Vibrational spectroscopy of articular cartilage

Articular cartilage is a connective tissue that is located at the ends of long bones. Type II collagen, proteoglycans, water, and chondrocytes are the main constituents of articular cartilage. Osteoarthritis, the most common joint disease in the world, causes degenerative changes in articular cartilage tissue. Fourier transform infrared, Raman, and near infrared spectroscopic techniques offer versatile tools to assess biochemical composition and quality of articular cartilage. These vibrational spectroscopic techniques can be used to broaden our understanding about the compositional changes during osteoarthritis, and they also hold promise in disease diagnostics. In this article, the current literature of articular cartilage spectroscopic studies is reviewed.     

Calcifications in human osteoarthritic articular cartilage: ex vivo assessment of calcium compounds using XANES spectroscopy

Calcium (Ca²⁺)‐containing crystals (CCs), including basic Ca²⁺ phosphate (BCP) and Ca²⁺ pyrophosphate dihydrate (CPPD) crystals, are associated with severe forms of osteoarthritis (OA). Growing evidence supports a role for abnormal articular cartilage mineralization in the pathogenesis of OA. However, the role of Ca²⁺ compounds in this mineralization process remains poorly understood. Six patients, who underwent total knee joint replacement for primary OA, have been considered in this study. Cartilage from femoral condyles and tibial plateaus in the medial and lateral compartments was collected as 1 mm‐thick slices cut tangentially to the articular surface. First, CCs presence and biochemical composition were assessed using Fourier transform infrared spectroscopy (FT‐IR). Next, Ca²⁺ compound biochemical form was further assessed using X‐ray absorption spectroscopy (XAS) performed at the Ca²⁺K‐absorption edge. Overall, 12 cartilage samples were assessed. Using FT‐IR, BCP and CPPD crystals were detected in four and three out of 12 samples, respectively. Ca²⁺ compound biochemical forms differed between areas with versus without CCs, when compared using XAS. The complete set of data shows that XANES spectroscopy can be used to accurately characterize sparse CCs in human OA cartilage. It is found that Ca²⁺ compounds differ between calcified and non‐calcified cartilage areas. In calcified areas they appear to be mainly involved in calcifications, namely Ca²⁺ crystals.     

在多层结构的生物组织中近红外光子迁移的研究

在无损近红外光学诊断领域中,研究光子在多层生物组织中的迁移十分重要。本文以猪的脂肪和肌肉组成的两层结构作为研究的样品。将近红外光源和检测器置于脂肪的表面,由光源发出被两层组织反射的光子的一部分由检测器所接收。本文给出了光电流与光源到检测器的距离的关系以及光电流与脂肪厚度的关系。为了分析实验结果,用蒙特卡罗仿真计算光子在均匀介质中迁移轨迹,用菲涅耳定律来决定光子包在脂肪和肌肉边界处的折射分量和反射分量。结果表明,仿真数据与实验符合得很好。结论是：本文中所提供的实验和仿真方法对于分析光子在生物组织中的迁移以及优化传感器设计十分有用。     

Applications of near-infrared spectroscopy (NIRS) in biomass energy conversion processes: A review

Biomass used in energy conversion processes is typically characterized by high variability, making its utilization challenging. Therefore, there is a need for a fast and non-destructive method to determine feedstock/product properties and directly monitor process reactors. The near-infrared spectroscopy (NIRS) technique together with advanced data analysis methods offers a possible solution. This review focuses on the introduction of the NIRS method and its recent applications to physical, thermochemical, biochemical and physiochemical biomass conversion processes represented mainly by pelleting, combustion, gasification, pyrolysis, as well as biogas, bioethanol, and biodiesel production. NIRS has been proven to be a reliable and inexpensive method with a great potential for use in process optimization, advanced control, or product quality assurance.     

Raman spectroscopic analysis of cataract lens: A compendious review

Age-related cataracts is a pressing health issue with the increase in elderly populations. This creates an imminent demand for the development of an early, noninvasive method of cataracts diagnosis. Early detection of cataracts will improve quality of life and may prevent morbidity associated with advanced cataracts and surgery. Raman spectrum of proteins provides characteristic information regarding molecular interactions of peptide residues. Hence Raman spectroscopy is a promising tool for the study of protein-related diseases, such as cataracts. We surveyed the literature to assess the use of Raman technology in the studies of human lens and animal models. These studies included analysis of amino acids (i.e., cysteine, tryptophan, and tyrosine, etc.) and secondary protein structures (i.e., α-helix and β-sheet) in various Raman profiles. Other studies used Raman spectroscopy to analyze and monitor the development of cataracts in lens. Technological advances in the instrumentation of laser Raman spectroscopy, including Fourier transform Raman spectroscopy, Raman microspectroscopy, and confocal Raman microspectroscopy have improved the performance of Raman spectroscopic analysis. How to take advantage of these developments and make it closer to reality using Raman spectroscopic methods to diagnose cataracts in a timely manner is a key challenge for the scientific community of Raman spectroscopy.     

Near-infrared photoluminescence and thermally stimulated current in Cu3Ga5Se9 layered crystals: A comparative study

Near-infrared photoluminescence (PL) and thermally stimulated current (TSC) spectra of Cu₃Ga₅Se₉ layered crystals grown by Bridgman method have been studied in the photon energy region of 1.35–1.46 eV and the temperature range of 15–115 K (PL) and 10–170 K (TSC). An infrared PL band centered at 1.42 eV was revealed at T = 15 K. Radiative transitions from shallow donor level placed at 20 meV to moderately deep acceptor level at 310 meV were suggested to be the reason of the observed PL band. TSC curve of Cu₃Ga₅Se₉ crystal exhibited one broad peak at nearly 88 K. The thermal activation energy of traps was found to be 22 meV. An energy level diagram demonstrating the transitions in the crystal band gap was plotted taking account of results of PL and TSC experiments conducted below room temperature.     

A spectroscopic resolution of the structure of Zn(CN)2

Two different cubic structures of the negative thermal expansion (NTE) material zinc cyanide have been reported in the literature: one, an ordered structure (space group P4 3m) in which the ZnC₄ tetrahedra are linked to neighbouring ZnN₄ tetrahedra with CN bonds and vice versa, and the other, a disordered structure (space group Pn4 3m) where N and C sites are indistinguishable. Here, we present group theoretical analyses to classify the phonons of different symmetries in the two structures and report Raman and infrared spectroscopic studies to resolve the ambiguity about the structure. On the basis of the number of Raman and IR modes expected and observed, we conclude that the compound exists in a disordered structure. Copyright © 2006 John Wiley & Sons, Ltd.     

Structural and spectroscopic investigations of non‐planar tris(dialkylamino)cyclopropenium cations

The mixed triaminocyclopropenium cation bis(diisopropylamino)dimethylaminocyclopropenium was prepared from bis(diisopropylamino)chlorocyclopropenium by reaction with dimethylamine. It was isolated as the perchlorate salt and found to have a distorted structure in the solid state. Tris(diisopropylamino)cyclopropenium was prepared by reaction of pentachlorocyclopropane with diisopropylamine in a refluxing dichloroethane solution for 2 days. The solid state structure was found by X‐ray crystallography to have two planar amino groups and one pyramidal amino group, however, the ¹H‐NMR and infrared solution spectra show equivalent isopropyl groups in solution. The compounds were also characterised by Raman and infrared spectroscopy. Additionally, a new polymorph of [C₃(NMe₂)₃]ClO₄ is described as well as the X‐ray structure of bis(diisopropylamino)cyclopropenone. Copyright © 2007 John Wiley & Sons, Ltd.     

LAMOST medium-resolution spectroscopic survey of binarity and exotic star (LAMOST-MRS-B): Observation strategy and target selection

LAMOST-MRS-B is one of the sub-surveys of LAMOST medium-resolution ($Rsim7500$) spectroscopic survey. It aims at studying the statistical properties (e.g., binary fraction, orbital period distribution, mass ratio distribution) of binary stars and exotic stars. We intend to observe about 30000 stars ($10 {rm mag}leq G < 14.5$ mag) with at least 10 visits in five years. We first planned to observe 25 plates around the galactic plane in 2018. Then the plates were reduced to 12 in 2019 because of the limitation of observation. At the same time, two new plates located at the high galactic latitude were added to explore binary properties influenced by the different environments. In this survey project, we set the identified exotic and low-metallicity stars with the highest observation priorities. For the rest of the selected stars, we gave the higher priority to the relatively brighter stars in order to obtain high quality spectra as many as possible. Spectra of 49129 stars have been obtained in LAMOST-MRS-B field and released in DR8, of which 28828 and 3375 stars have been visited more than twice and ten times with $rm SNR geq 10$, respectively. Most of the sources are B-, A-, and F-type stars with $rm -0.6< [Fe/H] < 0.4 $ dex. We also obtain 347 identified variable and exotic stars and about 250 stars with $rm [Fe/H] <-1$ dex. We measure radial velocities (RVs) by using 892233 spectra of the stars. The uncertainties of RV achieve about $1$ ${rm km cdot s^{-1}}$and $10$ ${rm km cdot s^{-1}}$ for 95% of late- and early-type stars, respectively. The datasets presented in this paper are available at http://www.doi.org/10.57760/sciencedb.j00113.00035.     

The hydrates and deuterates of ferrous sulfate (FeSO4): a Raman spectroscopic study

A comparative analysis has been carried out on the Raman spectra of FeSO₄·nH₂O (n = 1, 4, 7) including the ²D‐analogs. The effects of changing the degrees of hydration have been found from the lattice, SO₄²⁻ internal, and H₂O internal modes. Increasing degrees of hydration shift the intense ν₁(SO₄) peak to lower wavenumbers and reduce the amount of splitting on the ν₃(SO₄) peaks. Some of the water librational bands cause the broadening of the ν₄(SO₄) peaks in FeSO₄·7H₂O and the ν₂(SO₄) peaks in FeSO₄·7D₂O. The ν₂(H₂O) band in FeSO₄·H₂O is red‐shifted in excess of 100 cm⁻¹ relative to the unperturbed H₂O band. Between 240 and 190 K and between 140 and 90 K in the spectra of FeSO₄.4H₂O, two potential phase transitions have been identified from the changes in the lattice and water‐stretching regions. The resolution of the ν₁(H₂O) and ν₃(H₂O) bands in FeSO₄·4H₂O and FeSO₄·H₂O also improved sharply at low temperatures. The capability of distinguishing various forms of FeSO₄ hydrates unambiguously makes the Raman technique a potential analytical tool for the identification of sulfate minerals on planetary surfaces. Copyright © 2006 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of the antimony mineral klebelsbergite Sb4O4(OH)2(SO4)

Many minerals based upon antimonite and antimonate anions remain to be studied. Most of the bands occur in the low wavenumber region, making the use of infrared spectroscopy difficult. This problem can be overcome by using Raman spectroscopy. The Raman spectra of the mineral klebelsbergite Sb₄O₄(OH)₂(SO₄) were studied and related to the structure of the mineral. The Raman band observed at 971 cm⁻¹ and a series of overlapping bands are observed at 1029, 1074, 1089, 1139 and 1142 cm⁻¹ are assigned to the SO₄²⁻ν₁ symmetric and ν₃ antisymmetric stretching modes, respectively. Two Raman bands are observed at 662 and 723 cm⁻¹, which are assigned to the Sb O ν₃ antisymmetric and ν₁ symmetric stretching modes, respectively. The intense Raman bands at 581, 604 and 611 cm⁻¹ are assigned to the ν₄ SO₄²⁻ bending modes. Two overlapping bands at 481 and 489 cm⁻¹ are assigned to the ν₂ SO₄²⁻ bending mode. Low‐intensity bands at 410, 435 and 446 cm⁻¹ may be attributed to O Sb O bending modes. The Raman band at 3435 cm⁻¹ is attributed to the O H stretching vibration of the OH units. Multiple Raman bands for both SO₄²⁻ and Sb O stretching vibrations support the concept of the non‐equivalence of these units in the klebelsbergite structure. It is proposed that the two sulfate anions are distorted to different extents in the klebelsbergite structure. Copyright © 2010 John Wiley & Sons, Ltd.     

基于近红外光谱的玉米籽粒CNCPS组分分析及预测研究

试验旨在研究应用近红外光谱技术快速测定玉米籽粒粉末CNCPS组分的可行性。65个样品来自黑龙江省,选用偏最小二乘法(PLS)为建模方法,采用二阶导数和Norris导数滤波法处理光谱数据后,建立了玉米籽粒粉末中干物质(DM)、粗蛋白质(CP)、粗脂肪(Fat)、粗灰分(Ash)、淀粉(Starch)、中性洗涤纤维(NDF)、酸性洗涤纤维(ADF)、可溶性蛋白(SP)、酸性洗涤不溶蛋白(ADIP)和中性洗涤不溶蛋白(NDIP)等的近红外预测模型。其中DM,CP,Fat,Ash,Starch,NDF和ADF的决定系数分别为0.974 3,0.968 3,0.947 8,0.909 8,0.977 7,0.935 4和0.926 9,标准差(SD)与预测均方根(RMSEP)的比值(SD/RMSEP)值分别为3.96,4.78,3.75,4.25,4.13,3.88和3.12。SP的决定系数为0.857 5,SD/RMSEP值为3.06。ADIP和NDIP的决定系数分别为0.531 9和0.683 3,SD/RMSEP值分别为5.50和2.85。试验结果表明,近红外技术可以用于玉米籽粒粉末CNCPS组分的快速测定,但降低ADIP和NDIP测定误差有待进一步研究。     

Nondestructive discrimination of internal defects in jujube (Huizao) of Xinjiang based on visible and near-infrared spectroscopy

Abstract

During harvest and transport, defects are most likely to affect the interior of jujubes and thus shorten their storage period. This study applied visible and near-infrared transmission spectroscopy to detect such internal defects. Spectra were acquired on the equator area at 0, 90, 180, and 270 degrees of each sample, and a model was constructed to obtain three-dimensional damage and defect detection model. The first derivative, multiplicative scatter correction, standard normal variate, and median filtering were used for preprocessing. Modeling by mean spectra achieved a better effect than using unidirectional spectra. Then, naive Bayes classifier and support vector machine were employed for the model establishment at 600–950?nm and 680–950?nm bands, respectively, using mean spectra. Median filtering effectively improved the signal to noise ratio and the discrimination accuracy of the support vector machine model at 600–950?nm reached 96.77%, which was the best value among all models. This result indicates that the support vector machine model was the optimum model and 600–950?nm was a suitable data range for the detection of internal defects. This research confirms the feasibility of implementing visible and near-infrared spectroscopy for the detection of internal defects in jujubes.     

Growth of manganese silicide films by co-deposition of Mn and Si on Si(1 1 1): A spectroscopic and morphological investigation

MnSi is a ferromagnetic compound with a Curie temperature of 29 K. Recent theoretical studies predict that 2 ML of MnSi epitaxially grown on Si show a ferromagnetic metallic ground state with spin polarization of about 50%. This would allow the development of spintronic devices based on the injection of spin-polarized current from a ferromagnetic metal into a semiconductor.In this context the possibility of growing in situ MnSi on the Si(1 1 1) surface has been explored. Thermal reaction, crystalline structure and electronic properties of the grown films have been studied in situ by photoemission spectroscopy (PES), X-ray absorption spectroscopy (XAS), and low energy electron diffraction (LEED). Depositing a thin film of Mn on Si(1 1 1) the formation of ordered islands (with dimensions dependent on the amount of deposited Mn) is driven by annealing at selected temperatures, as already observed. Our preliminary studies show that by simultaneously depositing Mn and Si in 1:1 stoichiometry on Si(1 1 1) a large improvement in the homogeneity of the MnSi films is achieved.     

Determination of Total Petroleum Hydrocarbon (TPH) and Polycyclic Aromatic Hydrocarbon (PAH) in Soils: A Review of Spectroscopic and Nonspectroscopic Techniques

Abstract: In the analysis of petroleum hydrocarbon–contaminated soils for total petroleum hydrocarbons (TPHs) and polycyclic aromatic hydrocarbons (PAHs), the roles of spectroscopic and nonspectroscopic techniques are inseparable. Therefore, spectroscopic techniques cannot be discussed in isolation. In this report, spectroscopic techniques including Raman, fluorescence, infrared, and visible and near-infrared (Vis-NIR) spectroscopies, as well as mass spectroscopy (coupled to a gas chromatograph) and nonspectroscopic techniques such as gravimetry, immunoassay, and gas chromatography with flame ionization detection are reviewed. To bridge the perceived gap in coverage of the quantitative applications of Vis-NIR spectroscopy in the rapid determination of TPHs and PAHs in soils, a detailed review of studies from the period 1999–2012 are presented. This report also highlights the strengths and limitations of these techniques and evaluates their performance from the perspective of their attributes of general applicability, namely economic portability, operational time, accuracy, and occupational health and safety considerations. Overall, the fluorescence spectroscopic technique had the best performance (85% total score) in comparison to the others, and the gravimetric technique performed the least (60% total score). Method-specific solutions geared toward performance improvement are also suggested.     

Challenges and opportunities in quantitative analyses of lead,cadmium, and hexavalent chromium in plant materials by laser-induced breakdown spectroscopy: A review

Bearing the merits of rapid, minimally destructive, and simultaneous multi-element analyses, laser-induced breakdown spectroscopy (LIBS) shows its unique advantages in quantitative analyses of lead, cadmium, and hexavalent chromium in plant materials. However, the greatest challenge LIBS must confront is calibration. Various methods for calibration are proposed and put into effect; nevertheless, limits of detection acquired by LIBS are not acceptable when they are compared with the maximum residue limits drawn up by governments, and LIBS's performances in quantitative analyses are to be improved. This review summarizes recent studies of analyzing lead, cadmium, and hexavalent chromium in plant materials quantitatively by LIBS; weighs the strengths and weaknesses of their calibration methods; and recommends the combination of matrix-matched standards based on spiked sample materials and internal standard as well as chemometrics in complicated situations for calibration in LIBS. Selecting the emission line of the analyte, sample enrichment and signal enhancement are measures that this review puts forward to improve the performances of LIBS in calibration. These quantitative analyses of lead, cadmium, and hexavalent chromium in plant materials by LIBS provide an opportunity to be utilized in mapping distributions and remediation for soil and water, as well as supervision for agricultural products safety and pollution treatments.     

高重复频率脉冲功率技术及其应用：（7）主要技术问题和未来发展趋势

综合论述了高重复频率脉冲功率技术所面临的主要技术障碍和工程问题。从实用的角度归纳了脉冲功率源设计时经常遇到的矛盾关系。结合目前的技术发展动态,探讨了未来这项技术的发展趋势和主要方向。目前,高重复频率脉冲功率系统的主要瓶颈是开关技术;主要技术障碍包括冷却、效率及可靠性;主要矛盾体现在系统的紧凑性与绝缘要求、上升时间与峰值功率、工作参数与可变范围及技术性能与制作成本等方面;未来发展趋势主要包括模块化、通用化和智能化。     

高重复频率脉冲功率技术及其应用:(7)主要技术问题和未来发展趋势

综合论述了高重复频率脉冲功率技术所面临的主要技术障碍和工程问题。从实用的角度归纳了脉冲功率源设计时经常遇到的矛盾关系。结合目前的技术发展动态,探讨了未来这项技术的发展趋势和主要方向。目前,高重复频率脉冲功率系统的主要瓶颈是开关技术;主要技术障碍包括冷却、效率及可靠性;主要矛盾体现在系统的紧凑性与绝缘要求、上升时间与峰值功率、工作参数与可变范围及技术性能与制作成本等方面;未来发展趋势主要包括模块化、通用化和智能化。     

Laser-induced breakdown spectroscopy in archeological science: a review of its application and future perspectives

Laser-induced breakdown spectroscopy (LIBS) in the last decades has become a promising analytical technique for a broad variety of archeological objects with great results obtained either alone or in combination with complementary techniques. It is mainly advantageous due to no sample preparation, minimally destructive, rapid analysis and depth profiling analysis spur LIBS technique to become a significant attractive technique for the characterization and conservation of archeological samples or artworks. The present paper describes in brief the basic principles and instrumentation of LIBS, and reviews several case studies on metallic alloys, ceramic, glass, painted artworks, historical buildings and biomaterials in the most recent 7 years (2011–2017) that demonstrate the applicability and prospects of LIBS in the field of archeological science.     

Raman spectroscopic study of the metatellurate mineral: xocomecatlite Cu3TeO4(OH)4

The mineral xocomecatlite is a hydroxy metatellurate mineral with Te⁶⁺ O₄ units. Tellurates may be subdivided according to their formula into three types of tellurate minerals: type (a) (AB)_m (TeO₄)_pZ_q, type (b) (AB)_m(TeO₆)^·xH₂O and (c) compound tellurates in which a second anion including the tellurite anion, is involved. The mineral xocomecatlite is an example of the first type. Raman bands for xocomecatlite at 710, 763 and 796 cm⁻¹, and 600 and 680 cm⁻¹ are attributed to the ν₁(TeO₄)²⁻ symmetric and ν₃ antisymmetric stretching mode. Raman bands observed at 2867 and 2926 cm⁻¹ are assigned to TeOH stretching vibrations and enable estimation of the hydrogen bond distances of 2.622 Å (2867 cm⁻¹), 2.634 Å (2926 cm⁻¹) involving these OH units. The hydrogen bond distances are very short implying that they are necessary for the stability of the mineral. Copyright © 2008 John Wiley & Sons, Ltd.