Laser spectroscopy imaging technique coupled withnanomaterials for cancer diagnosis: A review

Laser spectroscopic imaging techniques have received tremendous attention in the-eld of cancer diagnosis due to their high sensitivity,high temporal resolution,and short acquisition time.However,the limited tissue penetration of the laser is still a challenge for the in vivo diagnosis of deep-seated lesions.Nanomaterials have been universally integrated with spectroscopic imaging techniques for deeper cancer diagnosis in vivo.The components,morphology,and sizes of nanomaterials are delicately designed,which could realize cancer diagnosis in vivo or in situ.Considering the enhanced signal emitting from the nanomaterials,we emphasized their combination with spectroscopic imaging techniques for cancer diagnosis,like the surface-enhanced Raman scattering(SERS),photoacoustic,fluorescence,and laser-induced breakdown spectroscopy(LIBS).Applications ofthe above spectroscopic techniques offer new prospectsfor cancer diagnosis.

Control and data acquisition system for collinear laser spectroscopy experiments

A control and data acquisition system was implemented for the recently developed collinear laser spectroscopy setup.This system is dedicated to data recording,storage,processing,monitoring of the beam intensity and energy,and visualization of various spectra.In comparison to the conventional resonance nuclear reaction system,the key technique is the precise synchronization of the detected counts with the actual scanning voltage(or probing laser frequency).The functions of the system were tested by measuring the hyperfine structure spectra of stable calcium(e.g.,^(40)Ca^(+))and radioactive potassium(e.g.,^(38)K)in the bunched and continuous modes,respectively.This system will be routinely applied and further improved in subsequent laser spectroscopy experiments on unstable isotopes at the Beijing Radioactive Ion-beam Facility(BRIF).

Commissioning of a high-resolution collinear laser spectroscopy apparatus with a laser ablation ion source

Collinear laser spectroscopy is a powerful tool for studying the nuclear spins,electromagnetic moments,and charge radii of exotic nuclei.To study the nuclear properties of unstable nuclei at the Beijing Radioactive Ion-beam Facility(BRIF)and the future High Intensity Heavy-ion Accelerator Facility(HIAF),we developed a collinear laser spectroscopy apparatus integrated with an offline laser ablation ion source and a laser system.The overall performance of this state-of-the-art technique was evaluated,and the system was commissioned using a bunched stable ion beam.The high-resolution optical spectra for the 4s ^(2)S_(1/2)→4p^(2)P_(3/2)(D2)ionic transition of ^(40;42;44;48)Ca isotopes were successfully measured.The extracted isotope shifts relative to ^(40)Ca showed excellent agreement with the literature values.This system is now ready for use at radioactive ion beam facilities such as the BRIF and paves the way for the further development of higher-sensitivity collinear resonance ionization spectroscopy techniques.

Cs 5D_(5/2)-6F 728 nm Laser Spectroscopy with Single Pumping Laser

The sub-Doppler absorption laser spectroscopy at 728nm transition from the 5D5/2 state to the 6F state of cesium with linewidth near 10 MHz is first experimentally performed with indirect pumping from the ground state 6S1/2 to the state 7P3/2 by a 455.5nm diode laser. Using a 455.5nm diode laser as an indirect pump laser, several excited states will be populated due to spontaneous decay from the 7P state. We first implement the sub-Doppler absorption laser spectroscopy at 728nm from the 5D5/2 state to the 6F state when Cs atoms within thermal glass cell decay to the 5D5/2 state. Due to velocity transfer effect, the hyperfine structure of 5D5/2 shows a mixed and complicated pattern but very e/ear structure when the 455.5nm pumping laser is counter-propagating （or co-propagating） with the 728nm probing laser.

Radiative lifetime measurements of odd-parity highly-excited levels of Sn I by time-resolved laser spectroscopy

Natural radiative lifetimes of five higher-lying odd-parity levels 5pTs ^3P1^0, 5p5d 1P1^0, 5p6d 3F2^0, 3D1^0 and 3F3^0 in neutral tin are measured by the time-resolved laser-induced fluorescence （TR-LIF） technique and the atomic beam method. All these lifetimes are not longer than 100 ns and they are found to be shorter than the lifetimes of evenparity levels in the same energy region. The results reported in this paper provide important transition parameters for highly-excited atomic Sn, which may be useful for theoretically calculating excited heavy atoms.

Ultrafast laser system based on noncollinear optical parametric amplification for laser spectroscopy

We report the experimental demonstration of transform-limited sub-6 fs pulses at an optimal central wavelength by a tunable noncollinear optical parametric amplification（NOPA） source. Meanwhile, a white light continuum in the near-infrared（NIR） range from 900 to 1100 nm is also successfully generated by focusing the unconverted800 nm beam during NOPA generation on a sapphire rod. Both visible-pump/visible-probe and visible-pump/NIR-probe experiments are realized using the same laser system. As examples, ultrafast photo-induced exciton dynamics inside two kinds of materials are investigated by the visible-pump/visible-probe and visible-pump/NIR-probe spectroscopy, respectively.

Determination of Gum Arabic (<i>Acacia nilotica</i>) Constituents Using Laser Induced Breakdown Spectroscopy

In this work, Laser Induced Breakdown Spectroscopy (LIBS) was used to determine the constituent of Gum Arabic (Acacia nilotica) collected from five different locations in Sudan. Gum samples were irradiated with 80 mJ pulse energy of Nd-YAG laser (1064 nm) and Atomic spectra Database was used for the spectral analysis of the plasma emitted from these samples. It was found that the samples contain the elements C, O, H, S, N, P, Na, Mg, Ca, Fe, Cr, Mn, Co with different amounts. Some elements like (Ti, Br, Ar, Th, Kr, Sc and Pr) are recorded here for the first time.

Influence of the position relationship between gas–liquid interface and laser focus on plasma evolution characteristics in jet LIBS technology

In order to understand the characteristics of breakdown process,plasma evolution and spectral emission in liquid jets laser-induced breakdown spectroscopy methods under the influence of the position variation between laser focus and gas–liquid interface,this work takes the plasma generated by laser-induced liquid jets as the object of study and discusses the changes in the spatial and temporal evolution characteristics and spectral radiation of the plasma when the position parameters between the laser focal point and the gas–liquid interface are different.The initial breakdown position is always between the front interface and the focus when the laser focus moves along the vertical direction of the interface,forming a phenomenon like’interface effect’.The relationship between laser pulse energy and breakdown probability exhibits a law similar to a‘hysteresis curve’in the study of breakdown threshold.In this work,plasma with smaller size,rounder shape,stronger radiation,higher temperature,and higher density can be produced when the focus position is in the liquid column 0.2 mm away from the front interface.Simultaneously,the spectral signal intensity and signal-to-back ratio of the characteristic peaks of target elements in water reach maximum values,and the spectral signal becomes more stable(relative standard deviation value reaches 2%).The Ca element’s ion radiation at 393.366 nm and atomic radiation at 422.673 nm are studied using narrow-band filtering imaging and time-space resolution spectroscopy.The findings demonstrate that the laws of ion and atomic radiation are not perfectly consistent in space and time.

Single-mode GaSb-based laterally coupled distributed-feedback laser for CO_(2)gas detection

We report on a GaSb-based laterally coupled distributed feedback(LC-DFB)laser with Cr gratings operating at 2004 nm for CO_(2)detection application.Butterfly packaged with single-mode fiber pigtailed,the laser diode operates in the continuous-wave mode in a temperature range from-10℃to 60℃,with a maximum output power of 2 mW and a maximum side-mode suppression ratio over 30 dB.Wavelength-modulated absorption spectroscopy of CO_(2)demonstrates the applicability of the LC-DFB laser to tunable diode laser absorption spectroscopy.Furthermore,the diode junction temperature,which is measured by using the wavelength shift method,exhibits a maximum value of 17℃in the single-mode operation range.

High-Resolution Stark Spectroscopy of Ba Highly-Excited States by Diode Laser Technique

High-resolution atomic-beam laser spectroscopy has been performed to study Stark effect of Ba atom. Stark spectra have been observed at various electric fields for Ba highly excited states. The scalar polarizability of the transition from 6s5d3D2 to 5d6p3F3 at 728.0 nm and the tensor polarizability of the 3F3 level have been determined for the first time, to be αs = -89.8 (12) kHz/(kV/cm)2 and αt = -133.7 (20) kHz/(kV/cm)2, respectively.

Influence of laser intensity in second-harmonic detection with tunable diode laser multi-pass absorption spectroscopy

Tunable diode laser absorption spectroscopy （TDLAS） has been widely employed in atmospheric trace gases detection. The ratio of the second-harmonic signal to the intensity of laser beam incident to the multi-pass cell is proved to be proportional to the product of the path length and the gas concentration under any condition. A new calibration method based on this relation in TDLAS system for the measurement of trace gas concentration is proposed for the first time. The detection limit and the sensitivity of the system are below 110 and 31ppbv （parts-per-billion in volume）, respectively.

Heavy Metal Detection in Soils by Laser Induced Breakdown Spectroscopy Using Hemispherical Spatial Confinement

Spatial confinement has great potential for Laser Induced Breakdown Spectroscopy （LIBS） instruments after it has been proven that it has the ability to enhance the LIBS signal strength and repeatability. In order to achieve in-situ measurement of heavy metals in farmland soils by LIBS, a hemispherical spatial confinement device is designed and used to collect plasma spectra, in which the optical fibers directly collect the breakdown spectroscopy of the soil samples. This device could effectively increase the stability of the spectrum intensity of soil. It also has other advantages, such as ease of installation, and its small and compact size. The relationship between the spectrum intensity and the laser pulse energy is studied for this device. It is found that the breakdown threshold is 160 cm-2, and when the laser fluence increases to 250 J/cm2, the spectrum intensity reaches its maximum. Four different kinds of laser pulse energy were set up and in each case the limits of detection of Cd, Cu, Ni, Pb and Zn were calculated. The results show that when the laser pulse fluence was 2.12 GW/cm2, we obtained the smallest limits of detection of these heavy metals, which are all under 10 mg/kg. This device can satisfy the needs of heavy metal in-situ detection, and in the next step it will be integrated into a portable LIBS instrument.

Spectral Enhancement of Laser-Induced Breakdown Spectroscopy in External Magnetic Field

In this paper the spectral enhancement of laser-induced breakdown spectroscopy （LIBS） for copper plasma in the presence of a magnetic field is investigated and the temporal- and spatial-resolved plasma emission spectra are analyzed. Experimental results show that the copper plasma atomic and ion spectra have been enhanced in the presence of the external magnetic field. In addition, the Cu I 521.82 nm spectral intensity evolution with delay time appears to have a double peak around the delay time of 2 μs, but that of Cu II 507.57 nm has a sharp decrease because of the electron-atom three body recombination process. The plasma temperature with magnetic confinement is lower than that of the case in the absence of magnetic fields. Finally, the spectral enhancement mechanisms of laser induced breakdown spectroscopy with magnetic confinement are analyzed.

Measurements of argon metastable density using the tunable diode laser absorption spectroscopy in Ar and Ar/O2

Densities of Ar metastable states 1s5 and 1s3 are measured by using the tunable diode laser absorption spectroscopy（TDLAS） in Ar and Ar/O2 mixture dual-frequency capacitively coupled plasma（DF-CCP）. We investigate the effects of high-frequency（HF, 60 MHz） power, low-frequency（LF, 2 MHz） power, and working pressure on the density of Ar metastable states for three different gas components（0%, 5%, and 10% oxygen mixed in argon）. The dependence of Ar metastable state density on the oxygen content is also studied at different working pressures. It is found that densities of Ar metastable states in discharges with different gas components exhibit different behaviors as HF power increases. With the increase of HF power, the metastable density increases rapidly at the initial stage, and then tends to be saturated at a higher HF power. With a small fraction（5% or 10%） of oxygen added in argon plasma, a similar change of the Ar metastable density with HF power can be observed, but the metastable density is saturated at a higher HF power than in the pure argon discharge. In the DF-CCP, the metastable density is found to be higher than in a single frequency discharge, and has weak dependence on LF power. As working pressure increases, the metastable state density first increases and then decreases,and the pressure value, at which the density maximum occurs, decreases with oxygen content increasing. Besides, adding a small fraction of oxygen into argon plasma will significantly dwindle the metastable state density as a result of quenching loss by oxygen molecules.

Evaluation of gases'molecular abundance ratio by fiber-optic laser-induced breakdown spectroscopy with a metal-assisted method

A metal-assisted method is proposed for the evaluation of gases’molecular abundance ratio in fiber-optic laser-induced breakdown spectroscopy(FO-LIBS).This method can reduce the laser ablation energy and make gas composition identification possible.The principle comes from the collision between the detected gases and the plasma produced by the laser ablation of the metal substrate.The interparticle collision in the plasma plume leads to gas molecules dissociating and sparking,which can be used to determine the gas composition.The quantitative relationship between spectral line intensity and molecular abundance ratio was developed over a large molecular abundance ratio range.The influence of laser ablation energy and substrate material on gas quantitative calibration measurement is also analyzed.The proposed metal-assisted method makes the measurement of gases’molecular abundance ratios possible with an FO-LIBS system.

Quantitative Analysis of Cr in Milk Powder by Laser Induced Breakdown Spectroscopy( LIBS)

At present, heavy metal pollution in food occurs frequently, which requires a novel method for rapid detection. Laser induced breakdown spectroscopy （LIBS） is a new technique for rapid and environmental friendly detection, but it lacks high sensitivity and stability which restrict its development. In this study, Cr-polluted infant milk powder was used as experimental material to explore the feasibility of the application of LIBS technique in food safety detection. Aiming at improving the precision and accuracy of Cr detection by LIBS technique, LIBS spectra of samples were collected by a spectrometer with an intensified charge-cou- pled device （ICCD） using three gratings with different resolutions to comprehensively compare and analyze the stability, sensitivity and quantitative analysis accura- cy of LIBS detection. The results showed that average relative standard deviation （RSD） of LIBS spectral intensity was below 10%, indicating good stability. LIBS signals were collected by three gratings for quantitative analysis, and the results demonstrated that the linear correlation coefficient R2 of fitting curves was 0. 248 87, 0.903 12 and 0.992 81, respectively; the relative errors between actual and predicted concentrations were 38.23%, 8.84% and 7.43%, respectively, indicating that gratings with higher resolutions could lead to higher linear correlation coefficient and better detection accuracy. According to the results, high-resolu- tion spectrometer could significantly improve the accuracy of LIBS detection of Cr concentration in milk powder, suggesting that it is feasible to detect heavy metals in food by LIBS technique with the improvement of core device performance.

Aqueous ruthenium detection by microwave-assisted laser-induced breakdown spectroscopy

Aqueous ruthenium was detected in real-time under ambient conditions using microwaveassisted laser-induced breakdown spectroscopy(MW-LIBS).A 10 mJ laser energy and 750 W microwave power were directed at an open liquid jet sample of ruthenium.It was observed that,for liquid flow,the coupling efficiency between the microwave and the laser-induced plasma was limited to 43%.The improvement in the ruthenium’s signal-to-noise ratio with MW-LIBS,with respect to LIBS,was 76-fold.Based on MW-LIBS,the limit of detection for aqueous ruthenium was determined to be 957±84 ppb.

Laser absorption spectroscopy for high temperature H_2O time-history measurement at 2.55 μm during oxidation of hydrogen

Concentration time-histories of H20 were measured behind reflected shock waves during hydrogen combustion. Experiments were conducted at temperatures of 1117-1282 K, the equivalence ratios of 0.5 and 0.25, and a pressure at 2 atm using a mixture of H2/O2 highly diluted with argon. H2O was monitored using tunable mid-infrared diode laser absorption at 2.55 μm （3920.09 cm-1）. These time-histories provide kinetic targets to test and refine reaction mechanisms for hydrogen. Comparisons were made with the predictions of four detailed kinetic mechanisms published in the last four years. Such comparisons of H2O concentration profiles indicate that the AramcoMech 2.0 mechanism yields the best agreement with the experimental data, while CRECK, San Diego, and HP-Mech mechanisms show significantly poor predictions. Reaction pathway analysis for hydrogen oxidation indicates that the reaction H ＋ OH ＋ M = H20 ＋ M is the key reaction for controlling the H2O formation by hydrogen oxidation. It is inferred that the discrepancy of the conversion percentage from H to H20 among these four mechanisms induces the difference of performance on H2O time-history predictions. This work demonstrates the potential of time-history measurement for validation of large reaction mechanisms.

LASER FLASH SPECTROSCOPY STUDIES OF THE ANTHRACENEN,N-DIETHYLANILINE EXCIPLEX FORMATION IN γ-CYCLODEXTRIN

Gamma-cyclodextrin (γ-CD) was used to induce the formation of N,N-diethylaniline (DEA) exciplex in 15:85{φ=0.15)v/v EtOH-H_2O binary mixture.Measurements of the fluorescence spectra of anthracene in the presence or absence of DEA and γ-CD show that γ-CD can form 1:1:1 host/guest-Ⅰ/guest-Ⅱ inclusion complex with anthracene and DEA.

Investigation of Laser Induced Breakdown Spectroscopy(LIBS)for the Differentiation of Nerve and Gland Tissue-A Possible Application for a Laser Surgery Feedback Control Mechanism

Laser surgery provides clean,fast and accurate modeling of tissue.However,the inability to determine what kind of tissue is being ablated at the bottom of the cut may lead to the iatrogenic damage of structures that were meant to be preserved.In this context,nerve preservation is one of the key challenges in any surgical procedure.One example is the treatment of parotid gland pathologies,where the facial nerve（N.VII） and its main branches run through and fan out inside the glands parenchyma.A feedback system that automatically stops the ablation to prevent nerve-tissue damage could greatly increase the applicability and safety of surgical laser systems.In the present study,Laser Induced Breakdown Spectroscopy（LIBS） is used to differentiate between nerve and gland tissue of an ex-vivo pig animal model.The LIBS results obtained in this preliminary experiment suggest that the measured spectra,containing atomic and molecular emissions,can be used to differentiate between the two tissue types.The measurements and differentiation were performed in open air and under normal stray light conditions.