InfoMat
·
2022
·Vol. 4
·期 12
·e12349
·
IF 24.798
Hong Zhou,Dongxiao Li,Zhihao Ren,Xiaojing Mu,Chengkuo Lee
Metamaterials have proven their ability to possess extraordinary physical properties distinct from naturally available materials, leading to exciting sensing functionalities and applications. However, metamaterial-based sensing applications suffer from severe performance limitations due to noise interference and design constraints. Here, we propose a dual-phase strategy that leverages loss-induced different Fano-resonant phases to access both destructive and constructive signals of molecular vibration. When the two reverse signals are innovatively combined, the noise in the detection system is effectively suppressed, thereby breaking through the noise-related limitations. Additionally, by utilizing loss optimization of the plasmon-molecule coupling system, our dual-phase strategy enhances the efficiency of infrared energy transfer into the molecule without any additional fabrication complex, thereby overcoming the trade-off dilemma between performance and fabrication cost. Thanks to the pioneering breakthroughs in the limitations, our dual-phase strategy possesses an overwhelming competitive advantage in ultrasensitive vibrational spectroscopy over traditional metamaterial technology, including strong signal strength (×4), high sensitivity (×4.2), effective noise suppression (30%), low detection limit (13 ppm), and excellent selectivity among CO 2 , NH 3 , and CH 4 mixtures. This work not only opens the door to various emerging ultrasensitive detection applications, including ultrasensitive in-breath diagnostics and high-information analysis of molecular information in dynamic reactions, but also gains new insights into the plasmon-molecule interactions in advanced metamaterials.
研究领域:
光学
·
材料科学
·
传感技术
✓ 已验证
产品关联
DOI
高影响因子
ACS Central Science
·
2021
·
IF 14.553
Yuchen Tang,Yongpeng Zhuang,Shaohua Zhang,Zachary J. Smith,Yuee Li,Xijiao Mu,Mengna Li,Caili He,Xingxing Zheng,Fangfang Pan,Tingjuan Gao,Lizhi Zhang
Raman scattering provides stable narrow-banded signals that potentially allow for multicolor microscopic imaging. The major obstacle for the applications of Raman spectroscopy and microscopy is the small cross section of Raman scattering that results in low sensitivity. Here, we report a new concept of azo-enhanced Raman scattering (AERS) by designing the intrinsic molecular structures using resonance Raman and concomitant fluorescence quenching strategies. Based on the selection of vibrational modes and the enhancing unit of azobenzenes, we obtained a library of AERS molecules with specific Raman signals in the fingerprint and silent frequency regions. The spectral characterization and molecular simulation revealed that the azobenzene unit conjugated to the vibrational modes significantly enhanced Raman signals due to the mechanism of extending the conjugation system, coupling the electronic–vibrational transitions, and improving the symmetry of vibrational modes. The nonradiative decay of azobenzene from the excited state quenched the commitment fluorescence, thus providing a clean background for identifying Raman scattering. The most sensitive AERS molecules produced Raman signals of more than 4 orders of magnitude compared to 5-ethynyl-2′-deoxyuridine (EdU). In addition, a frequency tunability of 10 distinct Raman bands was achieved by selecting different types of vibrational modes. This methodology of AERS allows for designing small-molecule Raman probes to visualize various entities in complex systems by multicolor spontaneous Raman imaging. It will open new prospects to explore innovative applications of AERS in interdisciplinary research fields.
研究领域:
生物物理学
·
分析化学
·
分子生物学
✓ 已验证
DOI
PubMed
高影响因子
ADVANCED MATERIALS
·
2021
·Vol. 34
·期 8
·2109088
·
IF 30.849
Kaizhen Liu,Guangyan Huang,Xiang Li,Guangpeng Zhu,Wei Du,Tao Wang
Vibrational strong coupling (VSC), the strong coupling between optical resonances and the dipolar absorption of molecular vibrations at mid-infrared frequencies, holds the great potential for the development of ultrasensitive infrared spectroscopy, the modification of chemical properties of molecules, and the control of chemical reactions. In the realm of ultracompact VSC, there is a need to scale down the size of mid-infrared optical resonators and to elevate their optical field strength. Herein, by using single quartz micropillars as mid-infrared optical resonators, the strong coupling is demonstrated between surface phonon polariton (SPhP) resonances and molecular vibrations from far-field observation. The single quartz micropillars support sharp SPhP resonances with an ultrasmall mode volume, which strongly couples with the molecular vibrations of 4-nitrobenzyl alcohol (C 7 H 7 NO 3 ) molecules featuring pronounced mode splitting and anticrossing dispersion. The coupling strength depends on the molecular concentration and reaches the strong coupling regime with only 7300 molecules. The findings pave the way for promoting the VSC sensitivity, miniaturing the VSC devices, and will boost the development of ultracompact mid-infrared spectroscopy and chemical reaction control devices.
研究领域:
物理化学
·
光学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Chemical Science
·
2024
·
IF 7.6
Xiaoxuan Zheng,Quanbing Pei,Junjun Tan,Shiyu Bai,Yi Luo,Shuji Ye
Plasmonic nanocavities enable the generation of strong light–matter coupling and exhibit great potential in plasmon-mediated chemical reactions (PMCRs). Although an electric field generated by nanocavities (En) has recently been reported, its effect on the vibrational energy relaxation (VER) of the molecules in the nanocavities has not been explored. In this study, we reveal the impact of an electric field sensed by molecules (para-substituted thiophenol derivatives) in a nanocavity (Ef) on VER processes by employing advanced time-resolved femtosecond sum frequency generation vibrational spectroscopy (SFG-VS) supplemented by electrochemical measurements. The magnitude of En is almost identical (1.0 ± 0.2 V nm−1) beyond the experimental deviation while Ef varies from 0.3 V nm−1 to 1.7 V nm−1 depending on the substituent. An exponential correlation between Ef and the complete recovery time of the ground vibrational CC state (T2) of the phenyl ring is observed. Substances with a smaller T2 are strongly correlated with the reported macroscopic chemical reactivity. This finding may aid in enriching the current understanding of PMCRs and highlights the possibility of regulating vibrational energy flow into desired reaction coordinates by using a local electric field.
研究领域:
物理化学
·
材料科学
·
光化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2019
·
IF 2.12
Lijuan Huang,Xin Zhang,Zhuoyong Zhang
Terahertz time-domain spectroscopy (THz-TDS) provides a novel approach for the coordination compounds characterization. In this paper, the THz absorption spectra of iron complexes and M-EDTA (M = Cd 2+ , Cu 2+ , Ni 2+ , Co 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Cr 3+ ) complexes were investigated. Comparing to the infrared (IR) spectra of those compounds, the THz spectra can provide unique chemical and intermolecular vibrational information. The M − O and M − N vibrational modes in the THz-TDS spectra of M-EDTA complexes reveal the vibrational information of intermolecular interactions . Characteristic absorption bands in the THz spectra of various complexes and ligands are observed. THz absorption spectra of iron complexes and different ligands exhibited characteristic absorption bands in 0–2.2 THz region. These characteristic bands can be used to characterize and identify different complexes and ligands. The molecular vibrational information in the THz spectral band provides the unique fingerprint for further study of coordination compounds identification and structure characterization.
研究领域:
化学
·
材料科学
·
光谱学
✓ 已验证
产品关联
DOI
高影响因子
Nano Energy
·
2021
·
IF 17.881
Haitao Li,Hui Yin,Han Dai,Hiang Kwee Lee,Yanying Cui,Fuwei Sun,Yihe Zhang,Qi An
Promoting the quality of surface-enhanced Raman spectra (SERS) holds immense significance in various research fields, such as high-sensitive detection or real-time in situ monitoring. However, obtaining rich molecular information from the vibration modes in SERS remains difficult due to the surface selection rules. Herein, we develop an electrically enhanced, composite SERS substrate by combining flower-like Ag nanostructures with a piezoelectric-dielectric polymeric film . The piezoelectricity generated in the polymeric film transforms into combined quasi-static electrical fields with multi-directional distributions and intensified plasmonic hotspots in the Ag nanoflowers . Molecules adsorbed on the Ag nanoflowers are propelled by the quasi-static electrical fields and deviate from the absorption equilibrium states, a key criterion to present additional SERS peaks. In addition, the intensified hotpots generate SERS peaks with higher intensities (> ~ 2 times). Dual-enhanced SERS in both the intensity and the number of vibration peaks e.g., 3 peaks more for 4-Mpy, are obtained from a variety of widely used molecular Raman probes as well as pesticide contaminants. The universality of the dual enhancement effects from our SERS design with increasing detection sensitivity demonstrates high applicability in the rapid and on-site detection of real samples. The changes to SERS spectra, and thus the molecular vibrational fingerprints, in the combined static and plasmonic electrical fields may also inspire scientific understanding in photoelectrical catalytic processes.
研究领域:
材料科学
·
光谱学
·
化学
✓ 已验证
DOI
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2021
·
IF 3.498
Xiao-Shuo Wu,Ru Zhang,Jian-Lan Liu
A new 2D phosphorescence lead metal cluster-based coordination polymer (CP) [Pb 4 ( μ 2 -OH) ( μ 3 -OH) ( μ 4 -O) (3-qlc) 4 ] n ( 1 ; 3-qlc = 3-quinolinecarboxylate) has been successfully synthesized by solvothermal reaction. CP 1 is a robust Pb(II) CP constructed by a rare [Pb 8 ( μ 2 -OH) 2 ( μ 3 -OH) 2 ( μ 4 -O) 2 (COO) 8 ] cluster units and 3-qlc ligands. The bulky clusters provide architectural stability to the framework of 1 . Interestingly, CP 1 exhibited almost pure room-temperature orange phosphorescence with absolute phosphorescence quantum yields of 3.3% and a phosphorescence lifetime of 1.52 ms benefiting from the restriction of molecular vibrations/rotations of organic luminogens (3-qlc) and the heavy-atom effect of Pb(II).
研究领域:
材料化学
·
配位化学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Optical Materials
·
2018
·Vol. 6
·期 17
·1800436
·
IF 7.43
Nannan Li,Hang Yin,Xiaolu Zhuo,Baocheng Yang,Xiao-Ming Zhu,Jianfang Wang
Surface-enhanced infrared absorption (SEIRA) spectroscopy, the enhancement of molecular vibrational signals using resonant metal nanostructures, has recently attracted much attention owing to its potential use in molecular detection in chemistry, biology, and medicine. This study reports on the growth of high-aspect-ratio metal nanocrystals and their application for SEIRA. Highly uniform Ag nanorods are synthesized through Au nanobipyramid-directed Ag overgrowth, and Au nanotubes are further prepared through the galvanic replacement reaction from the Ag nanorods. Both Ag nanorods and Au nanotubes possess narrow distributions in diameter and length and exhibit highly tunable plasmon wavelengths in the near and mid-infrared regions. The Ag nanorods are employed as plasmonic nanoantennas to enhance the molecular vibration signals of cetyltrimethylammonium bromide molecules that are embedded in a mesostructured silica layer coated on the Ag nanorods. The dimension-dependent SEIRA performances are carefully investigated both experimentally and numerically. The experimental and simulated SEIRA enhancement factors are in good agreement and both determined to be of the order ≈10 3 . The results point out a promising route to the utilization of chemically synthesized, colloidal metal nanostructures as SEIRA platforms. The synthesis method also provides high-quality metal nanostructures for exploring various plasmon-based optical and sensing applications in the infrared region.
研究领域:
化学
·
纳米科技
·
光学
·
生物医学工程
✓ 已验证
DOI
高影响因子
Advanced Optical Materials
·
2022
·Vol. 10
·期 8
·2101973
·
IF 10.05
Yan Zhao,Shuo-Hui Cao,Jia-Dai Wang,Na Li,Guo-Chun Lin,Yao-Qun Li
Probing light−matter interactions at the nanoscale is essential for elucidation of their fundamentals and construction of novel nano-optical devices. In this work, it is proposed that polarization- and angle-dependent plasmonic synchronous fluorescence spectroscopy could be powerful to resolve UV–vis plasmon mediated molecular couplings, even under vibrational sublevels. Taking studies of polycyclic aromatic hydrocarbons (PAHs, one general class of graphene analogs with emission range of 350–550 nm) as demonstration, a simple but efficient device of PAHs nanolayer (with thickness in tens to hundreds of nanometers) on an Al nano-film is fabricated. By synchronously scanning excitation and emission wavelengths in a high resolution to depict polarization- and angle-dependent spectrographic profiles, the vibrational transitions coupled to the Al plasmons could be identified, while these could not be attained by conventional fluorescence measurement. As a result, the featured molecular vibrational couplings for both surface plasmon- and plasmonic waveguide-mediated PAHs–Al interactions have been successfully observed at room temperature. Even toward crowded and overlapped spectral components containing multiple vibrations, the transitions could be individually distinguished. These efforts will contribute to the further exploitation and construction of efficient light-emitting devices via luminant molecules on a metal surface.
研究领域:
光学
·
纳米科技
·
材料科学
✓ 已验证
DOI
高影响因子
ANALYTICAL CHEMISTRY
·
2025
·
IF 6.7
Pengfei Wang,Weifang Han,Yu Wu,Chengqian You,Chunyi Zhang,Qiuhong Qu,Xiaohong Sun,Xiaonan Yang,Mingxia He
Pharmaceutical cocrystals have attracted extensive interest to optimize the physicochemical properties of active pharmaceutical ingredients (APIs), which benefits nonsteroidal anti-inflammatory drugs (NSAIDs) by linking them with cocrystal formers (CCFs) via intermolecular interactions. The energy level matching between terahertz (THz) photons and intermolecular interactions makes THz spectroscopy sensitive to characterizing API-CCF cocrystals by spectral fingerprint. However, the limited frequency bandwidth and temperature range restrict the comprehensive understanding of spectral evolution and the molecular vibrational pattern. In this work, THz time-domain spectroscopy (THz-TDS) and synchrotron radiation-based broadband THz (SRBB-THz) are combined to extend the frequency range to 0.5–18 THz. A naproxen-proline (NAP-Pro) cocrystal is selected to conduct experiments from room temperature to 4.2 K. As the temperature decreases, the spectral evolution is characterized by peak sharpening, new peak appearance, peak shift, and peak splitting. The parameters of full width at half maximum (FWHM) and frequency shift are quantitatively fitted by a quadratic function and Bose–Einstein statistics, respectively. Quantum chemical calculations are further carried out to assign fingerprint frequencies to specific molecular vibrations, where collective vibrational modes govern low frequencies of 2–6 THz and individual modes dominate high frequencies of 6–17 THz. Based on oscillation theory, this is attributed to distinct force constants with respect to a specific vibrational mode. This study elucidates the evolutionary pattern of temperature-induced spectral features and molecular vibrational modes, which is insightful for investigating the pharmaceutical cocrystal system and systematically understanding the THz spectral characteristics.
研究领域:
药物晶体工程
·
光谱分析化学
·
分子物理药剂学
·
低温光谱学
·
计算药物化学
·
固态化学
·
太赫兹生物医学成像
✓ 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）