Relevance of Reflection in Static and Dynamic Light Scattering Experiments

Using a monodisperse PMMA dispersion, it was shown that light reflection at the sample cuvette walls may greatly influence the results of both static (SLS) and dynamic (DLS) light scattering experiments. Considering SLS, this reflection phenomenon mostly causes an overestimation of the scattered intensity at high scattering angles, which may give rise to the emergence of an additional, artificial peak in the lower region of the particle size distribution. On the other hand, the influcence of reflection on DLS measurements was shown to be particularly important in the upper region of the particle size distribution. The experimentally observed phenomena were explained from the basic principles of both particle sizing methods. Finally, it was shown that the disturbing effect of reflection could be avoided by modifying either the hardware or the software of the static and dynamic light scattering technique.     

动态光散射测量粒径分布的格雷码编码遗传算法反演运算

采用格雷码编码的遗传算法对动态光散射测量的粒径分布进行反演运算,数字测试结果表明,对于无噪声的分布,算法能精确的反演出各种粒子分布图像;对于加了一定噪声的分布,算法显示出较好的稳定性,能反演出主峰的分布图像.聚苯乙烯乳球的实验结果表明,该算法能反演双分布的粒径分布图像.与标准遗传算法和反演蒙特卡罗算法相比,该算法具有较高的搜索效率,能够用较少的计算时间快速搜索到最优解.格雷码编码遗传算法是一种更有效的随机反演算法.     

Temperature-sensitive poly(N-Isopropyl-Acrylamide) microgel particles: A light scattering study

We present a light scattering study of aqueous suspensions of microgel particles consisting of poly(N-Isopropyl-Acrylamide) cross-linked gels. The solvent quality for the particles depends on temperature and thus allows tuning of the particle size. The particle synthesis parameters are chosen such that the resulting high surface charge of the particles prevents aggregation even in the maximally collapsed state. We present results on static and dynamic light scattering (SLS/DLS) for a highly diluted sample and for diffuse optical transmission on a more concentrated system. In the maximally collapsed state the scattering properties are well described by Mie theory for homogenous hard spheres. Upon swelling we find that a radially inhomogeneous density profile develops.     

Appearance of an artifact peak in the particle size distribution measured by DLS at low concentrations

The dynamic light scattering (DLS) method allows the determination of the particle size distribution of suspensions. At high dilutions, an artifact peak appears in the size distribution, which does not correspond to actual particles, but is caused by crossing the scattering volume boundaries by individual particles. The parameters of this peak are analyzed, the causes of its appearance and its effect on determined particle sizes are studied.     

基于颗粒粒度信息分布特征的动态光散射加权反演

宽分布和双峰分布颗粒的准确反演是动态光散射技术至今未能有效解决的难题,尤其峰值位置比小于2:1且含有大粒径颗粒(350 nm)的双峰分布.造成这一难题的主要原因包括:1)单角度测量数据的粒度信息含量不足;2)常规反演方法对测量数据的噪声抑制以及粒度信息利用缺乏针对性.对测量数据(即光强自相关函数)的研究发现,数据噪声主要分布在长延迟时段,而粒度信息集中分布在衰减延迟时段.基于此,本文提出了采用粒度信息分布为底数、调节参数为指数的权重系数对自相关函数进行加权反演的约束正则化方法.由于采用了与粒度信息分布一致的权重系数,该方法既充分利用了衰减延迟时段的粒度信息,又有效地抑制了长延迟时段的数据噪声.不同噪声水平下,宽分布和双峰分布颗粒体系的反演结果表明,与常规反演方法相比,这一方法可以获得更为准确的宽分布和近双峰分布的反演结果.     

Characterisation of nanoparticle size and state prior to nanotoxicological studies

Before commencing any nanotoxicological study, it is imperative to know the state of the nanoparticles to be used and in particular their size and size distribution in the appropriate test media is particularly important. Particles satisfying standards can be commercially purchased; however, these invariably cannot be used directly and need to be dispersed into the relevant biological media. Often such changes in the environment or ionic strength, or a change in the particle concentration, results in some aggregation or a shift in the particle size distribution. Such unexpected aggregation, dissolution or plating out, if unaccounted for, can have a significant effect on the available nanoparticle dose and on interpretation of any results obtained thereafter. Here, we demonstrate the application of characterisation instrumentation that sizes nanoparticles based on their Brownian motion in suspension. Unlike classical light-scattering techniques, the nanoparticle tracking and analysis (NTA) technique allows nanoparticles to be sized in suspension on a particle-by-particle basis allowing higher resolution and therefore better understanding of aggregation than ensemble methods (such as dynamic light scattering (DLS) and differential centrifugation sedimentation (DCS)). Results will be presented from gold (standard) nanoparticles in biologically relevant media that emphasise the importance of characterisation of the nanoparticle dispersion. It will be shown how the NTA technique can be extended to multi-parameter analysis, allowing for characterization of particle size and light scattering intensity on an individual basis. This multi-parameter measurement capability allows sub-populations of nanoparticles with varying characteristics to be resolved in a complex mixture. Changes in one or more of such properties can be followed both in real time and in situ.     

Determination of Particle Size Distribution by the analysis of intensity-constrained multi-angle photon correlation spectroscopic data

Laser light scattering (LLS), especially dynamic laser light scattering (DLS), also known as photon correlation spectroscopy (PCS), is a well established method for particle size distribution analysis. It usually involves a Laplace inversion of the field autocorrelation function. However, the resolution is limited because of the ill-conditioned nature of this Laplace inversion. No unique solution exists when noise is present on the data. In contrast with this ill-conditioned nature, the angular dependence of scattered (static) intensities is precisely not ill-conditioned, which allows the resolution of the ill-conditioned inversion of DLS data to be improved. In order to characterize samples with more complicated size distributions, an intensityconstrained multi-angle PCS data analysis program has been developed, which is an alternative way of normalizing the field correlation function to that reported by Cummins and Staples [12]. In this program, the field autocorrelation function is normalized to the scattering intensity by using a predetermined coherent factor at each angle, which provides an additional constraint on the Laplace inversion of multi-angle PCS data analysis. The alternative analysis improves the resolution of PCS and provides a more reliable particle size distribution than single-angle data analysis. Both simulated and measured LLS data are used to illustrate its application, resolution and limitations.     

Swelling/deswelling of polyacrylamide gels in aqueous NaCl solution: Light scattering and macroscopic swelling study

Swelling kinetics of water-swollen polyacrylamide (PAAm) hydrogels (WSG) was investigated in various concentrations of aqueous NaCl by macroscopic swelling measurements. For lower concentration of NaCl, WSG showed exponential swelling whereas at higher concentration of NaCl it underwent deswelling at short times and exponential swelling at long times. From these studies, collective diffusion coefficient, D, of the polymer network and polymer?Csolvent interaction parameter, ??, were calculated and found to decrease with increase in [NaCl]. Collective diffusion coefficients measured from dynamic light scattering (DLS) and that obtained from macroscopic swelling measurements are found to agree well. Measured ensemble-averaged dynamic structure factor f(q,t) for WSG and salt-swollen gels (SSG) showed an initial decay followed by a plateau at long times and it can be described by harmonically bound Brownian particle (HBBP) model. Enhanced scattering intensity at low scattering angles using static light scattering (SLS) measurements revealed the presence of inhomogeneities in PAAm gels. The reasons for increased scattering intensity of SSG over WSG gel and the linear decrease of D with increase in NaCl concentration are explained.     

颗粒系的可见消光光谱分析及最佳波长的选择

在光全散射法颗粒粒径测量中,被测颗粒系的消光光谱包含有颗粒粒径、折射率等信息。对常用的单峰及双峰R-R分布的可见消光光谱进行模拟,分析了可见消光光谱随粒径和相对折射率变化的规律。选取二阶微分可见消光光谱不连续点对应的波长作为测量波长,并将可见光边界波长同时作为测量波长,在非独立模式下,采用遗传优化算法反演粒径分布。仿真计算与实验验证结果表明,通过消光光谱分析,可以预先确定被测颗粒系的分布状况,缩小优化算法中反演参数的搜索范围。结合最佳波长选择方法,使测量的精度和可靠性明显提高。对测量光谱加入1%随机噪声时,单峰及多峰分布粒径反演均能得到满意的结果。     

Characterization of Nanoparticles by Scattering Techniques

Basic principles and applications of different scattering techniques (including static and dynamic light scattering (SLS and DLS), small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD) and small-angle neutron scattering (SANS)) on the characterization of nanoparticles are reviewed in this paper. By choosing a suitable scattering technique or a combination of different techniques for nanoparticle characterization, the particles' molecular weight, radius of gyration, hydrodynamic radius, size distribution, shape and internal structure as well as interparticle interactions of nanoparticles, can be determined. Examples including some sophisticated colloidal systems are presented.     

Resolving Concentrated Particle Size Mixtures Using Dynamic Light Scattering

Dynamic light scattering (DLS) is a technique used for measuring the size of molecules and particles undergoing Brownian motion by observing time‐dependent fluctuations in the intensity of scattered light. The measurement of samples using conventional DLS instrumentation is limited to low concentrations due to the onset of a phenomenon called multiple scattering. The problems of multiple scattering have been addressed in a light scattering instrument incorporating non‐ invasive backscatter optics (NIBS). This novel optic arrangement maximizes the detection of scattered light while maintaining signal quality and allows for measurements of turbid samples. This paper discusses the ability of backscatter detection to accurately determine particle sizes at 1 %w/v sample concentrations and demonstrates the correct resolution of different size populations using a series of latex standard mixtures with known volume ratios. The concentration of 1 %w/v is much higher than can be measured on conventional dynamic light scattering instruments.     

Characterization of nanoparticles of lidocaine in w/o micro emulsions using small-angle neutron scattering and dynamic light scattering

Microemulsions (MEs) are of special interest because a variety of reactants can be introduced into the nanometer-sized aqueous domains, leading to materials with controlled size and shape [1,2]. In the past few years, significant research has been conducted in the reverse ME-mediated synthesis of organic nanoparticles [3,4]. In this study, a w/o ME medium was employed for the synthesis of lidocaine by direct precipitation in w/o microemulsion systems: water/isopropylpalmitat/Tween80/Span80. The particle size as well as the location of nanoparticles in the ME droplet were characterized by means of dynamic light scattering (DLS) and small angle neutron scattering (SANS). It is observed that lidocaine precipitated in the aqueous cores because of its insolubility in water. Hydrodynamic radius and gyration radius of microemulsion droplets were estimated as ∼15 nm and ∼4.50 nm from DLS and SANS respectively. Furthermore, different size parameters obtained by DLS and SANS experiments were compared     

Measurement of optical constants for dense media by low-coherence dynamic light scattering

We perform the optical constants measurements for different absorption dense media by low-coherence dynamic light scattering (DLS) technique. The estimated particle size is used to calculate the scattering coefficient of particles suspended in dense media. The path-length resolved intensity distributions of light backscattered from the absorbing dense media are investigated experimentally by virtue of path-length resolved performance in low-coherence DLS measurements. The absorption coefficient can be obtained by applying the measured path-length resolved intensity distributions to the modified Lambert-Beer law. As a result, we proposed a new low-coherence DLS technique in simultaneous measurement of the scattering and absorption coefficients of absorbing dense media.     

初始模型对含噪动态光散射数据正则化反演结果的影响

分别采用最小模型矩阵、最平坦模型矩阵、最光滑模型矩阵作为初始化模型,对加入5种不同水平随机噪声的90 nm窄单峰、90 nm宽单峰和250 nm窄单峰、250 nm宽单峰颗粒体系的模拟分布进行了正则化反演,并对反演结果进行比较。结果表明：当噪声水平为0时,正则化初始模型的选择对反演结果没有明显影响。随着噪声水平的增加,采用三种初始化模型反演得到的峰值误差和粒度分布误差都随之变大,但采用最平坦模型和最光滑模型反演得到的峰值和粒度分布误差明显小于采用最小初始模型的反演误差。当噪声水平大于0.01时,选择最平坦初始模型获得的粒度分布结果优于采用最光滑初始模型和最小初始模型获得的结果,而采用最光滑初始模型反演得到的峰值优于最平坦初始模型和最小初始模型的反演峰值。因此,采用正则化算法处理含噪动态光散射数据时,为得到最优的粒度分布信息,宜采用最平坦初始模型,若需要获取最准确的峰值信息,则应选择最光滑初始模型。     

可见-红外波段光全散射法颗粒粒径测量范围的研究

在光全散射法颗粒粒径测量中,采用独立模式算法在可见-红外波段对粒径测量范围进行了深入的研究。通过对多种R-R分布函数反演结果进行分析,比较,以确定光全散射法颗粒粒径测量范围。同时在消光系数计算中,采用修正的消光系数代替原始的消光系数,以便得到更准确的粒径测量范围。仿真计算结果表明,在可见-红外光谱区,相对折射率m=1.235时的粒径测量范围为0.05～18 μm。在此区域内测量粒径分布,反演结果与真值基本吻合。随着颗粒相对折射率、波长范围的变化,粒径测量范围也随之发生改变。采用限制最小二乘算法能够最大限度地克服随机噪声对测量结果的影响,使测量的精度和可靠性明显提高。对测量的消光值加入±1%随机噪声时,颗粒粒径分布的反演均能得到满意的结果。     

降雨粒子的无线紫外光散射特性

紫外光与降雨粒子相互作用发生散射,散射光特性改变能够反映降雨粒子的相关物理特性（如粒子尺寸参数、浓度、形态）,因此研究粒子的物理参数对散射光特性的影响对有效提高光谱法定量探测降水的精度有很大意义。由于雨滴在非球形降水粒子中具有代表性,以群雨滴粒子为例,采用T矩阵理论,利用紫外光直视和非直视单次散射模型,分析了入射光波长、群雨滴粒子形态、降雨强度、粒径大小与散射光强之间的关系。并用蒙特卡洛方法仿真分析了非球形群雨滴粒子在不同降雨强度和粒径下散射角与散射光强之间的关系,以及降雨环境中的风切变对紫外光散射特性的影响。通过理论及仿真分析,得到了不同群雨滴粒子形态下的路径损耗,不同降雨强度、风切变率和粒径下的散射光强分布。仿真结果表明：在紫外光直视与非直视通信方式下,降雨环境中的通信质量比晴天条件下的通信质量差,即路径损耗增大。当粒径分布已知时,随着降雨强度的增大,衰减系数增大,路径损耗增加,且直视通信方式的路径损耗比非直视降低7 dB左右。随着降雨强度、风切变率和粒子粒径的增大,散射光强曲线整体呈下降趋势,其中,降雨强度的变化对散射光强分布影响程度最大。相同通信距离时,不同降雨强度下的紫外光散射光强分布均随着散射角的增大而减小,当散射角继续增大到90°时,有效散射体体积逐渐减小,接收到的光子能量减小,暴雨中的散射光强衰减程度最大。相同降雨强度下考虑风切变时,相比较无风时的路径损耗增大5 dB左右。除此之外,还研究了椭球形和切比雪夫形粒子对紫外光散射光强的影响,结果表明当粒子粒径分布相同时,椭球形粒子的散射光强衰减较广义切比雪夫形粒子大。根据散射粒子的散射光强分布以及路径损耗能够区分雨滴粒子是否由相同粒径及形态组成,为粒子测量提供理论基础。分析降水中群雨滴粒子的光散射特性,为提高光谱法评估降水衰减的数值模拟方面提供理论依据,为光学技术在探测识别降水现象等气象领域的广泛应用提供了设计参考。     

Dynamic Light Scattering Measurement of Nanometer Particles in Liquids

Dynamic light scattering (DLS) techniques for studying sizes and shapes of nanoparticles in liquids are reviewed. In photon correlation spectroscopy (PCS), the time fluctuations in the intensity of light scattered by the particle dispersion are monitored. For dilute dispersions of spherical nanoparticles, the decay rate of the time autocorrelation function of these intensity fluctuations is used to directly measure the particle translational diffusion coefficient, which is in turn related to the particle hydrodynamic radius. For a spherical particle, the hydrodynamic radius is essentially the same as the geometric particle radius (including any possible solvation layers). PCS is one of the most commonly used methods for measuring radii of submicron size particles in liquid dispersions. Depolarized Fabry-Perot interferometry (FPI) is a less common dynamic light scattering technique that is applicable to optically anisotropic nanoparticles. In FPI the frequency broadening of laser light scattered by the particles is analyzed. This broadening is proportional to the particle rotational diffusion coefficient, which is in turn related to the particle dimensions. The translational diffusion coefficient measured by PCS and the rotational diffusion coefficient measured by depolarized FPI may be combined to obtain the dimensions of non-spherical particles. DLS studies of liquid dispersions of nanometer-sized oligonucleotides in a water-based buffer are used as examples.     

Surface Modification of Magnetic Nanoparticles Using Gum Arabic

Magnetite nanoparticles were synthesized and functionalized by coating the particle surfaces with gum arabic (GA) to improve particle stability in aqueous suspensions (i.e. biological media). Particle characterization was performed using transmission electron microscopy (TEM) and dynamic light scattering (DLS) to analyze the morphology and quantify the size distribution of the nanoparticles, respectively. The results from DLS indicated that the GA-treated nanoparticles formed smaller agglomerates as compared to the untreated samples over a 30-h time frame. Thermogravimetric analyses indicated an average weight loss of 23%, showing that GA has a strong affinity toward the iron oxide surface. GA most likely contributes to␣colloid stability via steric stabilization. It was determined that the adsorption of GA onto magnetite exhibits Langmuir behavior.     

基于后向散射的高浓度纳米颗粒粒度分布测量方法研究

传统的动态光散射法通常采集侧向散射进行纳米颗粒粒度分布的测量,由于多次散射的影响,利用侧向散射不能准确测量高浓度样品的颗粒粒度分布。针对该问题,对后向散射测量方法进行了研究,在实验基础上提出了后向散射最佳光程的判断准则。在不同样品浓度下,用侧向散射和后向散射方法对标称粒径分别为110 nm、220 nm的聚苯乙烯乳胶球颗粒进行了测量。实验结果表明,对于高浓度的待测样品,后向散射测量方法通过自适应调整光程,在最优光程处进行测量,能够有效得到高浓度纳米颗粒的粒径及粒度分布,测量结果相对误差为2.72%。     

Small-angle neutron and dynamic light scattering study of gelatin coacervates

The state of intermolecular aggregates and that of folded gelatin molecules could be characterized by dynamic laser light and small-angle neutron scattering experiments, which implied spontaneous segregation of particle sizes preceding coacervation, which is a liquid-liquid phase transition phenomenon. Dynamic light scattering (DLS) data analysis revealed two particle sizes until precipitation was reached. The smaller particles having a diameter of ～50 nm (stable nanoparticles prepared by coacervation method) were detected in the supernatant, whereas the inter-molecular aggregates having a diameter of ～400 nm gave rise to coacervation. Small-angle neutron scattering (SANS) experiments revealed that typical mesh size of the networks exist in polymer dense phase (coacervates) [1]. Analysis of the SANS structure factor showed the presence of two length scales associated with this system that were identified as the correlation length or mesh size, ξ = 10.6 Å of the network and the other is the size of inhomogeneities = 21.4 Å. Observations were discussed based on the results obtained from SANS experiments performed in 5% (w/v) gelatin solution at 60°C (ξ = 50 Å, ζ = 113 Å) and 5% (w/v) gel at 28°C (ξ = 47 Å, ζ = 115 Å) in aqueous phase [2] indicating smaller length scales in coacervate as compared to sol and gel.