Anti-Stokes/Stokes Raman peak intensity ratio was used to infer sample temperatures,but the influence factors of system correction factors were not clear.Non-contact in-situ anti-Stokes/Stokes temperature calibration ...Anti-Stokes/Stokes Raman peak intensity ratio was used to infer sample temperatures,but the influence factors of system correction factors were not clear.Non-contact in-situ anti-Stokes/Stokes temperature calibration was carried out for up to 1500 K based on six different samples under two excitation light sources(±50 K within 1000 K,±100 K above1000 K),and the system correction factorγwas systematically investigated.The results show that the correction factorγof anti-Stokes/Stokes thermometry is affected by the wavelength of the excitation light source,Raman mode peak position,temperature measurement region and other factors.The anti-Stokes/Stokes thermometry was applied to the laser-heating diamond anvil cell(LHDAC)experiment to investigate the anharmonic effect of h BN under high temperature and high pressure.It is concluded that the strong anharmonic effect caused by phonon scattering at low pressure gradually changes into the predominance of localized molecular lattice thermal expansion at high pressure.展开更多
In broadband coherent anti-Stokes Raman scattering (CARS) spectroscopy with supercontinuum (SC), the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of variou...In broadband coherent anti-Stokes Raman scattering (CARS) spectroscopy with supercontinuum (SC), the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of various molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactions in the fields of biology, chemistry and material science.展开更多
Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy is used to investigate gaseous molecular dynamics. Due to the spectrally broad laser pulses, usually poorly resolved spectra result...Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy is used to investigate gaseous molecular dynamics. Due to the spectrally broad laser pulses, usually poorly resolved spectra result from this broad spectroscopy. However, it can be demonstrated that by the electronic resonance enhancement optimization control a selective excitation of specific vibrational mode is possible. Using an electronically resonance-enhanced effect, iodine molecule specific CARS spectroscopy can be obtained from a mixture of iodine-air at room temperature and a pressure of 1 atm (corresponding to a saturation iodine vapour as low as about 35 Pa). The dynamics on either the electronically excited state or the ground state of iodine molecules obtained is consistent with previous studies (vacuum, heated and pure iodine) in the femtoseeond time resolved CARS spectroscopy, showing that an effective method of suppressing the non-resonant CARS background and other interferences is demonstrated.展开更多
Femtosecond coherent anti-Stokes Raman scattering (CARS) suffers from poor selectivity between neighbouring Raman levels due to the large bandwidth of the femtosecond pulses. This paper provides a new method to real...Femtosecond coherent anti-Stokes Raman scattering (CARS) suffers from poor selectivity between neighbouring Raman levels due to the large bandwidth of the femtosecond pulses. This paper provides a new method to realize the selective excitation and suppression of femtosecond CARS by manipulating both the probe and pump (or Stokes) spectra. These theoretical results indicate that the CARS signals between neighbouring Raman levels are differentiated from their indistinguishable femtosecond CARS spectra by tailoring the probe spectrum, and then their selective excitation and suppression can be realized by supplementally manipulating the pump (or Stokes) spectrum with the π spectral phase step.展开更多
We performed femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) measurements on liquid toluene and PVK film. For both samples, we selectively excited the CH stretching vibrational modes and ob...We performed femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) measurements on liquid toluene and PVK film. For both samples, we selectively excited the CH stretching vibrational modes and observed the expected quantum beat signals. The frequency of the well-defined beats is in good agreement with the energy difference between the two simultaneously excited modes, which demonstrates that a coherent coupling between the vibrational modes of the C H chemical bonds exists at the different positions of the molecules. The dephasing times of the excited modes are obtained simultaneously.展开更多
Coherent anti-Stokes Raman scattering(CARS)is able to enhance molecular signals by vibrational coherence compared to weak Raman signal.The surface or tip enhancement are successful technologies,which make it possible ...Coherent anti-Stokes Raman scattering(CARS)is able to enhance molecular signals by vibrational coherence compared to weak Raman signal.The surface or tip enhancement are successful technologies,which make it possible for Raman to detect single molecule with nanometer resolution.However,due to technical diffculties,tip-enhanced CARS(TECARS)is not as successful as expected.For single molecular detection,high sensitivity and resolution are two main challenges.Here,we reported the first single atom layer TECARS imaging on Graphene with the highest resolution about 20 nm,which has ever been reported.The highest EF_(TECARS/CARS) is about 10^(4),the similar order of magnitude with SECARS(EF of tip is usually smaller than that of substrates).Such resolution and sensitivity is promising for medical,biology and chemical applications in the future.展开更多
The fluorozirconate glasses ZBLANP( ZrF\-4-BaF\-2-LaF\-3-AlF\-3-NaF-PbF\-2) doped with different Yb\+ 3+ concentration were prepared. The Raman spectra and absorption spectra are measured to substantiate the existenc...The fluorozirconate glasses ZBLANP( ZrF\-4-BaF\-2-LaF\-3-AlF\-3-NaF-PbF\-2) doped with different Yb\+ 3+ concentration were prepared. The Raman spectra and absorption spectra are measured to substantiate the existence of phonon-assisted emission. After analyzing the normalized absorption spectra of samples with different Yb\+ 3+-doped concentration, we calculated the maximum cooling effect in the 3 wt% Yb\+ 3+-doped sample pumped at 1 012.5 nm. The corresponding cooling capability is about -4.09 ℃/W and the cooling efficiency reaches 1.76%.展开更多
Coherent anti-Stokes Raman scattering(CARS)microscopy is used to visualize the release of a model drug(theophylline)from a lipid(tripalmitin)based tablet during dissolution.The effects of transformation and dissolutio...Coherent anti-Stokes Raman scattering(CARS)microscopy is used to visualize the release of a model drug(theophylline)from a lipid(tripalmitin)based tablet during dissolution.The effects of transformation and dissolution of the drug are imaged in real time.This study reveals that the manufacturing process causes significant differences in the release process:tablets prepared from powder show formation of theophylline monohydrate on the surface which prevents a controlled drug release,whereas solid lipid extrudates did not show formation of monohydrate.This visualization technique can aid future tablet design.展开更多
We propose and implement a wide-field vibrational phase contrast detection to obtain imaging of imaginary components of third-order nonlinear susceptibility in a coherent anti-Stokes Raman scattering (CARS) microsco...We propose and implement a wide-field vibrational phase contrast detection to obtain imaging of imaginary components of third-order nonlinear susceptibility in a coherent anti-Stokes Raman scattering (CARS) microscope with full suppression of the non-resonant background. This technique is based on the unique ability of recovering the phase of the generated CARS signal based on holographic recording. By capturing the phase distributions of the generated CARS field from the sample and from the environment under resonant illumination, we demonstrate the retrieval of imaginary components in the CARS microscope and achieve background free coherent Raman imaging.展开更多
In the implementation of CARS nanoscopy, signal strength decreases with focal volume size decreasing. A crucial problem that remains to be solved is whether the reduced signal generated in the suppressed focal volume ...In the implementation of CARS nanoscopy, signal strength decreases with focal volume size decreasing. A crucial problem that remains to be solved is whether the reduced signal generated in the suppressed focal volume can be detected. Here reported is a theoretical analysis of detection limit (DL) to time-resolved CARS (T-CARS) nanoscopy based on our proposed additional probe-beam-induced phonon depletion (APIPD) method for the low concentration samples. In order to acquire a detailed shot-noise limited signal-to-noise (SNR) and the involved parameters to evaluate DL, the T-CARS process is described with full quantum theory to estimate the extreme power density levels of the pump and Stokes beams determined by saturation behavior of coherent phonons, which are both actually on the order of ~ 109 W/cm2. When the pump and Stokes intensities reach such values and the total intensity of the excitation beams arrives at a maximum tolerable by most biological samples in a certain suppressed focal volume (40-nm suppressed focal scale in APIPD method), the DL correspondingly varies with exposure time, for example, DL values are 103 and 102 when exposure times are 20 ms and 200 ms respectively.展开更多
We report on the theoretical and the experimental investigations of the coherent phonon dynamics in sapphire crystal using the femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) technique. The...We report on the theoretical and the experimental investigations of the coherent phonon dynamics in sapphire crystal using the femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) technique. The temporal chirped white-light continuum (WLC) is used for the Stokes pulse, therefore we can perform the selective excitation of the phonon modes without using a complicated laser system. The expected quantum beat phenomenon is clearly observed. The theoretical formulas consist very well with the experimental results. The dephasing times of the excited phonon modes, the wavenumber difference, and the phase shift between the simultaneously excited modes are obtained and discussed. This work opens up a way to study directly high-frequency coherent phonon dynamics in bulk crystals on a femtosecond time scale and is especially helpful for understanding the nature of coherent phonons.展开更多
Coherent anti-Stokes Raman scattering(CA RS)microscopy can resolve the chemical compo-nents and distribution of living biological systems in a label-firee manner and is favored in several disciplines.Current CA RS mic...Coherent anti-Stokes Raman scattering(CA RS)microscopy can resolve the chemical compo-nents and distribution of living biological systems in a label-firee manner and is favored in several disciplines.Current CA RS microscopes typically use bulky,high-performance solid-state lasers,which are expensive and sensitive to environmental changes.With their relatively low cost and environmental sensitivity,supercontinum fiber(SF)lasers with a small footprint have found increasing use in biomedical applications.Upon these features,in this paper,we homebuilt a low-cost CARS microscope based on a SF laser module(scCA RS microscope).This SF laser module is specially customized by adding a time synchronized seed source channel to the SF laser to form a dual-channel output laser.The performance of the scCARS microscope is evaluated with dimethyl sulfoxide,whose results confirm a spatial resolution of better than 500nm and a detection sensitivity of millimolar concentrations.The dual-color imaging capability is further demonstrated by imaging different species of mixed microspheres.We finally explore the potential of our scCARS microscope by mapping lipid droplets in different cancer cells and corneal stromal lenses.展开更多
The widely used energy transfer theory is a foundation of luminescence, in which the rates of Stokes and anti-Stokes processes have the same calculation formula. An improvement on the anti-Stokes energy transfer to ex...The widely used energy transfer theory is a foundation of luminescence, in which the rates of Stokes and anti-Stokes processes have the same calculation formula. An improvement on the anti-Stokes energy transfer to explain the fluorescence intensity reversal between the red and green fluorescence of Er(0.5)Yb(9.5):FOV is reported in the present article. The range of the intensity reversal Z was measured to be 877. Dynamic processes for 16 levels were simulated. A coefficient, the improvement factor of the intensity ratio of Stokes to anti-Stokes processes in quantum Raman theory compared to classical Raman theory, is introduced to successfully describe the anti-Stokes energy transfer. A new method to calculate the distance between the rare earth ions, which is critical for the energy transfer calculation, is proposed. The validity of these important improvements is also proved by experiment.展开更多
The improvement on the calculation of anti-Stokes energy transfer rate is studied in the present work. The additional proportion coefficient between Stokes and anti-Stokes light intensities of quantum Raman scattering...The improvement on the calculation of anti-Stokes energy transfer rate is studied in the present work. The additional proportion coefficient between Stokes and anti-Stokes light intensities of quantum Raman scattering theory as compared with the classical Raman theory is introduced to successfully describe the anti-Stokes energy transfer. The theoretical formula for the improvement on the calculation of anti-Stokes energy transfer rate is derived for the first time in this study. The correctness of introducing coefficient exp{△E/kT} from well-known Raman scatter theory is demonstrated also. Moreover, the experimental lifetime measurement in Er0.01YbxY1-0.01-xVO4 crystal is performed to justify the validity of our important improvement in the original phonon-assisted energy transfer theory for the first time.展开更多
In this paper, we experimentally study the selective excitation of two-pulse femtosecond coherent anti-Stokes Raman scattering (CARS) in a mixture of dibromomethane (CH2Br2) and chloroform (CHCl3) by adaptive pulse sh...In this paper, we experimentally study the selective excitation of two-pulse femtosecond coherent anti-Stokes Raman scattering (CARS) in a mixture of dibromomethane (CH2Br2) and chloroform (CHCl3) by adaptive pulse shaping based on genetic algorithm. Second harmonic generation frequency-resolved optical gating (SHG-FROG) traces indicate that the spectral amplitude and phase of the optimal pulse are both modulated. Finally, we discuss the physical mechanism for the selective excitation of femtosecond CARS based on the retrieved information from SHG-FROG traces.展开更多
Raman lasers based on integrated silica whispering gallery mode resonant cavities have enabled numerous applications from telecommunications to biodetection. To overcome the intrinsically low Raman gain value of silic...Raman lasers based on integrated silica whispering gallery mode resonant cavities have enabled numerous applications from telecommunications to biodetection. To overcome the intrinsically low Raman gain value of silica, these devices leverage their ultrahigh quality factors(Q), allowing submilliwatt stimulated Raman scattering(SRS) lasing thresholds to be achieved. A closely related nonlinear behavior to SRS is stimulated anti-Stokes Raman scattering(SARS). This nonlinear optical process combines the pump photon with the SRS photon to generate an upconverted photon. Therefore, in order to achieve SARS, the efficiency of the SRS process must be high. As a result, achieving SARS in on-chip resonant cavities has been challenging due to the low lasing efficiencies of these devices. In the present work, metal-doped ultrahigh Q(Q > 10~7) silica microcavity arrays are fabricated on-chip. The metal-dopant plays multiple roles in improving the device performance. It increases the Raman gain of the cavity material, and it decreases the optical mode area, thus increasing the circulating intensity. As a result, these devices have SRS lasing efficiencies that are over 10× larger than conventional silica microcavities while maintaining low lasing thresholds. This combination enables SARS to be generated with submilliwatt input powers and significantly improved anti-Stokes Raman lasing efficiency.展开更多
Conventional anti-Stokes materials-involved deep photodynamic therapy(dPDT)requires much high-intensity irradiance due to low photosensitization efficiency.Herein,we proposed a"booster effector"approach to c...Conventional anti-Stokes materials-involved deep photodynamic therapy(dPDT)requires much high-intensity irradiance due to low photosensitization efficiency.Herein,we proposed a"booster effector"approach to construct highly efficient hot band absorption phototherapeutics for low/biosafety power anti-Stokes light-triggered d PDT.Se,as"booster effector",was introduced into hot band absorption luminophores(HBAs),which not only significantly facilitated intersystem crossing,but also simultaneously enhanced hot band excitation efficiency atν808,as a result successfully enabling excellent photogenerated singlet oxygen capability of HBAs under ultra-low power anti-Stokes excitation(10 mW cm^(-2)in vitro).As far as we know,such low laser power-initiated photosensitization activity has never been reported in the existing anti-Stokes material systems.Importantly,FUC-Se ME can self-assemble into uniform nanospheres in water,greatly boosting cellular uptake(>25-fold larger than FUC-Se),and achieve superior cancer-killing effect(808 nm,10 mW cm^(-2),5 min,the half-maximal inhibitory concentration IC50=1.36μM).After further PEGylation with folate-attached polymer,the resultant FUC-Se ME@FA can effectively enrich at the tumor(signal-to-background ratio,10).Under safety irradiation(330 mW cm^(-2)),FUC-Se ME@FA effectively inhibits deep-seated tumor progression(the tumor growth inhibition rate,84%).This work provides a successful paradigm,possibly being more clinically beneficial than conventional anti-Stokes materials.展开更多
Coherent anti-Stokes Raman scattering spectroscopy(CARS) is a well-known detecting tool in biosensing and nonlinear spectroscopy. It can provide a non-invasive alternative without the need for exogenous labels,while...Coherent anti-Stokes Raman scattering spectroscopy(CARS) is a well-known detecting tool in biosensing and nonlinear spectroscopy. It can provide a non-invasive alternative without the need for exogenous labels,while the enhancement factor for surface plasmon resonances(SPR) are extensively used to increase the local field close to the oscillators and which can obtain high enhancement. In this work, we investigate the enhancement factor of our structure for surface-enhanced coherent anti-Stokes Raman scattering. The absorption spectrum of the structure has been studied, a wide range of absorption has been realized. The enhancement can be as high as 10^(16) over standard CARS. Our design is very useful for improving the enhancement factor of surface-enhanced coherent anti-Stokes Raman scattering.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant No.U2030107)the Fundamental Research Funds for the Central Universities(Grant No.2020SCUNL107)。
文摘Anti-Stokes/Stokes Raman peak intensity ratio was used to infer sample temperatures,but the influence factors of system correction factors were not clear.Non-contact in-situ anti-Stokes/Stokes temperature calibration was carried out for up to 1500 K based on six different samples under two excitation light sources(±50 K within 1000 K,±100 K above1000 K),and the system correction factorγwas systematically investigated.The results show that the correction factorγof anti-Stokes/Stokes thermometry is affected by the wavelength of the excitation light source,Raman mode peak position,temperature measurement region and other factors.The anti-Stokes/Stokes thermometry was applied to the laser-heating diamond anvil cell(LHDAC)experiment to investigate the anharmonic effect of h BN under high temperature and high pressure.It is concluded that the strong anharmonic effect caused by phonon scattering at low pressure gradually changes into the predominance of localized molecular lattice thermal expansion at high pressure.
基金Project supported by the National Natural Science Foundation of China(Grant No.60627003)the Foundation for Creative Team in Institution of Higher Education of Guangdong Province,China(Grant No.06CXTD009)
文摘In broadband coherent anti-Stokes Raman scattering (CARS) spectroscopy with supercontinuum (SC), the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of various molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactions in the fields of biology, chemistry and material science.
基金supported by the National Natural Science Foundation of China (Grant Nos.60878018 and 61008023)the Natural Scientific Research Innovation Foundation in Harbin Institute of Technology,China (Grant No.HIT.NSRIF.2009009)the Science and Technology Innovation Foundation,Harbin,China (Grant No.RC2007QN017030)
文摘Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy is used to investigate gaseous molecular dynamics. Due to the spectrally broad laser pulses, usually poorly resolved spectra result from this broad spectroscopy. However, it can be demonstrated that by the electronic resonance enhancement optimization control a selective excitation of specific vibrational mode is possible. Using an electronically resonance-enhanced effect, iodine molecule specific CARS spectroscopy can be obtained from a mixture of iodine-air at room temperature and a pressure of 1 atm (corresponding to a saturation iodine vapour as low as about 35 Pa). The dynamics on either the electronically excited state or the ground state of iodine molecules obtained is consistent with previous studies (vacuum, heated and pure iodine) in the femtoseeond time resolved CARS spectroscopy, showing that an effective method of suppressing the non-resonant CARS background and other interferences is demonstrated.
基金Project supported by Programme for Changjiang Scholars and Innovative Research Team in University(PCSIRT)Shanghai Leading Academic Discipline Project(Grant No.B408)+3 种基金National Key Project for Basic Research of China(Grant Nos.2006CB806006 and 2006CB921105)Ministry of Education of China(Grant No.30800)Shanghai Municipal Natural Science Foundation(Grant No.09ZR1409300)Shanghai Municipal Science and Technology Commission(Grant No.07DZ22025)
文摘Femtosecond coherent anti-Stokes Raman scattering (CARS) suffers from poor selectivity between neighbouring Raman levels due to the large bandwidth of the femtosecond pulses. This paper provides a new method to realize the selective excitation and suppression of femtosecond CARS by manipulating both the probe and pump (or Stokes) spectra. These theoretical results indicate that the CARS signals between neighbouring Raman levels are differentiated from their indistinguishable femtosecond CARS spectra by tailoring the probe spectrum, and then their selective excitation and suppression can be realized by supplementally manipulating the pump (or Stokes) spectrum with the π spectral phase step.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 20573028 and 20973050)
文摘We performed femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) measurements on liquid toluene and PVK film. For both samples, we selectively excited the CH stretching vibrational modes and observed the expected quantum beat signals. The frequency of the well-defined beats is in good agreement with the energy difference between the two simultaneously excited modes, which demonstrates that a coherent coupling between the vibrational modes of the C H chemical bonds exists at the different positions of the molecules. The dephasing times of the excited modes are obtained simultaneously.
基金We gratefully acknowledge the support from the National Natural Science Foundation of China(Nos.21735006 and 21127901),and the CAS Key Technology Talent Program.
文摘Coherent anti-Stokes Raman scattering(CARS)is able to enhance molecular signals by vibrational coherence compared to weak Raman signal.The surface or tip enhancement are successful technologies,which make it possible for Raman to detect single molecule with nanometer resolution.However,due to technical diffculties,tip-enhanced CARS(TECARS)is not as successful as expected.For single molecular detection,high sensitivity and resolution are two main challenges.Here,we reported the first single atom layer TECARS imaging on Graphene with the highest resolution about 20 nm,which has ever been reported.The highest EF_(TECARS/CARS) is about 10^(4),the similar order of magnitude with SECARS(EF of tip is usually smaller than that of substrates).Such resolution and sensitivity is promising for medical,biology and chemical applications in the future.
文摘The fluorozirconate glasses ZBLANP( ZrF\-4-BaF\-2-LaF\-3-AlF\-3-NaF-PbF\-2) doped with different Yb\+ 3+ concentration were prepared. The Raman spectra and absorption spectra are measured to substantiate the existence of phonon-assisted emission. After analyzing the normalized absorption spectra of samples with different Yb\+ 3+-doped concentration, we calculated the maximum cooling effect in the 3 wt% Yb\+ 3+-doped sample pumped at 1 012.5 nm. The corresponding cooling capability is about -4.09 ℃/W and the cooling efficiency reaches 1.76%.
基金supported by NanoNed,a nanotechnology program of the Dutch Ministry of Economic Affairs and partly financed by the Stichting voor Fundamenteel Onderzoek der Materie(FOM),which is financially supported by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek(NWO).The Marie Curie Fellowship and the Galenos Network are acknowledged for financial support(MEST-CT-2004-404992).
文摘Coherent anti-Stokes Raman scattering(CARS)microscopy is used to visualize the release of a model drug(theophylline)from a lipid(tripalmitin)based tablet during dissolution.The effects of transformation and dissolution of the drug are imaged in real time.This study reveals that the manufacturing process causes significant differences in the release process:tablets prepared from powder show formation of theophylline monohydrate on the surface which prevents a controlled drug release,whereas solid lipid extrudates did not show formation of monohydrate.This visualization technique can aid future tablet design.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11174019,61322509 and 11121091the National Basic Research Program of China under Grant No 2013CB921904
文摘We propose and implement a wide-field vibrational phase contrast detection to obtain imaging of imaginary components of third-order nonlinear susceptibility in a coherent anti-Stokes Raman scattering (CARS) microscope with full suppression of the non-resonant background. This technique is based on the unique ability of recovering the phase of the generated CARS signal based on holographic recording. By capturing the phase distributions of the generated CARS field from the sample and from the environment under resonant illumination, we demonstrate the retrieval of imaginary components in the CARS microscope and achieve background free coherent Raman imaging.
基金Project supported by the National Basic Research Program of China(Grant No.2012CB825802)the Major Scientific Instruments Equipment Development of China(Grant No.2012YQ15009203)+1 种基金the National Natural Science Foundation of China(Grant Nos.60878053 and 11004136)the State Key Laboratory of Precision Measurement Technology and Instruments,Tsinghua University,China(Grant No.DL12-01)
文摘In the implementation of CARS nanoscopy, signal strength decreases with focal volume size decreasing. A crucial problem that remains to be solved is whether the reduced signal generated in the suppressed focal volume can be detected. Here reported is a theoretical analysis of detection limit (DL) to time-resolved CARS (T-CARS) nanoscopy based on our proposed additional probe-beam-induced phonon depletion (APIPD) method for the low concentration samples. In order to acquire a detailed shot-noise limited signal-to-noise (SNR) and the involved parameters to evaluate DL, the T-CARS process is described with full quantum theory to estimate the extreme power density levels of the pump and Stokes beams determined by saturation behavior of coherent phonons, which are both actually on the order of ~ 109 W/cm2. When the pump and Stokes intensities reach such values and the total intensity of the excitation beams arrives at a maximum tolerable by most biological samples in a certain suppressed focal volume (40-nm suppressed focal scale in APIPD method), the DL correspondingly varies with exposure time, for example, DL values are 103 and 102 when exposure times are 20 ms and 200 ms respectively.
基金supported by the National Natural Science Foundation of China (Grant No. 20973050)
文摘We report on the theoretical and the experimental investigations of the coherent phonon dynamics in sapphire crystal using the femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) technique. The temporal chirped white-light continuum (WLC) is used for the Stokes pulse, therefore we can perform the selective excitation of the phonon modes without using a complicated laser system. The expected quantum beat phenomenon is clearly observed. The theoretical formulas consist very well with the experimental results. The dephasing times of the excited phonon modes, the wavenumber difference, and the phase shift between the simultaneously excited modes are obtained and discussed. This work opens up a way to study directly high-frequency coherent phonon dynamics in bulk crystals on a femtosecond time scale and is especially helpful for understanding the nature of coherent phonons.
基金This work was supported in part by the National Key R&D Program of China(2018YFC0910600)the National Natural Science Foundation of China(81871397)+4 种基金the National Young Talent Program,the Shaanxi Science Fund for Distinguished Young Scholars(2020JC-27)the Key Research and Development Program of Shaanxi(2021ZDLSF04-05)the Shaanxi Young Top-notch Talent Program,the Best Funded Projects for the Scientific and Technological Activities for Excellent Overseas Researchers in Shaanxi Province(2017017)the Fundamental Research Funds for Central Universities(QTZX2105)Xueli Chen would like to thank Dr.Chi Zhang at Purdue University for his help in building the CARS microscope.
文摘Coherent anti-Stokes Raman scattering(CA RS)microscopy can resolve the chemical compo-nents and distribution of living biological systems in a label-firee manner and is favored in several disciplines.Current CA RS microscopes typically use bulky,high-performance solid-state lasers,which are expensive and sensitive to environmental changes.With their relatively low cost and environmental sensitivity,supercontinum fiber(SF)lasers with a small footprint have found increasing use in biomedical applications.Upon these features,in this paper,we homebuilt a low-cost CARS microscope based on a SF laser module(scCA RS microscope).This SF laser module is specially customized by adding a time synchronized seed source channel to the SF laser to form a dual-channel output laser.The performance of the scCARS microscope is evaluated with dimethyl sulfoxide,whose results confirm a spatial resolution of better than 500nm and a detection sensitivity of millimolar concentrations.The dual-color imaging capability is further demonstrated by imaging different species of mixed microspheres.We finally explore the potential of our scCARS microscope by mapping lipid droplets in different cancer cells and corneal stromal lenses.
基金Project supported by the National Natural Science Foundation of China (Grant No 10674019)
文摘The widely used energy transfer theory is a foundation of luminescence, in which the rates of Stokes and anti-Stokes processes have the same calculation formula. An improvement on the anti-Stokes energy transfer to explain the fluorescence intensity reversal between the red and green fluorescence of Er(0.5)Yb(9.5):FOV is reported in the present article. The range of the intensity reversal Z was measured to be 877. Dynamic processes for 16 levels were simulated. A coefficient, the improvement factor of the intensity ratio of Stokes to anti-Stokes processes in quantum Raman theory compared to classical Raman theory, is introduced to successfully describe the anti-Stokes energy transfer. A new method to calculate the distance between the rare earth ions, which is critical for the energy transfer calculation, is proposed. The validity of these important improvements is also proved by experiment.
基金supported by the National Natural Science Foundation of China (Grant No.10674019)
文摘The improvement on the calculation of anti-Stokes energy transfer rate is studied in the present work. The additional proportion coefficient between Stokes and anti-Stokes light intensities of quantum Raman scattering theory as compared with the classical Raman theory is introduced to successfully describe the anti-Stokes energy transfer. The theoretical formula for the improvement on the calculation of anti-Stokes energy transfer rate is derived for the first time in this study. The correctness of introducing coefficient exp{△E/kT} from well-known Raman scatter theory is demonstrated also. Moreover, the experimental lifetime measurement in Er0.01YbxY1-0.01-xVO4 crystal is performed to justify the validity of our important improvement in the original phonon-assisted energy transfer theory for the first time.
文摘In this paper, we experimentally study the selective excitation of two-pulse femtosecond coherent anti-Stokes Raman scattering (CARS) in a mixture of dibromomethane (CH2Br2) and chloroform (CHCl3) by adaptive pulse shaping based on genetic algorithm. Second harmonic generation frequency-resolved optical gating (SHG-FROG) traces indicate that the spectral amplitude and phase of the optimal pulse are both modulated. Finally, we discuss the physical mechanism for the selective excitation of femtosecond CARS based on the retrieved information from SHG-FROG traces.
基金Northrop GrummanOffice of Naval Research(ONR)(N00014-17-2270)
文摘Raman lasers based on integrated silica whispering gallery mode resonant cavities have enabled numerous applications from telecommunications to biodetection. To overcome the intrinsically low Raman gain value of silica, these devices leverage their ultrahigh quality factors(Q), allowing submilliwatt stimulated Raman scattering(SRS) lasing thresholds to be achieved. A closely related nonlinear behavior to SRS is stimulated anti-Stokes Raman scattering(SARS). This nonlinear optical process combines the pump photon with the SRS photon to generate an upconverted photon. Therefore, in order to achieve SARS, the efficiency of the SRS process must be high. As a result, achieving SARS in on-chip resonant cavities has been challenging due to the low lasing efficiencies of these devices. In the present work, metal-doped ultrahigh Q(Q > 10~7) silica microcavity arrays are fabricated on-chip. The metal-dopant plays multiple roles in improving the device performance. It increases the Raman gain of the cavity material, and it decreases the optical mode area, thus increasing the circulating intensity. As a result, these devices have SRS lasing efficiencies that are over 10× larger than conventional silica microcavities while maintaining low lasing thresholds. This combination enables SARS to be generated with submilliwatt input powers and significantly improved anti-Stokes Raman lasing efficiency.
基金supported by the National Natural Science Foundation of China (22090011)the NSFC-Liaoning United Fund (U1908202)。
文摘Conventional anti-Stokes materials-involved deep photodynamic therapy(dPDT)requires much high-intensity irradiance due to low photosensitization efficiency.Herein,we proposed a"booster effector"approach to construct highly efficient hot band absorption phototherapeutics for low/biosafety power anti-Stokes light-triggered d PDT.Se,as"booster effector",was introduced into hot band absorption luminophores(HBAs),which not only significantly facilitated intersystem crossing,but also simultaneously enhanced hot band excitation efficiency atν808,as a result successfully enabling excellent photogenerated singlet oxygen capability of HBAs under ultra-low power anti-Stokes excitation(10 mW cm^(-2)in vitro).As far as we know,such low laser power-initiated photosensitization activity has never been reported in the existing anti-Stokes material systems.Importantly,FUC-Se ME can self-assemble into uniform nanospheres in water,greatly boosting cellular uptake(>25-fold larger than FUC-Se),and achieve superior cancer-killing effect(808 nm,10 mW cm^(-2),5 min,the half-maximal inhibitory concentration IC50=1.36μM).After further PEGylation with folate-attached polymer,the resultant FUC-Se ME@FA can effectively enrich at the tumor(signal-to-background ratio,10).Under safety irradiation(330 mW cm^(-2)),FUC-Se ME@FA effectively inhibits deep-seated tumor progression(the tumor growth inhibition rate,84%).This work provides a successful paradigm,possibly being more clinically beneficial than conventional anti-Stokes materials.
基金Project supported by the National Key Research Program of China(No.2011ZX01015-001)the National Basic Research Program of China(Nos.2011CBA00608,2012CB619203,2015CB351902,2015CB932402)
文摘Coherent anti-Stokes Raman scattering spectroscopy(CARS) is a well-known detecting tool in biosensing and nonlinear spectroscopy. It can provide a non-invasive alternative without the need for exogenous labels,while the enhancement factor for surface plasmon resonances(SPR) are extensively used to increase the local field close to the oscillators and which can obtain high enhancement. In this work, we investigate the enhancement factor of our structure for surface-enhanced coherent anti-Stokes Raman scattering. The absorption spectrum of the structure has been studied, a wide range of absorption has been realized. The enhancement can be as high as 10^(16) over standard CARS. Our design is very useful for improving the enhancement factor of surface-enhanced coherent anti-Stokes Raman scattering.