Switchable photoluminescence of CdTe nanocrystals by temperature-responsive microgels

In the present study, we report a method for preparing a fluorescent thermosensitive hybrid material based on monodisperse, thermosensitive poly( N-isopropyl acrylamide) (PNIPAM) microgels covered with CdTe nanocrystals of 3.2 nm diameter. The CdTe nanocrystals were covalently immobilized on the surface of PNIPAM microgels. The chemical environment around the CdTe nanocrystals was modified by changing the temperature and inducing the microgel volume-phase transition. This change provoked a steep variation in the nanocrystal photoluminescence (PL) intensity in such a way that when the temperature was under the low critical solution temperature (LCST) of the polymer (36 degrees C) the PL of the nanocrystals was strongly quenched, whereas above the LCST the PL intensity was restored.     

Prototype of immunochromatographic assay strips using colloidal CdTe nanocrystals as biological luminescent label

Colloidal semiconductor nanocrystals have attracted considerable attention as a novel biological luminescent label. The bioinorganic conjugates of luminescent CdTe nanocrystals and protein, including CdTe/BSA (bovine serum albumin) and CdTe/MAB (mouse monoclonal antibody against hepatities B surface antigen), were formed via electrostatic/coordination self-assembly. Pure CdTe nanocrystals, CdTe/BSA and CdTe/MAB were used in the immunochromatographic assay experiments, respectively. And the results indicated that CdTe nanocrystals could be used and developed as a novel label with good stability, high sensitivity and facile determination of several analytes in immunochromatographic assay strips.     

CdTe纳米晶与蛋白相互作用研究

当半导体纳米晶的直径小于其电子的玻尔直径时 ,半导体纳米晶对电子具有量子限域效应 ,其发光波长与纳米晶的尺寸相关 .与有机荧光分子相比 ,荧光半导体纳米晶具有以下优点 :(1 )其激发谱在吸收阈值以上几乎是连续的 ,利于多波长激发 ;(2 )高强荧光发射 ,谱峰窄 ,峰形对称 ;(3 )发射波长随着粒径的增大而有规律地红移 ,只需改变粒径即可获得多色发光 ;(4)纳米晶的发光稳定性好 ,不易被光分解和漂白 .因此 ,半导体纳米晶作为新一代荧光生物标记物已有研究[1～ 6] .荧光生物标记要求使用水溶性的纳米粒子 ,水相合成半导体纳米晶操作简便、重复…     

Synthesis and Surface Modification of CdTe Nanocrystals

IntroductionThe study on semiconductor nanocrystals has re-ceived considerable attention in the past decades[1—4].Because of the quantum confinement effect, smallnanocrystals show very special physical and chemicalproperties when their sizes are close to…     

Hydrogel microparticles as dynamically tunable microlenses

Tunable micro-optical elements were prepared by aqueous free-radical polymerization and electrostatic self-assembly techniques. Stimuli-responsive poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-AAc) microgels were used as lenses to generate dynamically tunable optical elements. By using optical microscopy to investigate the micrometer-scale dynamics of the self-assembled microlenses, we demonstrate focal length tuning through modulation of the solution pH and/or temperature.     

基于互穿网络结构的pH/温度双重刺激响应性微凝胶的研究

室温下采用氧化-还原引发体系,以低交联密度的聚(N-异丙基丙烯酰胺)(PNIPAM)微凝胶为种子,通过种子乳液聚合法合成由PNIPAM和聚丙烯酸(PAA)形成的具有互穿聚合物网络结构的微凝胶.傅立叶变换红外光谱分析结果表明微凝胶由PNIPAM和PAA两种聚合物组成,透射电镜表征结果证实微凝胶中PNIPAM和PAA两种聚合物形成了互穿网络结构.用动态激光光散射测试不同温度或pH值水介质中微凝胶的粒径,结果发现微凝胶具有良好的pH/温度双重刺激响应性.在水介质pH值大于5.5的情况下,PAA组分对微凝胶的体积相转变温度没有影响;而在水介质pH值为4.0的情况下,由于PAA与PNIPAM之间的氢键作用,微凝胶的体积相转变温度稍微降低.微凝胶中PAA组分含量越高,其pH刺激响应性越显著.     

Synthesis and aqueous solution properties of sterically stabilized pH-responsive polyampholyte microgels

Emulsion copolymerization of poly(methacrylic acid) and poly(2-(diethylamino)ethyl methacrylate) (PMAA/PDEA) yielded pH-responsive polyampholyte microgels of 200-300 nm in diameter. These microgels showed enhanced hydrophilic behavior in aqueous medium at low and high pH, but formed large aggregates of approximately 2500 nm at intermediate pH. To achieve colloidal stability at intermediate pH, a second batch of microgels of identical monomer composition were synthesized, where monomethoxy-capped poly(ethylene glycol)methacrylate (PEGMA) was grafted onto the surface of these particles. Dynamic light-scattering measurements showed that the hydrodynamic radius, Rh, of sterically stabilized microgels was approximately 100 nm at intermediate pH and increased to 120 and 200 nm at pH 2 and 10, respectively. Between pH 4 and 6, these microgels possessed mobility close to zero and a negative second virial coefficient, A2, due to overall charge neutralization near the isoelectric pH. From the Rh, mobility, and A2, cross-linked MAA-DEA microgels with and without PEGMA retained their polyampholytic properties in solution. By varying the composition of MAA and DEA in the microgel, it is possible to vary the isoelectric point of the colloidal particles. These new microgels are being explored for use in the delivery of DNA and proteins.     

Synthesis,Characterization, and Silver Nanoparticles Fabrication in N-isopropylacrylamide-Based Polymer Microgels for Rapid Degradation of p-Nitrophenol

Multiresponsive poly(N-isopropylacrylamide-co-methacrylic acid) microgels were synthesized by precipitation polymerization in aqueous medium. Then silver-poly(N-isopropylacrylamide-co-methacrylic acid) hybrid microgels were prepared by in-situ reduction of silver ions. Formation of microgels was confirmed by Fourier transform infrared spectroscopic analysis. pH and temperature sensitivity of microgel was studied by dynamic light scattering. Hydrodynamic radius of microgels decreases with increase in temperature at pH 8.20 and show volume phase transition temperature around 45°C. At pH 2.65, hydrodynamic radius decreases with increase in temperatures upto 35°C but further increase in temperature causes aggregation and microgel becomes unstable due to increase of hydrophobicity. With increase in pH of medium, the hydrodynamic radius of microgels increases sigmoidally. Formation of silver nanoparticles inside microgel and pH dependence of surface plasmon resonance wavelength of the hybrid microgels were investigated by ultraviolet-visible spectroscopy. The value of surface plasmon resonance band and absorbance associated with surface plasmon resonance band increases with increases in pH of the medium. The apparent rate constant of reduction of p-nitrophenol was found to be linearly dependent on volume of hybrid microgels used as catalyst. The system has a potential to be used as effective catalyst for rapid degradation of industrial pollutant.     

Microgels containing methacrylic acid: effects of composition on pH-triggered swelling and gelation behaviours

pH-responsive microgels are cross-linked polymer colloids that swell when the pH approaches the pK _a of the particles. In this work, we present a comprehensive investigation of pH-triggered particle swelling and gel formation for a range of microgels containing methacrylic acid (MAA). The microgels investigated have the general composition poly(A/MAA/X), where A and X are the primary co-monomer and cross-linking monomer, respectively. The primary co-monomers were methyl methacrylate (MMA), ethyl acrylate (EA) or butyl methacrylate. The cross-linking monomers were either butanediol diacrylate (BDDA) or ethyleneglycol dimethacrylate (EGDMA). The microgels were studied using scanning electron microscopy, photon correlation spectroscopy (PCS) and dynamic rheology measurements. Gel phase diagrams were also constructed. The particles swelled significantly at pH values greater than approximately 6.0. It was shown that poly(EA/MAA/X) microgels swelled more strongly than poly(MMA/MAA/X) microgels. Furthermore, greater swelling occurred for particles prepared using EGDMA than BDDA. Concentrated dispersions of all the microgels studied exhibited pH-triggered gel formation. It was found that the fluid-to-gel transitions for the majority of the six microgel dispersions investigated could be explained using PCS data. In those cases, gelation was attributed to a colloidal glass transition. Interestingly, the microgels that were considered to have the highest hydrophobic content gelation occurred under conditions where little particle swelling was evident from PCS. The data presented show that gelled poly(EA/MAA/BDDA) and poly(MMA/MAA/EGDMA) microgel dispersions have the strongest elasticities at pH = 7.     

Preparation and characterization of novel cationic pH-responsive poly(N,N'-dimethylamino ethyl methacrylate) microgels

Novel monodisperse cationic pH-responsive microgels were successfully prepared by dispersion polymerization in ethanol/water mixture using N,N'-dimethylamino ethyl methacrylate (DMAEMA) as the monomer, poly(vinyl pyrrolidone) (PVP) as the steric stabilizer and N,N'-methylenebisacrylamide (MBA) as the cross-linker. The effects of various polymerization parameters, such as medium polarity, concentration of cross-linker, concentration of monomer, and concentration and molecular weight of stabilizer on the final diameter and monodispersity of poly(N,N'-dimethylamino ethyl methacrylate) (PDMAEMA) microgels were systematically studied. The pH-responsive characteristics of PDMAEMA microgels were also investigated. The experimental results showed that these microgels exhibited excellent pH-responsivity and significantly swelled at low pH values. The maximum ratio of volume change of the prepared microgels in response to pH variation was more than 11 times. It was found that the prepared microgels completely aggregated at the isoelectric point (IEP) around pH 6. On the other hand, the microgels were stable in aqueous solution at both low and high pH values. The results can be used for effectively controlled separation of particles.     

Fabrication of free-standing multilayer films by using pH-responsive microgels as sacrificial layers

A facile way to prepare free-standing polyelectrolyte multilayer films of poly(sodium 4-styrenesulfonate)(PSS)/poly(diallyldimethylammonium)(PDDA) was developed by applying a new pH-dependent sacrificial system based on cross-linked poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) microgels. The tertiary amine groups of PDMAEMA microgels can be protonated in acidic environment, and the protonated microgels were deposited by layer-by-layer (LbL) technique with PSS. PSS/PDDA multilayer films were constructed on the top of the PSS/microgels sacrificial layers. The LbL assembly process was investigated by UV–vis spectroscopy. Further study shows that the free-standing PSS/PDDA multilayer films can be obtained within 3 min by treating the as-prepared films in alkali aqueous solution with a pH of 12.0. The pH-triggered exfoliation of PSS/PDDA multilayer films provides a simple and facile way to prepare LbL assembled free-standing multilayer films.     

Luminescence quenching in self-assembled adducts of [Ru(dpp)3]2+ complexes and CdTe nanocrystals

We have investigated chloroform solutions containing tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) and CdTe nanocrystal quantum dots (5.6 nm diameter). The electronic levels of these two components are such that the Ru complex can act as an energy donor towards the quantum dot, which can thus behave as an energy acceptor. Steady-state and time-resolved spectroscopic experiments indicate that the Ru complexes and the CdTe nanocrystals self-assemble to give stable 1?:?1 adducts, in which the luminescence of the former units is strongly quenched. Such a quenching can be ascribed to either energy transfer to the CdTe quantum dot, or to electron transfer from the CdTe valence band to the excited Ru complex. However, no supporting evidence for the occurrence of photoinduced energy transfer in the adduct could be found. The CdTe luminescence is also slightly quenched in the presence of the ruthenium complex. The strong association of the metal complexes with the nanocrystals suggests that self-assembly strategies may be effectively employed to achieve surface functionalization of semiconductor quantum dots with molecular units.     

Interaction of CdTe nanocrystals with thiol-containing amino acids at different pH: a fluorimetric study

3-Mercaptopropionic acid (MPA)-capped CdTe nanocrystals (NCs) were synthesized in aqueous medium, and their interaction with cysteine (Cys) and homocysteine (Hcy) was studied by steady-state and time-resolved fluorescence spectra at different pH. At 6.4?<?pH?<?8.0, the fluorescence of CdTe NCs can be effectively enhanced by Cys and Hcy. While pH?>?9.6, only Cys quenches the fluorescence of the CdTe NCs, no fluorescence changes are observed for Hcy. Mechanism study shows that these pH manipulating fluorescence responses can be attributed to the following two reasons: first, both the thiol–thiolate equilibrium of Cys (Hcy) and the number of undercoordinated NCs surface sites capped with dual coordinated ligands are strong pH-dependent; second, different thiol-containing amino acids, with different redox energy level, can lead to distinguishable fluorescence responses of NCs. Based on these unique fluorescence responses, the possibilities of developing a sensitive detecting technique for Cys/Hcy and Cys through pH modulation can be explored.     

Synthesis of Positively Charged Luminescent CdTe Nanocrystals in Aqueous Solution

Highly luminescent positively charged CdTe nanocrystals were prepared from a facile and reproducible approach by the reaction of Cd²⁺ and HTe^? in the presence of mercaptoethylamine. The influence of various experimental variables, including pH value, growth temperature, Te-to-Cd ratio, as well as Cd-to-ligand ratio, on the growth rate and optical properties of CdTe nanocrystals have been systematically investigated. Experimental results indicate that the pH value and Te-to-Cd molar ratio play the crucial role in determining luminescent properties of the obtained CdTe nanocrystals. The mechanism for the resulting high-quality optical properties of the resulting CdTe nanocrystals was also elucidated.     

利用水相合成的CdTe纳米晶构建超晶格结构研究--纳米晶聚集体的调控

用巯基丙酸作稳定剂,在水溶液中制备了CdTe纳米晶.通过加入Cd2+、聚丙烯酸(PAA)以及长期放置分别得到了CdTe纳米晶的聚集体,改变Cd2+浓度或PAA加入量可以调控聚集体的尺寸.过量的Cd2+加速了聚集体的形成,通过与纳米晶表面羧酸根的静电相互作用,Cd2+成为连接不同CdTe纳米晶的“桥梁”.PAA链上大量的羧基与CdTe纳米晶有较强的配位相互作用,可以诱导纳米晶聚集.新制CdTe纳米晶在长期放置时,表面的羧基与Cd2+的相互作用导致纳米晶逐渐聚集.在聚集过程中纳米晶表面结构得到改善,并引起荧光增强.这些结果表明通过控制各种聚集条件,可以得到不同尺寸的聚集体.     

Amphiphilic ABC triblock copolymer-assisted synthesis of core/shell structured CdTe nanowires

A new type of amphiphilic ABC triblock copolymer, poly(acrylic acid)(33)-poly(styrene)(47)-poly(ethylene oxide)(113) (PAA(33)-PS(47)-PEO(113)), was designed to assist the synthesis of core/shell structured CdTe nanowires via a one-step synthetic route. The PAA block was adopted to capture cadmium ions as the precursor of CdTe. Due to the bivalent coordination of Cd(2+), the copolymer in dioxane/H(2)O formed micelles with Cd(2+)-polychelate cores. Then CdTe nanocrystals were obtained within the micelles after introduction of NaHTe into the micelle solution. Transmission electron microscopy experiments revealed that the CdTe nanocrystals obtained simultaneously formed "pearl-necklace" aggregates in solution possibly driven by dipole interactions between neighboring particles, and then single crystalline CdTe nanowires upon reflux. Accompanying this morphology change, a phase transition from cubic zinc blende to wurtzite structure was observed by selected-area electron diffraction. The aggregation of the PS block in dioxane with a certain amount of H(2)O enabled the PS blocks to form a densely packed shell on the CdTe nanowires whose typical size is 700-800 nm in length and 15-20 nm in width. The third block of PEO was employed to render the finally formed CdTe nanowires dispersibility.     

Synthesis and characterization of novel pH-responsive microgels based on tertiary amine methacrylates

Emulsion polymerization of 2-(diethylamino)ethyl methacrylate (DEA) in the presence of a bifunctional cross-linker at pH 8-9 afforded novel pH-responsive microgels of 250-700 nm diameter. Both batch and semicontinuous syntheses were explored using thermal and redox initiators. Various strategies were evaluated for achieving colloidal stability, including charge stabilization, surfactant stabilization, and steric stabilization. The latter proved to be the most convenient and effective, and three types of well-defined reactive macromonomers were examined, namely, monomethoxy-capped poly(ethylene glycol) methacrylate (PEGMA), styrene-capped poly[2-(dimethylamino)ethyl methacrylate] (PDMA50-St), and partially quaternized styrene-capped poly[2-(dimethylamino)ethyl methacrylate] (10qPDMA50-St). The resulting microgels were pH-responsive, as expected. Dynamic light scattering and 1H NMR studies confirmed that reversible swelling occurred at low pH due to protonation of the tertiary amine groups on the DEA residues. The critical pH for this latex-to-microgel transition was around pH 6.5-7.0, which corresponds approximately to the known pKa of 7.0-7.3 for linear PDEA homopolymer. The microgel particles were further characterized by electron microscopy and aqueous electrophoresis studies. Their swelling and deswelling kinetics were investigated by turbidimetry. The PDEA-based microgels were compared to poly[2-(diisopropylamino)ethyl methacrylate] (PDPA) microgels prepared with identical macromonomer stabilizers. These PDPA-based microgels had a lower critical swelling pH of around pH 5.0-5.5, which correlates with the lower pKa of PDPA homopolymer. In addition, the kinetics of swelling for the PDPA microgels was somewhat slower than that observed for PDEA microgels; presumably this is related to the greater hydrophobic character of the former particles.     

Reversible loading and unloading of nanoparticles in "exponentially" growing polyelectrolyte LBL films

The exponentially growing layer-by-layer (LBL) films made from poly(diallyldimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA) were used to load and unload the CdTe nanoparticles (NPs). The reversible loading of NPs were investigated through UV-vis studies and further confirmed by confocal microscopy. In addition the LBL films were also compared for the release kinetics for pH 9 and 7 and films capped with (PDDA-PSS)10 layers. The amount of released particles at pH 9 was found to be at least 2 orders of magnitude higher than those at pH 7 and with (PDDA-PSS)10 capped layers after 25 h. This variation in film response for CdTe-particle release presents a route for studies in which highly swollen exponentially growing LBL films can be loaded with functionalized NPs for biological applications and explored as carriers to hold the NPs inside the films for self-assembly.     

Metal nanocrystals incorporated within pH-responsive microgel particles

Cross-linked sterically stabilized latexes of approximately 250 nm diameter were synthesized by emulsion polymerization of 2-(diethylamino)ethyl methacrylate using a bifunctional oligo(propylene oxide)-based diacrylate cross-linker and a poly(ethylene oxide)-based macromonomer as the stabilizer at pH 9. These particles exhibit reversible swelling properties in water by adjusting the solution pH. At low pH, they exist as swollen microgels as a result of protonation of the tertiary amine units. Deswelling occurs above pH 7 [the effective pK(a) of poly(2-(diethylamino)ethyl methacrylate)], leading to the formation of the original compact latex particles. The swollen microgels can be used as nanoreactors: efficient impregnation with Pt nanoparticles can be achieved by incorporating precursor platinum compounds, followed by metal reduction. Dynamic light scattering was used to compare two methods of Pt nanoparticle impregnation with respect to the size and stability of the final Pt-loaded microgel particles. In the first method, the H2PtCl6 precursor was added to hydrophobic latex particles at high pH, followed by metal reduction. In the second method, H2PtCl6 was added to hydrophilic swollen microgel particles at low pH, and then this metal salt was reduced in situ using NaBH4 and the pH was raised by the addition of base. Both the Pt salt-loaded (metalated) microgels and the final Pt nanoparticle-loaded microgels had well-defined structures that were independent of the synthesis route. Polymer-metal interactions were investigated by UV-visible absorption spectroscopy, which confirmed that the Pt salt was completely reduced to zero-valent Pt. Transmission electron microscopy and X-ray diffraction studies verified the formation of nanometer-sized Pt nanoparticles within these microgels, which can be used as recoverable colloidal catalyst supports for various organic reactions.     

水相中CdTe纳米晶的制备及其光学性质

用不同稳定剂(巯基乙酸(TGA)、巯基丙酸(MPA)、L-半胱氨酸(L-Cys)、3-巯基-1,2-丙二醇(TG))在水相中制备了CdTe纳米晶, 并用透射电子显微镜(TEM)、X射线光电子能谱(XPS)和X射线粉末衍射(XRD)等技术对其进行了表征. 研究了不同水相合成条件对CdTe纳米晶光学性质的影响, 结果表明, n(Cd):n(Te)、溶液pH值、回流时间以及稳定剂的性质, 对纳米晶的光学性质具有显著影响. 制得的CdTe纳米晶发射峰窄且对称(半高全宽达38 nm), 用不同稳定剂制备的纳米晶发光量子效率有所不同, 用不同的激发波长对纳米晶进行激发时, 发射峰并未表现出明显的移动.