Fabrication of Dendrimer－like PAMAM Based on Silica Nanoparticles

A G 4.0 dendrimer-like poly (amido amine) (PAMAM) based on silica nanoparticles was fabricated via a divergent approach.It was built from γ-aminopropyi silica nanoparfides (APSN) core via repetitive addition of acrylate (MA) and hexylenediamine (HDA). FT-IR and EA were used to monitor the progress of dendrimer during each step. The amino group content of the resulting product increased from 0.49 to 3.72 mmol/g after the 4th generation. In addition, the percentage of grafting increased with increasing generation and reached to 65.9% after 4th generation. It was found that the resulting silica nanoparticles could be dispersed in methanol with a mean hydrodynamic particle diameter of 152.7 nm although the silica nanoparticles had agglomerated during the storage period.     

A Simple Approach to Control the Growth of Non-spherical Gold Nanoparticles

A simple method to prepare the non-spherical gold particles was developed. The result solution included trigonal, truncated trigonal, hexagonal layers, and a pseudo-pentagonal shaped gold nanocrystals. The key factor is to control the relative rates of nucleation and cluster growth in this method. These attributes make seeding growth method as a useful tool in the fabrication of colloidal metal materials. A longitudinal plasmon resonance of 866 nm was observed, which is in the near-IR spectral regions (600-1000 nm). The excellent optical properties as near-IR labels are used to develop highly sensitive analvsis method.     

Preparation of Gold Nanoparticles Protected with Polyelectrolyte

Gold nanoparticles were synthesized through the reduction of tetrachlorauric acid (HAuCh) by NaBH4, with polyethyleneimine(PEI) as stabilizer. The nanoparticles were characterized by UV-vis spectroscopy and atomic force microscopy(AFM).     

Site-specific Deposition of Colloidal Pd Nanoparticles on Self-assembled Microtubules from Biolipid

Lipid microtubules with wound ribbon features were fabricated by self-assembling method, and the deposition patterns of colloidal Pd particles on tubular template were investigated. The result indicates that colloidal Pd nanoparticles are preferentially decorated on the helical markings in the interior and on the exterior of preformed tubule and to the edge of loosely helical ribbons to obtain helical deposition features. The multi-bilayer microstructure of tubules can be marked by fine Pd nanoparticles deposited at the edge of helical ribbon. There are the site-specific interactions between lipid tubular template and colloidal Pd particles at the helical edge. A new route was illustrated that colloidal Pd particles firstly attach at the edge of thin flat membranes, and then thin membranes roll up and reassemble into tubule together with particles to form helical deposition patterns. The site-specific deposition of Pd is unbeneficial to obtain the homogeneous metal film on tubules, but it can be utilized to reveal the different chemical nature of lipid molecular assembly.     

纳米二氧化钛粉体及薄膜制备的研究进展

本文对近几年有关纳米二氧化钛粉体及薄膜的制备研究进行综述。重点介绍及评述了以无机钛盐和有机钛盐为前驱体制备纳米二氧化钛粉体及利用自组装方法制备二氧钛薄膜的最新研究成果。对今后研究工作的趋势进行了探讨。     

Synthesis and Fluorescence Properties of Eu^2＋-Doped KMgF3 Nanoparticles

Introduction Nanomaterialsusuallyshowsomenoveloptical,electronic,magneticandchemicalpropertiessignifi cantlydifferentfromthoseofthebulkmaterialsbecause oftheirextremelysmallsize,largespecificsurfaceare asandpeculiarquantumsize.Thepotentialoftheirap plicat…     

A New Method for the Synthesis of Selenium Nanoparticles and the Application to Construction of H202 Biosensor

The well-distributed, stable selenium nanoparticles (10 nm) with good adhesive abilityand biocompatibility were successfully synthesized by using the template of chitosan cross-linkedwith glutaradehyde. The resulting selenium nanoparticles were used as a new carrier forhorseradish peroxidase to construct H2O2 biosensors with good performances.     

Size control synthesis of sulfur doped titanium dioxide （anatase） nanoparticles, its optical property and its photo catalytic reactivity for CO2 ＋ H2O conversion and phenol degradation

Sulfur doped anatase TiO2 nanoparticles (3 nm−12 nm) were synthesized by the reaction of titanium tetrachloride, water and sulfuric acid with addition of 3M NaOH at room temperature. The electro-optical and photocatalytic properties of the synthesized sulfur doped TiO2 nanoparticles were studied along with Degussa commercial TiO2 particles (24 nm). The results show that band gap of TiO2 particles decreases from 3.31 to 3.25 eV and for that of commercial TiO2 to 3.2 eV when the particle sizes increased from 3 nm to 12 nm with increase in sulfur doping. The results of the photocatalytic activity under UV and sun radiation show maximum phenol conversion at the particle size of 4 nm at 4.80% S-doping. Similar results are obtained using UV energy for both phenol conversion and conversion of CO2+H2O in which formation of methanol, ethanol and proponal is observed. Production of methanol is also achieved on samples with a particle size of 8 and 12 nm and sulfur doping of 4.80% and 5.26%. For TiO2 particle of 4 nm without S doping, the production of methanol, ethanol and proponal was lower as compared to the S-doped particles. This is attributed to the combined electronic effect and band gap change, S dopant, specific surface area and the light source used.     

Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.     

Cluster—cracking Reaction,a New Method to Synthesize Unsymmetrical Dithiolate Complexes for the Study of Third—Order Nonlinear Optical Properties

A new coluster-cracking method to synthesize dithiolate metal complexes was reported and four unsymmetric complexes with formula(Me4N)2[M(Ln)(SPh)2](M=Cd and Zn,L1=dmit=1,3-dithiole-2-thione4-5,dithiolate,L2=dmid=1,3-dithiole-2-one-4,5-dithiolate,SPh=thiophenolate)(1-4)were characterized by elemental analysis,IR,UV NMR spectra and so on.The advantages of this method are summarized in two aspects:(1) the preparation is very convenient;(2) the reaction usually completed giving the product with high pruity.The crystal structure of 1 showed that the bond distances of Cd(Ⅱ）to the sulfur of the thiophenolate group are shorter than those of Cd(Ⅱ）to the sulfur of dmit,so that the thiophenolate group does not be replaced in the reaction and thmixed ligand complexes are the dominant produxts.The dmit complexes showed well third-order NLO properties,but not of the dmid complexes,although dmid is an analogue to dmit.     

纳米TiO2识别色氨酸对映体的研究

以纳米TiO2为基底,L-色氨酸(L-Trp)为模板分子,采用溶胶凝胶法合成L-Trp印迹的纳米TiO2。采用扫描电镜和红外光谱对印迹纳米TiO2和非印迹纳米TiO2进行表征,表明模板分子L-Trp成功地印迹到纳米TiO2中。采用1%的氨水溶液去除印迹的纳米TiO2中的模板分子L-Trp,纳米TiO2上留下与L-Trp相匹配的空穴。采用荧光分光光度法研究了具有L-Trp铸型的纳米TiO2对L-Trp和D-色氨酸(D-Trp)的分离效果。实验表明,模板分子L-Trp与钛前驱体的最佳投料摩尔比为1∶0.2,富集溶液pH值为6.0时,印迹纳米TiO2对L-Trp具有优异的选择吸附性,其分离选择系数为2.42,可实现对色氨酸对映体的识别。     

二氧化钛纳米粒子催化合成Hantzsch酯和多氢喹啉衍生物(英文)

1,4-Dihydropyridine and polyhydroquinoline derivatives have been prepared efficiently in a one-pot synthesis via Hantzsch condensation using nanosized titanium dioxide as a heterogeneous catalyst.The present methodology offers several advantages such as excellent yields,short reaction times (30-120 min),environmentally benign,and mild reaction conditions.The catalyst can be readily separated from the reaction products and recovered in excellent purity for direct reuse.     

Spectro-Optical and Photochemical Properties of ZnS Nanoparticles

The spectro-optical properties of nanoparticles of ZnS have been studied and the structure of the long wavelength edge of the absorption bands of the semiconductor has been analyzed. The influence of the synthesis conditions on the size and optical properties of the nanoparticles of ZnS formed has been investigated. It has been established that oxidative photo-corrosion of zinc sulfide colloids is accompanied by a decrease in the average size of ZnS nanoparticles and an increase in the defectiveness of their surfaces.__________Translated from Teoreticheskaya i Eksperimental’naya Khimiya, Vol. 41, No. 2, pp. 105–109, March–April, 2005.     

Bioinspired Hierarchical Nanotubular Titania Immobilized with Platinum Nanoparticles for Photocatalytic Hydrogen Production

A bioinspired nanocomposite composed of platinum nanoparticles and nanotubular titania was fabricated in which the titania matter was templated by natural cellulose substance. The composite possesses three‐ dimensional hierarchical structures, and ultrafine metallic platinum particles with sizes of ca. 2 nm were immobilized uniformly on the surfaces of the titania nanotubes. Such a nanocomposite with 1.06 wt % of platinum content shows the optimal photocatalytic hydrogen production activity from water splitting of 16.44 mmol h^?1 g^?1, and excessive loading of platinum results in poorer photocatalytic performance. The structural integrity of the nanocomposite upon cyclic water‐splitting processes results in its sufficient photocatalytic stability.     

纳米四氧化三铁表面酸碱性质研究

制备了纳米Fe3O4, 并对其进行了表征和表面酸碱行为研究. 实验结果表明, Fe3O4表面在水溶液中有非常明显的酸碱性质. 随着纳米Fe3O4加入量的增多, 溶液pH缓冲能力增强, 二者之间成正比, 据此可定量地测定H+在纳米氧化铁表面的吸附量. 运用MEDUSA和WINSGW计算软件计算了表面组分在溶液中的分布， 并讨论了表面电荷对表面组分分布的影响.     

Carbonic Anhydrase Immobilized on Encapsulated Magnetic Nanoparticles for CO2 Sequestration

Bovine carbonic anhydrase (BCA) was covalently immobilized onto OAPS (octa(aminophenyl)silsesquioxane)‐functionalized Fe₃O₄/SiO₂ nanoparticles by using glutaraldehyde as a spacer. The Fe₃O₄ nanoparticles were coated with SiO₂, onto which was grafted OAPS, and the product was characterized using SEM, TEM, XRD, IR, X‐ray photoelectron spectroscopy (XPS), and magnetometer analysis. The enzymatic activities of the free and Fe₃O₄/SiO₂/OAPS‐conjugated BCA (Fe? CA) were investigated by hydrolyzing p‐nitrophenylacetate (p‐NPA), and hydration and sequestration of CO₂ to CaCO₃. The CO₂ conversion efficiency and reusability of the Fe? CA were studied before and after washing the recovered Fe? CA by applying a magnetic field and quantifying the unreacted Ca²⁺ ions by using ion chromatography. After 30 cycles, the Fe? CA displayed strong activity, and the CO₂ capture efficiency was 26‐fold higher than that of the free enzyme. Storage stability studies suggested that Fe? CA retained nearly 82 % of its activity after 30 days. Nucleation of the precipitated CaCO₃ was monitored by using polarized light microscopy, which revealed the formation of two phases, calcite and valerite, at pH 10 upon addition of serine. The magnetic nanobiocatalyst was shown to be an excellent reusable catalyst for the sequestration of CO_2.     

Spectroscopic Investigations of Porphyrin-TiO2 Nanoparticles Complexes

This study presents the spectral characterization of TiO₂ nanoparticles (NPs) functionalized with three porphyrin derivatives: 5,10,15,20-(Tetra-4-aminophenyl) porphyrin (TAPP), 5,10,15,20-(Tetra-4-methoxyphenyl) porphyrin (TMPP), and 5,10,15,20-(Tetra-4-carboxyphenyl) porphyrin (TCPP). UV-Vis absorption and Fourier transform infrared spectroscopy–attenuated total reflection (FTIR-ATR) spectroscopic studies of these porphyrins and their complexes with TiO₂ NPs were performed. In addition, the efficiency of singlet oxygen generation, the key species in photodynamic therapy, was investigated. UV-Vis absorption spectra of the NPs complexes showed the characteristic bands of porphyrins. These allowed us to determine the loaded porphyrins on TiO₂ NPs functionalized with porphyrins. FTIR-ATR revealed the formation of porphyrin-TiO₂ complexes, suggesting that porphyrin adsorption on TiO₂ may involve the pyrroles in the porphyrin ring, or the radicals of the porphyrin derivative. The quantum yield for singlet oxygen generation by the studied porphyrin complexes with TiO₂ was higher compared to bare porphyrins for TAPP and TMPP, while for the TCPP-TiO₂ NPs complex, a decrease was observed, but still maintained a good efficiency. The TiO₂ NPs conjugates can be promising candidates to be tested in photodynamic therapy in vitro assays.     

NaKCoFe普鲁士蓝类配合物纳米颗粒的磁性研究

在2-乙基己基琥珀酸酯磺酸钠(AOT)/异辛烷/水微乳液体系内,通过改变w值(水与AOT的物质的量之比)和反应物浓度比例得到了5nm球形至80nm立方状的NaKCoFe普鲁士蓝类配合物。发现w值和反应物浓度比不仅影响产物的形貌,而且影响配合物的结构。用UV、XRD、EDS、ICP、IR和超导量子干涉仪(SQUID)等对产品进行了结构和磁学性能的表征,发现影响产物磁性的主要因素是碱金属的含量。     

Tapioca Biofilm Containing Nitrogen‐doped Titanium Dioxide Nanoparticles for Electrochemical Detection of 17‐β Estradiol

A novel sensor architecture based on thin film of tapioca decorated within nitrogen‐doped titanium dioxide (N‐TiO₂) nanoparticles is reported. The nanostructures were characterized by scanning electron microscope, transmission electron microscope, X‐rays diffraction and voltammetric techniques. The proposed electrode was used for detection of low concentrations of 17‐β estradiol in without purification step, which was investigated by using linear sweep adsorptive stripping voltammetry. Under optimal conditions, the analytical curve was linear over a 17β‐estradiol concentration range of 9.9×10⁻⁶ to 1.4×10⁻⁵ mol L⁻¹, with a detection limit of 1.7×10⁻⁷ mol L⁻¹. The tapioca and N‐TiO₂ nanoparticles homogeneous film was applied for detection of 17‐β‐estradiol in tap water and synthetic urine samples, which presented satisfactory results.     

A Novel Method for the Background Signal Correction in SP-ICP-MS Analysis of the Sizes of Titanium Dioxide Nanoparticles in Cosmetic Samples

We discuss the features involved in determining the titanium dioxide nanoparticle (TiO₂NP) sizes in cosmetic samples via single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) in the millisecond-time resolution mode, and methods for considering the background signal. In the SP-ICP-MS determination of TiO₂NPs in cosmetics, the background signal was recorded in each dwell time interval due to the signal of the Ti dissolved form in deionized water, and the background signal of the cosmetic matrix was compensated by dilution. A correction procedure for the frequency and intensity of the background signal is proposed, which differs from the known procedures due to its correction by the standard deviation above the background signal. Background signals were removed from the sample signal distribution using the deionized water signal distribution. Data processing was carried out using Microsoft Office Excel and SPCal software. The distributions of NP signals in cosmetic product samples were studied in the dwell time range of 4–20 ms. The limit of detection of the NP size (LOD_size) with the proposed background signal correction procedure was 71 nm. For the studied samples, the LOD_size did not depend on the threshold of the background signal and was determined by the sensitivity of the mass spectrometer.