Detection of Biogenic Silica in Leaf Blade, Leaf Sheath, and Stem of Bermuda Grass (Cynodon dactylon) Using LIBS and Phytolith Analysis

Laser induced breakdown spectroscopy (LIBS) has been used to perform in situ analysis of major and minor elements present in the different parts of the Bermuda grass (Cynodon dactylon). In situ, point detection/analysis of the elements in plants without any sample preparation has been demonstrated. LIBS spectra of the different parts (leaf blade, leaf sheath and stem) of fresh C. dactylon plant have been recorded to study the pattern of silica deposition in its different parts. Atomic lines of Si, Mg, Ca, C, Al, Zn, N, Sr, etc. have been observed in the LIBS spectra of the C. dactylon. A close observation of LIBS spectra of the different parts of the plants shows that silica concentration is greater in leaf blades than leaf sheaths and stems. The results obtained with LIBS analysis are also compared with the number density of phytoliths deposited in different parts of C. dactylon. It is observed that the highest silicified cell frequency is present in leaf blades followed by leaf sheaths and stems which is in close agreement with LIBS analysis.     

Estimation of Wheat Grain Tissue Cohesion via Laser Induced Breakdown Spectroscopy

During the wheat milling process, the bran fractionation is related to its mechanical properties, which are measured using tensile tests on hand-isolated tissues. However, the dissection of wheat tissues implies a soaking stage in water that can modify tissue properties. New methodologies are required to evaluate wheat tissue properties directly on native grains. The aim of this work was to estimate wheat grain tissue cohesion by the ionization effectiveness via laser-induced breakdown spectroscopy (LIBS) technique. Isolated bran tissues and wheat grains were submitted to LIBS analysis using a pulsed argon fluoride (193 nm, 15 ns, 1 Hz, 2 J cm⁻²) excimer laser and a compact optic fiber spectrometer (HR2000). The first approach was to correlate the ratios of ionic to atomic emission lines (MgII/MgI and CaII/CaI) of isolated tissues to their mechanical measurements. The energy needed to rupture the tissue was correlated to MgII/MgI (R ² = 0.72). Secondly, native grains were irradiated and chemometrics was applied to discriminate tissue spectra. The aleurone layer isolated after the soaking step presented a higher MgII/MgI than the aleurone layer from native grains, indicating a possible water effect on the tissue cohesion. In conclusion, the LIBS technique may be a potential method for rapid structural analysis of vegetal material allowing wheat population screening of both compositional and mechanical properties.     

Nanoscale Dielectric Function of Fe,Pt, Ti,Ta, Al,and V: Application to Characterization of Al Nanoparticles Synthesized by Fs Laser Ablation

Development and applications of new nanomaterials and nanocomposites that include metal nanoparticles have received much attention in the last years. However, there are relatively few studies concerning basic physical characteristics of the dielectric function at the nanoscale, which is needed for predicting their optical and plasmonic response. The size-dependent complex dielectric function of metal Fe, Pt, Ti, Ta, Al, and V nanoparticles (NPs) is calculated for the first time for an extended wavelength range from UV to FIR, based on experimental bulk complex refractive index measurements in the mentioned range at room temperature. Calculation is based on a “top-down” approach, based on a stepwise modification of the Drude model. Bulk plasma frequency (ω _p) and damping constant (γ _free) in this model are determined using a method that improves the relative uncertainties in their values and provide an insight about the wavelength range over which the metal may be considered Drude like. Validation of ω _p and γ _free values is demonstrated by the improved accuracy with which the experimental bulk dielectric function is reproduced. For nanometric and subnanometric scales, dielectric function is made size dependent considering size-corrective terms for free and bound electron contributions to the bulk dielectric function. These results are applied to analyze the synthesis of Al NP suspensions using a 120-fs pulse laser to ablate an Al solid target in n-heptane and water. The presence of Al, Al-Al₂O₃, and air-Al core-shell structures is also reported for the first time in these type of colloids. Analysis of the structure, configuration, sizing, and relative abundance was carried out using optical extinction spectroscopy (OES). Sizing results are compared with those provided by atomic force microscopy (AFM) studies.     

Laser-induced Breakdown Spectroscopy: A New Approach for Nanoparticle's Mapping and Quantification in Organ Tissue

Emission spectroscopy of laser-induced plasma was applied to elemental analysis of biological samples. Laser-induced breakdown spectroscopy (LIBS) performed on thin sections of rodent tissues: kidneys and tumor, allows the detection of inorganic elements such as (i) Na, Ca, Cu, Mg, P, and Fe, naturally present in the body and (ii) Si and Gd, detected after the injection of gadolinium-based nanoparticles. The animals were euthanized 1 to 24 hr after intravenous injection of particles. A two-dimensional scan of the sample, performed using a motorized micrometric 3D-stage, allowed the infrared laser beam exploring the surface with a lateral resolution less than 100 μm. Quantitative chemical images of Gd element inside the organ were obtained with sub-mM sensitivity. LIBS offers a simple and robust method to study the distribution of inorganic materials without any specific labeling. Moreover, the compatibility of the setup with standard optical microscopy emphasizes its potential to provide multiple images of the same biological tissue with different types of response: elemental, molecular, or cellular.     

Optical diagnostics of lead and PbGa2S4 layered crystal laser plasmas

Laser plasmas produced at the surfaces of lead and a PbGa₂S₄ layered crystal irradiated by a neodymium laser with λ=1.06 μm, pulse duration τ=20 ns, and intensity W=(1–2)×10⁹ W/cm² are studied using optical diagnostics. It is shown that, in a lead plasma, the most intense (characteristic) lines are the PbI 405.7-nm, PbI 368.3-nm, PbI 364-nm, and PbII 220.4-nm lines. In a layered crystal plasma, the emission spectrum is an aggregation of the most intense PbI and GaI lines, whereas sulfur lines are absent. The bottlenecks of the recombination of the ionic and atomic components of the lead and PbGa₂S₄ crystal plasmas are determined. The average propagation velocity of the lead laser plume is 18–20 km/s. A comparative analysis of the emission dynamics of PbI and GaI lines in the laser plasmas of these metals and in the plasma of a PbGa₂S₄ crystal is carried out. The results obtained are important for the optical diagnostics of the plasmas of leadand gallium-containing crystals and for the optimization of laser deposition of the thin films of these substances. __________ Translated from Fizika Plazmy, Vol. 27, No. 7, 2001, pp. 658–663. Original Russian Text Copyright ? 2001 by Shuaibov, Dashchenko, Shevera.     

LIBS: A Quality Control Tool for Food Supplements

In the present paper the ability of calibration free laser induced breakdown spectroscopy (CF-LIBS) as a quality control tool to monitor the composition of different minerals present in food supplement samples belonging to Indian brands (brand-A and brand-B) has been demonstrated. LIBS spectra of these two food supplements (brand-A and brand-B) available in the form of tablet have been recorded. As reported by manufacturers of these two food supplements, LIBS spectra of brand-A contains the spectral signatures of minerals like Ca, Mg, C, P, Zn, Fe, Cu, and Cr whereas LIBS spectra of brand-B shows the presence of spectral lines like Ca, Mg and C. The spectral signatures of Na and K are also found in both brands whereas spectral signature of Ti is observed only in brand-B but these elements are not mentioned on the nutritional label of the brands. The quantitative analysis of mineral contents in food supplements has been done using CF-LIBS for brand A and brand B to verify the content of the minerals reported by the manufacturer of the food supplements. Our results show that Ca and Mg are the main matrix elements of these brands. The concentration of minor and trace elements estimated using CF-LIBS technique is found in agreement with the reported nutritional values of both the brands. The concentration of major elements Ca and Mg are also estimated from Atomic Absorption Spectroscopy which is in close agreement with CF-LIBS result.     

Application of LIBS in Detection of Antihyperglycemic Trace Elements in Momordica charantia

The present study exploits the information based on concentration of trace elements and minerals in understanding the role/mechanism of action of freeze-dried fruit powder suspended in distilled water of Momordica charantia (family: Cucurbitaceae) in diabetes treatment. Laser-induced break down spectroscopy (LIBS) spectra of plant product was recorded under optimized experimental conditions and analyzed. Several atomic lines such as Na, K, Mg, Ca, Fe, Al, etc. have been observed in the LIBS spectra of the above plant product. The concentrations of these minerals are determined by using calibration-free LIBS method. Correlation between the concentration of these elements/minerals and their defined role in diabetes management was studied in normal as well as diabetic animal models.     

Qualitative tissue differentiation by analysing the intensity ratios of atomic emission lines using laser induced breakdown spectroscopy (LIBS): prospects for a feedback mechanism for surgical laser systems

The research work presented in this paper focuses on qualitative tissue differentiation by monitoring the intensity ratios of atomic emissions using ‘Laser Induced Breakdown Spectroscopy’ (LIBS) on the plasma plume created during laser tissue ablation. The background of this study is to establish a real time feedback control mechanism for clinical laser surgery systems during the laser ablation process. Ex‐vivo domestic pig tissue samples (muscle, fat, nerve and skin) were used in this experiment. Atomic emission intensity ratios were analyzed to find a characteristic spectral line for each tissue. The results showed characteristic elemental emission intensity ratios for the respective tissues. The spectral lines and intensity ratios of these specific elements varied among the different tissue types. The main goal of this study is to qualitatively and precisely identify different tissue types for tissue specific laser surgery. (© 2013 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Investigation of the differentiation of ex vivo nerve and fat tissues using laser‐induced breakdown spectroscopy (LIBS): Prospects for tissue‐specific laser surgery

In the present study, the elemental compositions of fat and nerve tissue during their plasma mediated laser ablation are studied in the context of tissue differentiation for laser surgery applications by using Laser‐Induced Breakdown Spectroscopy (LIBS). Tissue samples of porcine fat and nerve were prepared as ex vivo experimental objects. Plasma mediated laser ablation is performed using an Nd : YAG laser in open air and under normal stray light conditions. The performed measurements suggest that the two tissue types show a high similarity in terms of qualitative elemental composition while at the same time revealing a distinct difference in the concentration of the constituent elements. Different analysis approaches are evaluated and discussed to optimize the tissue‐differentiation performance of the LIBS approach.

Plasma mediated laser tissue ablation.     

Laser-induced breakdown spectroscopy (LIBS): a novel technology for identifying microbes causing infectious diseases

With the advent of improved experimental techniques and enhanced precision, laser-induced breakdown spectroscopy (LIBS) offers a robust tool for probing the chemical constituents of samples of interest in biological sciences. As the interest continues to grow rapidly, the domain of study encompasses a variety of applications vis-à-vis biological species and microbes. LIBS is basically an atomic emission spectroscopy of plasma produced by the high-power pulsed laser which is tightly focused on the surface of any kinds of target materials in any phase. Due to its experimental simplicity, and versatility, LIBS has achieved its high degree of interest particularly in the fields of agricultural science, environmental science, medical science, forensic sciences, and biology. It has become a strong and sensitive elemental analysis tool as compared to the traditional gold standard techniques. As such, it offers a handy, rapid, and flexible elemental measurement of the sample compositions, together with the added benefits of less cumbersome sample preparation requirements. This technique has extensively been used to detect various microorganisms, extending the horizon from bacteria, molds, to yeasts, and spores on surfaces, while also being successful in sensing disease-causing viruses. LIBS-based probe has also enabled successful detection of bacteria in agriculture as well. In order for good quality processing of food, LIBS is also being used to detect and identify bacteria such as Salmonella enteric serovar typhimurium that causes food contamination. Differences in soil bacteria isolated from different mining sites are a very good indicator of relative environmental soil quality. In this connection, LIBS has effectively been employed to discriminate both the inter- and intra-site differences of the soil quality across varying mining sites. Therefore, this article summarizes the basic theory and use of LIBS for identifying microbes causing serious agricultural and environmental infectious diseases.     

New investigations on hematoxylin,hematein, and hematein-aluminium complexes

Summary Analytically pure hematoxylin (Htx), penta-acetylhematoxylin (PAHtx), and hematein (Hm) were isolated and characterized by ¹H-NMR spectroscopy. The VIS/UV spectra of Htx and Hm were recorded in MeOH and in H₂O at various pH values. The molar extinction coefficients of the long wavelength absorption bands are reported. The pK _a value for the 1st acidic dissociation step of Hm has been determined from the pH dependency of the absorption spectra of Hm in aqueous buffer solutions. Finally, the absorption spectra are qualitatively discussed.     

Raman Tweezers Spectroscopy of Live,Single Red and White Blood Cells

An optical trap has been combined with a Raman spectrometer to make high-resolution measurements of Raman spectra of optically-immobilized, single, live red (RBC) and white blood cells (WBC) under physiological conditions. Tightly-focused, near infrared wavelength light (1064 nm) is utilized for trapping of single cells and 785 nm light is used for Raman excitation at low levels of incident power (few mW). Raman spectra of RBC recorded using this high-sensitivity, dual-wavelength apparatus has enabled identification of several additional lines; the hitherto-unreported lines originate purely from hemoglobin molecules. Raman spectra of single granulocytes and lymphocytes are interpreted on the basis of standard protein and nucleic acid vibrational spectroscopy data. The richness of the measured spectrum illustrates that Raman studies of live cells in suspension are more informative than conventional micro-Raman studies where the cells are chemically bound to a glass cover slip.     

Analysis of major elements in pigmented melanocytic chicken skin using laser‐induced breakdown spectroscopy

The concentration difference of major elements in melanocytic skin with respect to pigmentation level is analysed by laser‐induced breakdown spectroscopy (LIBS) to investigate the applicability of LIBS as an in situ feedback tool for selective and complete laser removal of melanocytic skin tissue like nevus. The skin of black silkie chicken which had a characteristic darkly pigmented perifollicular skin surrounded by lightly pigmented extrafollicular skin was used as the sample. The results showed higher LIBS signal intensities of Ca²⁺ and Mg²⁺ but lower intensities of Na⁺, Cl^– and K⁺ in the perifollicular skin than in the extrafollicular skin, which demonstrated the feasibility to use LIBS as a reliable method to distinguish skin tissues with difference in pigmentation level.

Plasma emission of biochemical elements generated with a laser irradiation on melanocytic skin lesion.     

Electronic, magnetic and optical properties of Cu, Ag, Au-doped Si clusters

The structural, optical and magnetic properties of Cu, Ag, Au-doped Si₇ Clusters have been systematically investigated using density functional theory calculations. The global optimized structures of Cu, Ag, Au-doped Si clusters are predicted to have a lower HOMO–LUMO gap and higher magnetic moment. M-doping (M?=?Cu, Ag, Au) in Si cluster widens a range of adsorption wavelength, especially Au-doping. The characteristics in electronic density of states (DOSs) show that C_5v-Si₆Cu has a big asymmetrical spin-up and spin-down. The average atomic moment is 0.428 mμ_B per atom for the Si₆Cu cluster with C_5v symmetry, while the average paramagnetic moment is 0.143 mμ_B per atom for other M-doped (M?=?Cu, Ag, Au) Si₇ clusters.     

Use of a light-induced respiratory transient to measure the optical cross section of photosystem I in chlorella

A method has been developed whereby the magnitude of a transient in O₂ uptake attributable to photosystem (PS) I activity, following single-turnover laser flashes of varying energy, can be used to measure the optical cross section of PSI. As measurements are made under the identical physiological conditions for which the cross section of PSII has previously been determined (AC Ley, DC Mauzerall 1982 Biochim Biophys Acta 680: 96-105), it is now possible to simultaneously measure the cross section of both photosystems in intact, photosynthetically competent cells, without the use of inhibitors or artificial mediators of electron transport. Plots of light-saturation behavior of the respiratory oscillation following pulses at 596 nanometers indicate a mean optical cross section similar to that of PSII at this wavelength, but suggest significant heterogeneity in the cross section of PSI. If this method measures only PSI activity, this result implies that there exist units with different numbers of identical chromophores, or units having populations of chromophores with different absorption spectra.     

Spectroscopic characterization and conformation of oligo kappa carrageenans

Identification of oligo-carrageenans by ¹³C n.m.r., infrared spectroscopy and optical rotation is presented. ¹³C n.m.r. signals have been assigned for d-galactose 4-sulphate and oligomers of kappa carrageenan on the basis of model spectra of parent polymer and deuterium isotopic effect. Optical rotation measurements give evidence of the conformational transition of such oligomers, depending on their degree of polymerizations.     

兔血管对He—Ne激光的反射、透射、吸收系数和散射相函数的研究

本文运用光生物学、基础医学以及物理学的基本理论 ,探讨了兔血管组织的激光传播特性 ,定量测定了兔血管组织的激光传输参量。采用标准积分球测量了兔血管组织样品在 632 .8nmHe Ne激光照射下的透射率 (T)和反射率 (R) ,推算吸收率 (A)。并把分光仪改装为光散射测量装置 ,测量了 632 .8nmHe Ne激光照射下 ,- 90°～ 90°散射角范围内的散射相函数S(θ) ,计算平均散射余弦 μ。结果表明 :兔动脉对He Ne激光的漫反射率比静脉的大 (P <0 .0 1 ) ,而透射率却明显比静脉小 (P <0 .0 1 ) ,而动脉的吸收系数明显地比静脉要小 ,He Ne激光对静脉的穿透深度明显比动脉的要大。兔动脉和静脉对He Ne激光有较强的反向散射 (μa<0 .5 ,μν<0 .5) ,且静脉的反向散射明显较动脉的要强 ,其相应的散射相函数S(θ)有着明显的差别。兔动脉和静脉对He Ne激光的反射、透射、吸收系数及散射相函数等光学性质的明显不同提示在应用He Ne激光进行血管疾病的治疗时应加以考虑。     

Non-Gated Laser Induced Breakdown Spectroscopy Provides a Powerful Segmentation Tool on Concomitant Treatment of Characteristic and Continuum Emission

We demonstrate the application of non-gated laser induced breakdown spectroscopy (LIBS) for characterization and classification of organic materials with similar chemical composition. While use of such a system introduces substantive continuum background in the spectral dataset, we show that appropriate treatment of the continuum and characteristic emission results in accurate discrimination of pharmaceutical formulations of similar stoichiometry. Specifically, our results suggest that near-perfect classification can be obtained by employing suitable multivariate analysis on the acquired spectra, without prior removal of the continuum background. Indeed, we conjecture that pre-processing in the form of background removal may introduce spurious features in the signal. Our findings in this report significantly advance the prior results in time-integrated LIBS application and suggest the possibility of a portable, non-gated LIBS system as a process analytical tool, given its simple instrumentation needs, real-time capability and lack of sample preparation requirements.     

Geminate recombination of n-butyl isocyanide to myoglobin

Transient optical absorption spectra of myoglobin were measured following photolysis of the n-butyl isocyanide complex with 10-ns laser pulses at room temperature. The data were analyzed by using singular value decomposition to give the kinetics of ligand rebinding and spectral changes. Geminate recombination phases were observed at 30 ns and 1 microsecond following photodissociation. These processes were accompanied by simultaneous changes in the shape of the Soret band which indicate changes in protein conformation. These spectral changes are not present in the geminate recombination of photolyzed complexes of myoglobin with the diatomic ligands oxygen and carbon monoxide. This difference in behavior, as well as the slower overall association rate of n-butyl isocyanide to myoglobin, can be rationalized as arising from distortion of the protein structure by the larger isocyanide ligand along the binding pathway.     

Development of laser induced breakdown spectroscopy technique to study irrigation water quality impact on nutrients and toxic elements distribution in cultivated soil

This study is focused mainly on impact of irrigation water quality in cultivated soil on distribution of essentials nutrients (Al, Mg, Ca, Fe, S, Si, Na, P, and K) and relatively toxic metals (As, Ba, Cr, Cu, Ti, Sn, Mn, Ni, and Zn) using an elegant Laser induced breakdown spectroscopy (LIBS) technique. A pulsed Nd:YAG laser operating at 1064 nm in conjunction with suitable detector was applied to record soil emission spectra. The abundance of these elements were evaluated via standard calibration curve Laser Induced Breakdown Spectroscopy (CC-LIBS) and calibration free Laser Induced Breakdown Spectroscopy (CF-LIBS) approaches. Quantitative analyses were accomplished under conjecture of local thermodynamic equilibrium (L.T.E) and optically thin plasma. The average electron temperatures were estimated by Boltzmann plot method for cultivated soil samples in 7800 to 9300 K range. The electron number density was ~ 1.11 × 1017 cm − 3 to 1.60 × 1017 cm − 3. Prior to application on soil samples, the experimental setup was optimized at the following parameters: pulsed energy = 60 mJpulse-1, sample to lens distance of 9.0 cm, and the gate delay of 3.5 μs. It is noteworthy that nutritional elements content of cultivated soils were found strongly dependent upon the irrigation water quality. The cultivated soil from industrial area was found rich of toxins while the cultivated land using tube well water contains toxins in least amount. Our LIBS findings were also validated by comparing its results with contents measured using a standard inductively coupled plasma optical emission spectroscopy (ICP-OES) method and both were found in excellent agreement. The present study could be highly beneficial for agricultural applications and for farmers to produce safe food products and higher crops yield.