First order molecular hyperpolarizabilities and intramolecular charge transfer from the vibrational spectra of NLO material: ethyl‐3‐(3, 4‐dihydroxyphenyl)‐2‐propenoate

As part of the efforts for the design of new organic nonlinear optical(NLO) materials with high efficiency for present day technological requirements, a comprehensive investigation on the intramolecular charge transfer(CT) of an efficient π‐conjugated potential push–pull NLO chromophore, ethyl‐3‐(3,4‐dihydroxyphenyl)‐2‐propenoate(EDP) to a strong electron‐acceptor group through the π‐conjugated bridge has been carried out from their vibrational spectra. The first hyperpolarizabilities of caffeic derivatives are investigated by ab initio method. The NLO efficiency is experimentally measured by powder efficiency experiment. The strongest vibrational modes contributing to the electro‐optic effect from the simultaneous infrared(IR) and Raman activities of the ring CC stretching modes, in‐plane deformation modes, and the umbrella mode of the methyl groups have been identified and analyzed unambiguously. The influence of electronic effects, hyperconjugation and backdonation, on the C H stretching vibrations of both methyl and methylene groups causing the decrease of stretching wavenumbers and IR intensities has been extensively investigated. Copyright © 2009 John Wiley & Sons, Ltd.     

Fabrication of NIR‐Excitable SERS‐Active Composite Particles Composed of Densely Packed Au Nanoparticles on Polymer Microparticles

A simple fabrication method is demonstrated for surface‐enhanced Raman scattering (SERS)‐active plasmonic nanoballs, which consisted of Au nanoparticles (NPs) and core–shell polystyrene and amino‐terminated poly(butadiene) particles, by heterocoagulation and Au NP diffusion. The amount of Au NPs introduced into the core–shell particles increases with the concentration of Au NPs added to the aqueous dispersion of the core–shell particles. When the amount of Au NPs increases, closely packed, three‐dimensionally arranged and close‐packed Au NPs arrays are formed in the shells. Strong SERS signals from para‐mercaptophenol adsorbed onto composite particles with multilayered Au NPs arrays are obtained by near‐infrared (NIR) light illumination.     

Use of Multivariate Curve Resolution to Monitor an Esterification Reaction by Near‐Infrared Spectroscopy

Multivariate curve resolution–alternating least squares (MCR‐ALS) methodology was applied to near‐infrared (NIR) spectra with view to estimating the reaction profile for the esterification of a mixture of caprylic and capric acids with glycerol. The reaction was conducted in excess glycerol, so the major products were the monoglyceride and diglyceride; the triglyceride was obtained in considerably lower proportions. Esterification processes were performed in a laboratory‐scale reactor from which samples were withdrawn to record NIR spectra. Some samples were also analyzed by gas chromatography and acid‐base titration in order to determine the composition of the reaction mixture. Concentration and spectral profiles were obtained by using the MCR‐ALS algorithm. Subsequently, concentration values and the pure spectra of reagents and the triglyceride were used to refine the models. The spectra obtained were processed with MCR‐ALS in new esterification batches to obtain their concentration profiles.     

Near‐infrared surface‐enhanced Raman spectroscopy (NIR‐SERS) studies on oxyheamoglobin (OxyHb) of liver cancer based on PVA‐Ag nanofilm

A near‐infrared surface‐enhanced Raman spectroscopy (NIR‐SERS) method was employed for oxyheamoglobin (OxyHb) detection to develop a simple blood test for liver cancer detection. Polyvinyl alcohol protected silver nanofilm (PVA‐Ag nanofilm) used as the NIR‐SERS active substrate to enhance the Raman scattering signals of OxyHb. High quality NIR‐SERS spectrum from OxyHb adsorbed on PVA‐Ag nanofilm can be obtained within 16 s using a portable Raman spectrometer. NIR‐SERS measurements were performed on OxyHb samples of healthy volunteers (control subjects, n = 30), patients (n = 40) with confirmed liver cancer (stage I, II and III) and the liver cancer patients after surgery (n = 30). Meanwhile, the tentative assignments of the Raman bands in the measured NIR‐SERS spectra were performed, and the results suggested cancer specific changes on molecule level, including a decrease in the relative concentrations and the percentage of aromatic amino acids of OxyHb, changes of the vibration modes of the C_aH_m group and pyrrole ring of OxyHb of liver cancer patients. In this paper, principal component analysis (PCA) combined with independent sample T test analysis of the measured NIR‐SERS spectra separated the spectral features of the two groups into two distinct clusters with the sensitivity of 95.0% and the specificity of 85.7%. Meanwhile, the recovery situations of the liver cancer patients after surgery were also assessed using the method of discriminant analysis‐predicting group membership based on PCA. The results show that 26.7% surgeried liver cancer patients were distinguished as the normal subjects and 63.3% were distinguished into the cancer. Our study demonstrated great potentials for developing NIR‐SERS OxyHb analysis into a novel clinical tool for non‐invasive detection of liver cancers. Copyright © 2013 John Wiley & Sons, Ltd.     

Density functional study on the structural conformations and intramolecular charge transfer from the vibrational spectra of the anticancer drug combretastatin‐A2

Combretastatin‐A2 (CA2), a potential anticancer drug in advanced preclinical development, is extracted from the medicinal plant C ombretum caffrum. The NIR‐FT Raman and FT‐IR spectral studies of the molecule were carried out and a b initio calculations performed at the B3LYP/6‐31G(d) level to derive the equilibrium geometry as well as the vibrational wavenumbers and intensities of the spectral bands. The vibrational analysis showed that the molecule has a similar geometry as that of c is‐stilbene, and has undergone steric repulsion resulting in twisting of the phenyl ring with respect to the ethylenic plane. Vibrational analysis was used to investigate the lowering of the stretching modes, and enhancement of infrared band intensities of the C–H stretching modes of Me2 may be attributed to the electronic effects caused by back‐donation and induction from the oxygen atom. Analysis of phenyl ring modes shows that the CA2 stretching mode 8 and the aromatic C–H in‐plane bending mode are equally active as strong bands in both IR and Raman spectra, which can be interpreted as the evidence of intramolecular charge transfer (ICT) between the OH and OCH₃groups via conjugated ring path and is responsible for bioactivity of the molecule. Copyright © 2008 John Wiley & Sons, Ltd.     

基于高光谱数据研究应用近红外相机加装滤光片实现玉米叶片水分测量的关键参数

实现玉米等活体作物叶片不同区域以及近地冠层的水分含量检测,可为研究作物生长中的水分胁迫响应机制,以及旱情监测、精准灌溉等提供有效技术手段。大体积、大重量、低光通量的高光谱仪难以在田间实现活体检测,将小体积、小重量、高光通量近红外相机加装滤光片使其具有波长分辨能力,有望实现田间活体叶片水分含量成像检测。基于玉米叶片的近红外高光谱数据,对实现水分测量的特征波长位置及个数,以及特征波长带宽和偏移限度等关键参数进行研究;其中,不同带宽的仿真数据依据滤光片透光分布函数得到;固定带宽条件下的中心波长偏移仿真数据依据插值方法得到。研究结果表明：特征波长分别为1 150和1 400 nm,带宽小于100 nm时可满足要求,能够找到符合参数条件的滤光片产品;在带宽为25 nm下所建水分含量模型,其建模集的决定系数（R2）和均方根误差（RMSE）分别达到0.968,1.245%,预测集分别达到0.960,1.298%,可实现玉米叶片水分的准确检测。为推测加装滤光片所建模型受环境温度的影响,应用固定中心波长下的模型预测不同偏移量的仿真数据,当偏移量为0.05 nm时,模型预测误差为不漂移条件下3%左右,可忽略,由干涉滤光片中心波长漂移与温度的关系,相当于环境温度在50 ℃的范围对检测结果影响不大。该研究对近红外相机加装滤光片形成多光谱成像检测装置提供了重要技术参数支撑和环境工作范围建议,装置的搭建工作已开始,装置的实现可为现代农业作物生理、生产研究提供新型、有效手段。     

Polymer Optical Fiber Photosensitivities and Highly Tunable Fiber Gratings

In this paper, recent progress in the investigation of photosensitivities of polymer optical fibers and the development of polymer optical fiber grating is reported. Photosensitivities in various polymer fibers, including doped and undoped, multimode and single-mode polymer fibers, have been experimentally characterized and evaluated for fiber grating application. In particular, the wavelength dependence of material absorption and photosensitivity has been found essential to the fabrication of polymer optical fiber grating. Based on the results of photosensitivity research, polymer optical fiber gratings have been successfully fabricated. More importantly, polymer optical fiber grating has been demonstrated highly tunable, with a tuning range more than 70 nm. The unique feature of high tunability in polymer optical fiber grating has great potential in various applications including optical fiber WDM systems and fiber sensor systems. Several important issues that remain to be investigated will also be discussed.     

茶多酚中咖啡因的近红外光谱分析

采用近红外光谱分析技术对茶多酚中咖啡因进行了光谱及定量分析,原始光谱表明咖啡因在近红外波段有着很强且较为明显的吸收峰。通过对样品的漫反射原始吸光度光谱进行导数、散射校正及相关分析更清晰地给出了咖啡因在近红外光谱波段的光谱特性,为建立快速稳健的定标模型创造了条件。该技术能够解析出咖啡因中各主要基团在近红外波段的吸收特性,结合定标过程定量快速检测咖啡因在茶多酚中的含量,定标分析结果显示在很大的浓度范围内有很好的线性相关性,定标标准差SEC为0．49％,相关系数（r）为0．993,证实了近红外光谱分析技术作为一种新的快速分析茶多酚中咖啡因含量手段的可行性及优越性。     

电调谐液晶波导型光滤波器的理论分析

近年来,液晶光滤波器已成为频分复用和高密度波分复用光纤通信系统中的一种重要选频器件。传统液晶光滤波器的谐振腔一般由向列相液晶和镀有高反膜的两块中行介质镜形成,单模光纤与谐振腔之间由自聚焦透镜进行耦合,基模间耦合效率低。并且谐振腔内的大量高阶横模的存在严重影响了腔的选频特性。本文提出了一种液晶波导型谐振腔结构的滤渡器,谐振腔由两个自聚焦透镜的端面和液晶波导形成,这种谐振腔结构简单紧凑,在满足模式匹配条件时,可以大大减小谐振腔与自聚焦透镜间的模式转换损耗,并能有效地抑制腔内的高阶横模。本文着重分析了液晶光滤波器的调谐、滤波原理,推导出了液晶波导谐振腔与自聚焦透镜之间的模式耦合系数和模式最佳匹配条件。     

NIR‐Triggered Release of Nitric Oxide with Upconversion Nanoparticles Inhibits Platelet Aggregation in Blood Samples

There is a great challenge to overcome the limitation of tissue penetration depth, while maximizing the benefit of light‐triggered biochemical cascades in a well‐defined mode simultaneously. Here, a new method of near‐infrared (NIR) light‐triggered release of nitric oxide (NO) by developing upconversion nanoparticles (UCNPs)‐based conjugate chemistry is reported. As the key nanotransducer in the design, core–shell‐structured UCNPs are encapsulated with a layer of SiO₂ and then covalently linked with a potent NO‐releasing donor (S‐nitroso‐N‐acetyl‐dl ‐penicillamine, SNAP). It is featured with highly localized breakage of chemical bonds of SNAP molecules by NIR–UV upconversion, enabling simultaneous NO release in a light dosage‐dependent manner. The biological effects of NO releasing are demonstrated by cellular imaging and inhibition of platelet aggregation from blood samples. This work provides a flexible and robust platform to generate cell‐signaling gas molecules trigged by NIR laser with deep tissue penetration.     

Structural conformations and electronic interactions of the natural product,oroxylin: a vibrational spectroscopic study

The oroxylin, 5,7‐dihydroxy 6‐methoxy flavone is a potent natural product extracted from ‘Vitex peduncularis’. Density functional theory (DFT) at B3LYP/6‐311G(d,p) level has been used to compute energies of different conformers of oroxylin to find out their stability, the optimized geometry of the most stable conformer and its vibrational spectrum. The conformer ORLN‐1 with torsion angles 0, 180, 180 and 0 degrees, respectively, for H₁₃ O₁₂ C₆ C₅, H₁₄ O₁₀ C₄ C₅, H₁₃ O₁₂ C₆ C₅ and H₁₄ O₁₀ C₄ C₅ is found to be most stable. The optimized geometry reveals that the dihedral angle φ between phenyl ring B and the chrome part of the molecule in − 19.21° is due to the repulsive force due to steric interaction between the ortho‐hydrogen atom H₂₉ of the B ring and H₁₈ of the ring C (H₂₉·H₁₈ = 2.198 Å). A vibrational analysis based on the near‐infrared Fourier transform(NIR‐FT) Raman, Fourier transform‐infrared (FT‐IR) and the computed spectrum reveals that the methoxy group is influenced by the oxygen lone pair‐aryl p_z orbital by back donation. Hence the stretching and bending vibrational modes of the methoxy group possess the lowest wavenumber from the normal values of methyl group. The carbonyl stretching vibrations have been lowered due to conjugation and hydrogen bonding in the molecules. The intramolecular H‐bonding and nonbonded intramolecular interactions shift the band position of O₁₀ H₁₄ and O₁₂ H₁₃ stretching modes, which is justified by DFT results. Copyright © 2008 John Wiley & Sons, Ltd.     

水下目标跟踪的改进非线性滤波快速算法*

为了提升水下目标的跟踪精度,该文研究了测距误差有偏条件下的水下目标跟踪算法,基于水下目标跟踪中常用的无迹卡尔曼滤波(UKF)和容积卡尔曼滤波(CKF)算法,改进提出了将偏差系数作为状态变量之一进行联合估计的跟踪算法。结合水下目标跟踪场景的实际特点,进一步推导了这两种算法在线性状态方程条件下的简化形式,分别称为IS-UKF和IS-CKF算法。仿真实验和湖试实验结果表明,与常规无迹卡尔曼滤波和容积卡尔曼滤波算法相比,提出的两种改进算法(IS-UKF和IS-CKF算法)不仅具有同等运算量,而且提高了目标轨迹跟踪精度。     

Experimental investigation on the upconversion mechanism of 754 nm NIR luminescence of Ho/Yb:Y2O3, Gd2O3 under 976 nm diode laserexcitation

Upconversion (UC) spectra of Ho³⁺/Yb³⁺ codoped Y₂O₃, Gd₂O₃ bulk ceramics were obtained under the excitation of a 976 nm diode laser. Systematic experimental studies, including power dependence, luminescence lifetime, and the intensity ratio σ for the green to NIR emissions, were carried out in order to confirm the UC mechanism of Ho³⁺ ions. Our results demonstrated that the NIR emission was associated with the ⁵F₄/⁵S₂→⁵I₇ transition of Ho³⁺ ions without the contribution of the ⁵I₄→⁵I₈ transition for Ho³⁺/Yb³⁺ codoped Y₂O₃ and Gd₂O₃ bulk ceramics. Additionally, population saturation in the ⁵I₇ energy level had been observed in Ho³⁺/Yb³⁺ codoped Y₂O₃, Gd₂O₃ bulk ceramics. All experimental observations can be well explained by the steady-state rate equations.     

应用近红外可见光谱快速测量柴油十六烷值

快速测量十六烷值对检测柴油品质及控制炼制工艺具有重大意义。首先对采集到的381份柴油样品进行近红外可见光谱波段全光谱扫描,利用小波分析(WT)对原始数据进行去噪声处理,应用竞争性自适应重加权算法(CARS)进行特征波长选择,将CARS提取的22个特征波长输入至LS-SVM预测模型,决定系数r2为0.723,预测均方根误差RMSEP为1.878%。结果表明,使用WT-CARS变量选择算法获取光谱特征波长,结合LS-SVM建模,可以快速、准确的测量柴油中的十六烷值,为进一步实现柴油十六烷值的在线检测以及其他性能参数的快速测定奠定了基础。     

A Review of Recent Near-Infrared Research for Wood and Paper (Part 2)

Abstract: This review article introduces recent technical and scientific reports on near-infrared (NIR) spectroscopy in the wood and paper industry, which have increased during the last decade. Many researchers have reported that the NIR technique is useful for detection of both chemical and physical properties of wood materials and has been widely used in cases where the characteristic cellular structure of the material is retained. With regard to application of NIR spectroscopy to pulp and paper, many publications have reported its potential as an on-line measurement technique during paper-making process control. NIR spectroscopy is considered fundamental in applied research on wood and paper. Utilization of NIR spectroscopy in the wood and paper industry should take into account its applicability and limitations as a nondestructive technique.     

基于近红外的奶粉品质检测技术研究

奶粉种类繁多且检测的理化指标较多,为了进一步简化近红外光谱检测技术在奶粉生产过程中的应用步骤,文章首次提出了建立包含不同种类奶粉样品集的6个指标：酸度、脂肪、乳糖、蔗糖、蛋白和灰分的近红外模型,用于奶粉质量控制。该文采用全谱分析结合模型优化方法研究,分别建立了该混合奶粉样品集的6个指标的近红外模型。实验表明：除酸度外,该研究所建立混合奶粉的其他理化指标的近红外定标模型具有较好的稳定性和预测能力(RSD<10%,RPD>3)。因此该方法的提出可以简化近红外技术在奶粉定量分析中的步骤。     

湿度对近红外光谱检测的影响

光谱的检测过程会受诸如温度等很多条件的影响。本课题的目的在于研究在近红外检测过程中,环境湿度的变化对苹果检测结果的影响。建立一个自制湿度可控箱,通过改变箱内小环境的湿度值,对每个水果在40%～80%的湿度范围内每隔10%进行光谱采集。每个最终光谱是由水果的扫描光谱减去背景光谱获得的,由于不确定湿度随水果和背景的分别影响,光谱试验分两组进行：在不同的湿度下均采集背景和水果的光谱值(组1)和仅在40%的湿度值下采集背景(组2)。由20个苹果的样品集组成40组平行试验数据,运用单因素方差分析和马氏距离等处理方法进行分析。结果显示,无论在不同的湿度值下采集光谱和背景还是仅采集一个背景,其湿度值对近红外光谱的影响都不显著。     

Nd：YAG1064nm激发核黄素分子的表面增强拉曼光谱研究

本采用Ｎｄ：ＹＡＧ１０６４ｎｍ激光器作为发光源并改进银胶制备方法获得了核黄素的工外表面增强拉曼光谱（ＮＩＲ－ＳＥＲＳ）。发现少量的氢氧化钠可提高核黄素的ＮＩＲ－ＳＥＲＳ增强因子,其检测限可达３．２×１０＾－１０ｍｏｌ·Ｌ＾－１。证实核黄素在近红外区比可见区有更强的增强因子。