Production of Monodisperse Nanoparticles and Application of Discrete-Monodisperse Model in Plasma Reactors

The particle growth in plasma reactor were investigated by using the discrete-monodisperse (D-M) model for various process conditions. The monodisperse large sized particle distribution predicted by the D-M model are in good agreement with the large sized particles by the discrete-sectional model and also in the experiments by Shiratani et al. (1996). Some fractions of the small size particles are in a neutral state or even charged positively, but most of the large sized monodisperse particles are charged negatively. As the mass generation rate of monomers increases, the large sized particles grow more quickly and the production rate of nanoparticles of 100nm by plasma reactor increases. As the initial electron concentration or the monomer diameter increases, it takes longer time for the large sized particles to grow up to 100nm, but the large sized particle concentration of 100nm increases and the resulting production rate of large sized particles of 100nm increases. As the residence time increases, the time for the large sized particles to grow up to 100nm decreases and the large sized particle concentration of 100nm increases and, as a result, the production rate of large sized particles of 100nm increases. We propose that the plasma reactor can be a good candidate to produce monodisperse nanoparticles.     

One-Pot Scalable Fabrication of Chitosan-Capped Antibacterial Sulfur Nanoparticles from Elemental Sulfur

Sulfur nanoparticles (SNPs) have shown good potential in numerous fields due to their unique composition and properties. However, the direct utilization of abundant and inexpensive elemental sulfur for the large-scale fabrication of high-quality SNPs is still in its infancy. Herein, a simple one-pot approach for the preparation of SNPs is presented, and gram-scale SNPs can be readily prepared in one batch in the laboratory. By adding elemental sulfur-ethylenediamine precursor to the acidic chitosan (CS) solution, chitosan-capped sulfur nanoparticles (CS-SNPs) can be formed immediately. Benefiting from the capping of CS, CS-SNPs simultaneously possess small and uniform size with an average diameter of 19 nm, good aqueous dispersibility and stability, and favorable antioxidant capability against 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) free radicals. Moreover, CS-SNPs also exhibit fine antibacterial activity against Staphylococcus aureus, and the minimum and optimal inhibitory concentrations are 256 and 512 µg mL⁻¹, respectively. Considering the easy fabrication process and attractive attributes of CS-SNPs, this investigation not only offers an effective method for the scalable fabrication of robust SNPs but also provides a feasible way for the value-added utilization of elemental sulfur.     

The Formation of Porous Membranes by Filtration of Aerosol Nanoparticles

Flame-generated aerosol particles of Al₂O₃ were deposited by gas filtration on two types of porous and ceramic tubes of -Al₂O₃ with mean pore diameters of 450 and 2700nm, respectively. The particles were aggregates with average mobility diameters in the range of 30–100nm and primary particle diameters of 4–8nm. The particles are characterized by differential mobility analysis, transmission electron microscopy, and by their specific surface area. The deposited membranes are characterized by gas permeability measurements, scanning electron microscopy, and by their pore size distribution from nitrogen capillary condensation. The particles form a distinct, homogeneous membrane layer with a porosity of 90% on top of the substrate surface and only penetrate slightly into the substrate structure. The mean pore sizes of the deposited membranes determined by nitrogen condensation agree approximately with those determined by gas permeation and the specific surface area. The mean pore diameter varies in the range of 30–70nm. The gas permeability of the deposited membranes is related to the specific surface area but influenced by the high porosity. The mean pore size and the permeability of the membranes are almost independent of the substrate structure.The development of a membrane with uniform properties is preceded by a short initial period in which the deposited particles, with an equivalent membrane thickness of roughly 2m, have a significantly lower permeability than the ultimately developed uniform membrane layer. This effect is particularly significant for the aerosol particles with the lowest mean size, probably due to particles deposited in the pore mouths of the substrate.The particles and the deposited membranes are X-ray amorphous but retain their specific surface area on heating to even high temperatures. When the membranes are heated to 1473K for 10h, X-ray diffraction shows a mixture of - and -alumina, accompanied by a partial disintegration of the membrane and a considerable loss of surface area.     

Preparation of Photoluminescent Porous Silicon Nanoparticles by High‐Pressure Microfluidization

The use of high‐shear microfluidization as a rapid, reproducible, and high‐yield method to prepare nanoparticles of porous silicon (pSi) with a narrow size distribution is described. Porous films prepared by electrochemical etch of a single‐crystal silicon wafer are removed from the substrate, fragmented, dispersed in an aqueous solution, and then processed with a microfluidizer, which generates high yields (57%) of pSi nanoparticles of narrow size distribution (PDI = 0.263) without a filtration step. Preparation of pSi nanoparticles via microfluidization improves yields (by 2.4‐fold) and particle size uniformity (by 1.8‐fold), and it lowers the total processing time (by 36‐fold) over standard ultrasonication or ball milling methods. The average diameter of the nanoparticles can be adjusted over the range 150–350 nm by appropriate adjustment of processing steps. If the fluid carrier in the microfluidizer contains an oxidant for Si, the resulting pSi particles are prepared with a core–shell structure, in which an elemental Si core is encased in a silicon oxide shell. When an aqueous sodium tetraborate processing solution is used, microfluidization generates photoluminescent core–shell pSi particles with a quantum yield of 19% in a single step in less than 20 min.     

高速碰撞诱发闪光辐射温度的测量及误差分析

为实现对高速碰撞诱发的闪光辐射温度进行实验测量及误差分析,建立了二级轻气炮加载系统及闪光辐射温度测量系统。采用聚碳酸酯弹丸分别以6 km/s、3.9 km/s的速度垂直撞击2A12铝靶,利用瞬态光纤高温计采集闪光信号,通过比色法计算不同碰撞条件下的闪光辐射强度及辐射温度。依据普朗克辐射定律计算了不同波长及温度条件下的闪光辐射强度理论值,与实验测量结果相比较并进行了误差分析;分别采用双色测温法的不同波长组合及四色测温法计算了闪光辐射温度及其平均温度,通过计算标准差分析了波长的选取对闪光辐射温度的影响。结果表明：与理论计算结果相比较,实验测量得到的闪光辐射强度值偏低,采用双色测温法计算闪光辐射温度时波长的选取对计算结果影响很大,波长间隔越大计算结果误差越小（误差最小值实验No.1为68.25 K,实验No.2为30.67 K）;四色测温法计算得到的闪光辐射温度与平均温度相近（误差实验No.1为72.88 K,实验No.2为63.66 K）,因此采用比色法计算闪光辐射温度时应尽量选取大间隔波长或多个波长参与计算以降低误差。     

等离子体闪光法识别薄膜损伤的误判消除方法

传统的等离子体闪光法,是根据探测器是否接收到来自薄膜样片周围发射的闪光信号,对薄膜是否发生损伤进行评判,这样的评判方法极易把空气与薄膜的等离子体闪光混淆而发生误判。为了消除这种误判,提出通过比较空气和薄膜各自的等离子体闪光的点燃时间,利用两者时间上的差异,实现对传统等离子体闪光法误判现象的消除方法。为了验证新方法的可靠性,借助于多光子吸收和级联电离理论,建立了空气等离体子体点燃时间的计算模型,根据薄膜与激光的相互作用原理建立了薄膜被击穿时的等离子体点燃时间计算模型,利用建立的模型仿真计算了空气和薄膜的等离子体闪光点燃时间分别为1.856和7.843 ns;搭建实验装置以实现对传统等离子体闪光法的更新,在装置中的不同位置设置三个光电探测器分别采集入射激光信号、空气和薄膜等离子体闪光信号,采集入射激光信号的光电探测器置于聚焦透镜的侧面,另外两个探测器位于薄膜样片周围且左右对称放置,分别用于采集薄膜的等离子体闪光信号和空气的等离子体闪光信号,所有光电探测器采集的信号转换为电信号后同步传输至示波器,以入射激光信号为基准信号,其与空气和薄膜等离子体闪光信号的起始时刻之差,分别为空气和薄膜等离子体闪光点燃时间。脉宽为10 ns、波长为1 064 nm的Nd∶YAG脉冲激光以0.015 cm的聚焦光斑半径、82.4 mJ的入射能量作用于光学厚度为λ/4、直径为20 mm的单层Al₂O₃薄膜样片上后,采集上述激光作用条件下的各路信号,经处理后得到的空气和薄膜的等离子体闪光点燃时间测试值分别为2.7和7.8 ns;理论计算和实验测试结果表明,空气的点燃时间总是小于薄膜的点燃时间,二者有很好的一致性。说明当强激光作用于单层Al₂O₃薄膜表面时,空气等离子体闪光先于薄膜等离子体闪光发生。基于空气和薄膜等离子体闪光点燃时间上的这种差异,利用闪光信号时间上的差别就可准确分辨出薄膜是否发生损伤,从而获得识别薄膜损伤与否的判据,这种从时间差异上识别薄膜等离子体闪光损伤的新方法,无论从理论上还是实验上均为传统等离子体闪光法误判现象的消除提供了技术基础。     

超高速碰撞2A12铝板产生闪光辐射的空间演化规律

为了描述超高速碰撞2A12铝板产生闪光辐射的空间演化规律,利用瞬态光纤高温计测量系统并结合二级轻气炮加载系统,开展了弹丸以30°的入射角度和不同碰撞速度条件下的超高速撞击实验。基于闪光辐射强度和辐射温度的实验数据处理得到了超高速碰撞2A12铝板在撞击点附近产生的最大闪光辐射强度和最大闪光辐射温度,基于大量实验,建立了撞击点附近最大闪光辐射的空间演化模型。并结合Origin软件对实验所得数据的拟合,得到了最大闪光辐射强度和辐射温度随探测点到着靶点间距离变化的拟合函数关系式。实验结果还表明:在相近碰撞速度、相同碰撞角度条件下,在同一椭球面上不同探测点位置处的最大闪光辐射强度和最大闪光温度差别不大,验证了撞击产生的闪光辐射以近似椭球的形状向外膨胀,随着等离子体云的向外膨胀,离碰撞点越远产生的最大闪光辐射强度和最大闪光辐射温度均越小;在相同碰撞角度、不同碰撞速度条件下,在同一椭球面上不同探测点位置处的最大闪光辐射强度和最大闪光温度均随碰撞速度的增加而增大。该研究在导弹拦截、天体物理及深空探测领域具有重要的应用价值。     

苯甲酸及其甲基取代物的激光光解研究

研究了苯甲酸及其甲基取代物在248 nm激光作用下的光电离及光激发行为,测定了光电离量子产额和激发三线态寿命及其自猝灭速率常数。实验结果显示甲基在苯环不同位置的取代对苯甲酸化合物激发三线态的影响不明显。利用分步双激光技术对苯甲酸激发态进行共振激发,对可能生成的瞬态产物进行了初步探讨。     

水热法碱活化生物质乙醇木质素的化学结构变化

为了提高生物质乙醇木质素的反应活性,采用水热法在四种不同碱性条件下对生物质乙醇木质素进行催化活化处理。运用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H-NMR)、凝胶色谱(GPC)和有机元素分析手段研究了生物质乙醇木质素被四种碱(NaOH, KOH, K₂CO₃和Na₂CO₃)催化活化前后木质素的化学结构以及组分变化。FTIR结果表明生物质乙醇木质素碱经处理后,木质素的酚羟基特征吸收峰1 375 cm-1都有明显增大趋势,醚键振动吸收峰1 116 cm-1减弱,1 597和1 511 cm-1处苯环骨架振动吸收峰强度变化很小;1H-NMR分析结果表明酚羟基含量都有增大趋势,增加顺序为：KOH>NaOH>K₂CO₃>Na₂CO₃,其中KOH处理后的木质素酚羟基含量增加量为原木素的170%。这由于离子半径大的钾离子更容易与木质素β—O—4醚键上的氧形成加和物,进而发生醚键断裂反应,生成新的酚结构衍生物。GPC 表明生物质乙醇木质素碱处理后分子量分布向低分子区域扩展, 数均和重均分子量减小。元素分析结果显示木质素经过水热反应处理后,C含量都有所增加,而H和O含量则降低了,表明木质素经水热反应处理过程中有脱羧基作用,同时蛋白质的含量也有所降低,提高了木质素的纯度。这都有利于直接将木质素用于制备酚醛树脂胶黏剂。     

Monodisperse Branched Molybdenum‐Based Bioactive Nanoparticles Significantly Promote Osteogenic Differentiation of Adipose‐Derived Stem Cells

Adipose‐derived stem cells (ADSCs) are considered to be ideal stem cell sources for bone‐tissue regeneration owing to their ease of collection and high activity. However, the regulation of osteogenic differentiation of ADSCs using biomaterials without adding growth factors is still not satisfactory. For the first time, molybdenum‐doped bioactive glass nanoparticles with a radial porous morphology (Mo‐rBGNs) are reported and their role in the osteogenic differentiation of ADSCs is investigated. The results show that Mo‐rBGNs exhibit radially porous and spherical morphology, relatively homogeneous particle size (200–400 nm), and excellent apatite‐forming bioactivity. They do not affect the proliferation of ADSCs, but significantly regulate their osteogenic differentiation and biomineralization. 5% Mo‐rBGNs significantly enhance the alkaline phosphatase activity and biomineralization ability and promote the osteogenic gene expressions of collagen I secretion and bone sialo protein in ADSCs. A reasonable and promising strategy for designing nanoscale bioactive materials with the excellent osteogenic ability for stem cell–based bone tissue regeneration is provided.     

电化学刻蚀制备的荧光碳纳米颗粒

以纯石墨作电极、乙二胺四乙酸二钠溶液作电解液制备了具有荧光性质的碳纳米颗粒。利用紫外-可见分光光度计和荧光分光光度计分析了碳纳米颗粒的光吸收和荧光发射特征,利用透射电镜和电子能谱分析了碳纳米颗粒的尺寸、晶体状态和成分。结果表明,碳纳米颗粒仅有几纳米,呈分散状态;在325 nm附近具有强的光吸收并表现出强的蓝光发射特征。研究了电解质溶液的种类、浓度等对碳纳米颗粒荧光发射的影响,讨论了碳纳米颗粒的荧光发射机理。     

Facile synthesis of monodisperse silver nanoparticles by bio-template of squama inner coat of onion

This paper describes a facile sy]nthetic method for preparing monodisperse silver nanoparticles by bio-template of the squama inner coat of onion. The method is able to make silver nanoparticles with average diameters in the range of 4.6–7.9 nm with narrow size distribution. The important factors in the synthesis of monodisperse silver nanoparticles were discussed. The nanoparticles were characterized by transmission electron microscope, Powder X-ray diffraction and UV-Vis spectroscopy. A possible formation mechanism was also proposed. Because of its simple apparatus, high yield, convenient operation and mild conditions, this synthetic method will have potential application in preparing nanoparticles.     

Engineering the Internal Structure of Magnetic Silica Nanoparticles by Thermal Control

Calcination of hydrated iron salts in the pores of both spherical and rod‐shaped mesoporous silica nanoparticles (NPs) changes the internal structure from an ordered 2D hexagonal structure into a smaller number of large voids in the particles with sizes ranging from large hollow cores down to ten nanometer voids. The voids only form when the heating rate is rapid at a rate of 30 °C min^?1. The sizes of the voids are controlled reproducibly by the final calcination temperature; as the temperature is decreased the number of voids decreases as their size increases. The phase of the iron oxide NPs is α‐Fe₂O₃ when annealed at 500 °C, and Fe₃O₄ when annealed at lower temperatures. The water molecules in the hydrated iron (III) chloride precursor salts appear to play important roles by hydrolyzing Si? O? Si bonding, and the resulting silanol is mobile enough to affect the reconstruction into the framed hollow structures at high temperature. Along with hexahydrates, trivalent Fe³⁺ ions are assumed to contribute to the structure disruption of mesoporous silica by replacing tetrahedral Si⁴⁺ ions and making Fe? O? Si bonding. Volume fraction tomography images generated from transmission electron microscopy (TEM) images enable precise visualization of the structures. These results provide a controllable method of engineering the internal shapes in silica matrices containing superparamagnetic NPs.     

“反胶团法”合成的CdS半导体纳米粒子的光谱性质研究

反相胶束是指由介于油和水界面的表面活性剂分子, 稳定、且均匀分散于连续油介质中的微液滴。它可以作为“微反应器”合成性能优良的CdS粒子。文章研究了反相胶束的W值(W=[水]/[表面活性剂])、[Cd2+]与[S2-]的比例和Cd2+和S2- 离子的起始浓度对CdS纳米粒子发光特性均有明显影响。回流处理可以对CdS纳米粒子的表面进行修饰,可以使CdS粒子的缺陷发光减弱并消失而显著增强激子发射,同时可增大粒径使激子发射峰位红移,体现了明显的量子限域效应; 所得材料的室温最大荧光量子效率高达11%。     

Formation of ZnO,MgO and NiO Nanoparticles from Aqueous Droplets in Flame Reactor

Nanoparticles of ZnO, MgO and NiO were produced from droplets of aqueous salt solution in the flame spray pyrolysis reactor. Conventional spray pyrolysis, in which electrical furnace reactor is used, is reported to produce nanoparticles only from acetate precursor. If the reactor pressure is low (60torr), nitrate salt precursor is also known to produce nanoparticles. In this paper, we report that nanoparticles are produced from nitrate as well as acetate salt precursor solution when propane–oxygen diffusion flame is used to decompose aqueous aerosol droplets. At low flame temperature, however, nanoparticles are not formed and the particle morphology is similar to the morphology produced by the conventional spray pyrolysis. At high flame temperature, nanoparticles are formed, regardless of the salt type. Nanoparticles are formed at lower flame temperature from acetate salts than from nitrate salts. All nanoparticle prepared in this work were fully crystallized and the size measured from transmission electron microscopy images was 30nm. This size agreed well with the particle size calculated from X-ray diffraction and specific surface area data.     

The Mechanisms of Oxygen Accelerated Low-Temperature Bonding by Ag Nanoparticles

Low-temperature bonding (≤300 ^o C) using Ag nanoparticles (Ag NPs) is considered to be the new generation of bonding technology in power electronics. The oxygen-accelerated sintering has been observed by many researchers which is attributed to the decomposition of organics covered on Ag NPs. In this work, organic-free Ag NPs are fabricated to eliminate the influence of organics, and it is found that the accelerated bonding process by oxygen is strongly correlated to the self-confined amorphous Ag-O compound shell on the surface of Ag NPs. In experiments, the sintering process is apparently accelerated by the elevating oxygen content, and the amorphous shell is observed after sintering, which do not grow thicker even in pure oxygen ambient for a long time while performing active chemical evolutions. In simulations, the results match well with the experiments and indicate that the amorphous shell performed the dynamic oxidation and decomposition process. This dynamic equilibrium is caused by the instability of silver oxides, which would enable the amorphous shell to activate the mobility of the surface mass flow and promote the surface diffusion. The shear strength of SiC chip increased by 354% when bonding in pure oxygen, targeting a broad variety of applications in electronic packaging.     

气相爆炸流场中TiO_2纳米颗粒生长的数值分析初探

气相爆炸制备TiO2纳米颗粒的实验成果在近年来多有报道,但对颗粒成长的模拟尚不多见。引入一种气溶胶的单分散性物理模型(Kruis模型),将其应用于气相爆炸流场中TiO2纳米颗粒生长的数值模拟,结合气相爆炸制备实验进行对比分析。结果表明,通过控制前驱体反应组分,气相爆轰合成了直径范围为20~150nm的球形TiO2纳米颗粒。数值模拟得到的颗粒大小与实验观测结果基本一致。影响纳米颗粒生长的主要因素包括反应温度、颗粒浓度及反应时间。     

掺杂CdS纳米粒子聚合物的光折变效应研究

研究了掺杂CdS纳米粒子的有机聚合物体系的光折变效应,体系中以CdS纳米粒子为光敏剂,聚乙烯咔唑(PVK)为载流子输运剂,4-(4-硝基苯偶氮)苯胺染料(DO3)为非线性生色团,9-乙基咔唑(ECZ)为增塑剂。反胶束法合成的CdS胶束颗粒采用紫外可见吸收光谱和透射电子显微镜(TEM)表征,结果表明,具有纳米尺寸和量子限制效应。研究了PVK-CdS薄膜的光电导特性,实验结果表明,CdS纳米粒子与PVK之间的电荷转移可以有效的提高PVK的光电导率。双光束耦合实验证明了该体系的光折变特性,在无外加电场下,获得二波耦合增益系数78.4 cm-1,分析表明聚合物薄膜具有强的光致取向增强效应;样品在两相干光束作用下,可建立折射率光栅,其衍射效率达到4.4%。     

Quenched Emission of Fluorescence by Ligand Functionalized Gold Nanoparticles

A fluorescence-based detection scheme that uses ligand functionalized gold nanoparticles is proposed. The transduction scheme is based on the strong quenching of the fluorescence emission exerted by metallic surfaces on fluorophores positioned in their immediate vicinity (< 5 nm). Binding of fluorophore-labeled anti-biotin to biotinylated gold nanoparticles resulted in decreased fluorescence emission intensity. Subsequent competitive dissociation of labeled anti-biotin with D-biotin resulted in increased fluorescence emission intensity. These interactions occurred by means of specific molecular recognition because when the binding sites of anti-biotin were saturated with D-biotin prior to interaction with the gold nanoparticles; changes in the fluorescence emission intensity were not observed.     

Fluorescence Modulation of Acridine and Coumarin Dyes by Silver Nanoparticles

Silver nanoparticles were synthesized by chemical reduction of silver ions by sodium borohydride in the presence of poly-(N)-vinyl-2-pyrrolidone in solution of short chain alcohols. The nanoparticles are stable in 2-propanol, and the average diameter of the Ag colloid obtained in this solvent is about 6 nm. The photophysical properties of acridinium and coumarin dyes in 2-propanol are affected by the presence of silver nanoparticles. The interaction of silver nanoparticles with acridinium derivative leads to a spectral change of its intramolecular charge transfer (ICT) absorption band. The dye emission increases suddenly with the initial addition of the Ag metal nanoparticles, but at a high concentration of the colloid, static fluorescence quenching occurs with a progressive decrease of the fluorescence efficiency. Amino coumarin fluorescence is only quenched by the silver nanoparticles in solution.