Off-D-CMSN and On-Off-L-CMSN were regular spheres with concealed pore channels. The zeta potential analysis demonstrated that the grafting functional groups distributed on the inner and outer surfaces of On-Off-D-CMSN and On-Off-L-CMSN. Through dissolution experiment, the drug release of IMC loaded On-Off-D-CMSN (84%) and IMC loaded On-Off-L-CMSN (70%) were about 2.4 and 2.0 times higher than pure IMC (35%) in pH 6.8 phosphate buffer solution (PBS), respectively. IMC loaded On-Off-D-CMSN and IMC loaded On-Off-L-CMSN exerted different chiral recognition functions with On-Off mechanism in in-vitro chiral environment (pH 6.8 PBS-L and pH 6.8 PBS-D). The results of anti-inflammation pharmacodynamics further demonstrated that On-Off-D-CMSN and On-Off-L-CMSN can trigger chiral biological environment to achieve on or off chiral recognition functions. The unique advantages of On-Off chiral mesoporous silica nanoparticles in triggering chiral biological environment can provide valuable instruction for designing drug delivery system.
研究领域:
纳米技术
·
药学
·
材料科学
·
生物医学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ADVANCED MATERIALS
·
2022
·Vol. 34
·期 37
·2203956
·
IF 32.086
Mengjia Cen,Jiawei Wang,Jianxun Liu,Huilin He,Ke Li,Wenfeng Cai,Tun Cao,Yan Jun Liu
Chiral metasurfaces can exhibit a strong circular dichroism, but it is limited by the complicated fabrication procedure and alignment errors. Here, a new type of self-aligned suspended chiral bilayer metasurface with only one-step electron beam lithography exposure is demonstrated. A significant optical chirality of 221° µm −1 can be realized using suspended metasurfaces with a thickness of 100 nm. Furthermore, this study experimentally demonstrates that such a structure is capable of label-free discrimination of the chiral molecules at zeptomole level, exhibiting a much higher sensitivity (orders of magnitude) compared to the conventional circular dichroism spectroscopy. The fundamental principles for chiral sensing using molecules–metasurfaces interactions are explored. Benefiting from the giant chiroptical response, the proposed metadevice may offer promising applications for ultrathin circular polarizers, chiral molecular detectors, and asymmetry information processing.
研究领域:
光学
·
材料科学
·
纳米技术
·
分析化学
✓ 已验证
DOI
PubMed
高影响因子
MOLECULES
·
2016
·Vol. 21
·期 11
·1466
·
IF 2.465
Shengming Xie,Junhui Zhang,Nan Fu,Bangjin Wang,Cong Hu,Liming Yuan
Molecular organic cage compounds have attracted considerable attention due to their potential applications in gas storage, catalysis, chemical sensing, molecular separations, etc. In this study, a homochiral pentyl cage compound was synthesized from a condensation reaction of (S,S)-1,2-pentyl-1,2-diaminoethane and 1,3,5-triformylbenzene. The imine-linked pentyl cage diluted with a polysiloxane (OV-1701) was explored as a novel stationary phase for high-resolution gas chromatographic separation of organic compounds. Some positional isomers were baseline separated on the pentyl cage-coated capillary column. In particular, various types of enantiomers including chiral alcohols, esters, ethers and epoxides can be resolved without derivatization on the pentyl cage-coated capillary column. The reproducibility of the pentyl cage-coated capillary column for separation was investigated using nitrochlorobenzene and styrene oxide as analytes. The results indicate that the column has good stability and separation reproducibility after being repeatedly used. This work demonstrates that molecular organic cage compounds could become a novel class of chiral separation media in the near future.Keywords:porous organic cage;capillary column;chiral stationary phase;chiral separation;gas chromatography
研究领域:
分析化学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
APPLIED BIOCHEMISTRY AND BIOTECHNOLOGY
·
2016
·Vol. 181
·期 3
·972-985
·
IF 1.606
Wu Hua-Lei,Zhang Jian-Dong,Zhang Chao-Feng,Fan Xiao-Jun,Chang Hong-Hong,Wei Wen-Long
Four uncharacterized ω-transaminases (ωTAs) from Pseudomonas putida NBRC 14164 have been identified and cloned from the pool of fully sequenced genomes. The genes were functionally expressed in Escherichia coli BL21, and the enzymes were purified and characterized. Four TAs showed highly ( S )-selective ωTA activity and converted ( S )-α-methylbenzylamine and pyruvate to acetophenone and l -Ala. The maximum activity of cloned enzymes was in the pH range of 8.0– 8.5 (Pp36420), 8.5 –9. 5 (Pp21050), 9 .0– 9.5 (PpspuC), and 9.5 –1 0 . 5 (PpbauA), and the optimal temperatures were at 35 °C (Pp36420, Pp21050, and PpspuC) and 50 °C (PpbauA), respectively, with K
M of 161.3 mM (Pp21050), 136.7 mM (PpbauA), 398.5 mM (Pp36420), and 130.9 mM (PpspuC) and yielding a catalytic efficiency k
cat / K
M of 0.015, 0.003, 0.012, and 0.023 mM −1 s −1 . Several racemic amines and amino alcohols were resolved by the cloned ωTAs; perfect conversions (48–50 %) were obtained by at least one enzyme, and the residual substrates were left with 97–99 % ee. Kinetic resolution of racemic phenylglycinol was done with PpspuC in a 100-mL scale. Enaniomeric excess of ( S )-phenylglycinol reached 99 % with 45 % isolated yield. The high enantioselectivity and large substrate spectra of the cloned PpTAs showed an attractive potency for biotechnology application in production of chiral amines and amino alcohols.
研究领域:
生物化学
·
酶工程
·
生物技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nanoscale
·
2013
·Vol. 5
·期 16
·7589-7595
·
IF 6.233
Tiantian Cao,Shenshen Jin,Shuxin Wang,Dandan Zhang,Xiangming Meng,Manzhou Zhu
A 25-atom gold nanocluster capped with an achiral thiolate exhibits no chiroptical signals in circular dichroism (CD) measurements. Herein, we report a systematic study on the effects of the chiral environment on the CD response from the Au25 metal core. We found that Au25(SC2H4Ph)18−TOA+ dissolved in a chiral solvent did not give rise to a CD response, nor did Au25(SC2H4Ph)18− when associated with a chiral counterion (e.g., (−)-N-dodecyl-N-methylephedrinium, DME+). Both scenarios imply that the interaction of the chiral counterion (or chiral solvent molecules) with the achiral Au25(SC2H4Ph)18− nanocluster is not strong enough to induce CD signals from the metal core. In contrast, when the metal core is capped with chiral ligands (i.e., Au25(SCH2C*H(NH2)CH2Ph)18), strong CD signals in the visible wavelength range were observed. Thus, the induction of CD signals by surface chiral ligands is much stronger than that by the external chiral environment (including the chiral solvent or counterion). This work reveals some further insight into the origin of the chiroptical response of the Au nanoclusters. These chiral nanoclusters hold potential for practical applications in bioconjugation, sensing, and chiral catalysis.
研究领域:
材料科学
·
光学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）