Metal ion detection with oligo(ethylene glycol) monolayer-modified gold nanoparticles

Two colorimetric sensors of gold nanoparticles (AuNPs) modified with different oligo(ethylene glycol)-containing organic molecules have been developed to detect metal ions by ultraviolet-visible (UV-vis) extinction spectroscopy. These sensors display different responses to some metal ions. One exhibits high selectivity for Hg2+ over a variety of competitive metal ions and the other one can respond to a multitude of metal ions. These differences might result from the different functionalized end groups of the modified molecules. Coordination effect, pH response, and ionic strength were investigated to understand the mechanism of the responses to metal ions. The results suggested that the colorimetric responses were mainly induced by the coordination effect of the modified organic molecules and the removing of the modified organic molecules caused by metal ions.     

端糖基化聚(N-异丙基丙烯酰胺)的合成及其温敏性表征

制备了两种糖基引发剂(AcCDBr和AcG-lABr),以CuBr/三-(N,N-二甲基氨基乙基)胺(Me6TREN)为催化体系,应用原子转移自由基聚合方法,在60℃下引发N-异丙基丙烯酰胺聚合,脱去乙酰基保护后得到末端分别带有β-环糊精和2-氨基葡萄糖基团的线形聚(N-异丙基丙烯酰胺)(CD-PAM和GlA-PAM)。对产物的结构进行了表征,凝胶渗透色谱(GPC)测得聚合物分子量分布较窄(PDI=1.12～1.20)。采用紫外-可见吸收光谱仪(UV-Vis)和示差扫描量热仪(DSC)对聚合物水溶液的相转变行为进行了测试,结果表明末端引入糖类结构使得PNIPAM的最低临界溶解温度(LCST)升高,并随着分子量的增大而降低,而且相同聚合度的GlA-PAM的LCST比CD-PAM的高3.7℃左右。     

Preparation of highly stable oligo(ethylene glycol) derivatives-functionalized gold nanoparticles and their application in LSPR-based detection of PSA/ACT complex

A sandwich immunoassay for PSA/ACT complex detection based on gold nanoparticle aggregation using two probes was developed. The functionalized colloidal gold nanoparticles (AuNPs) showed highly stable not only in the presence of high ionic strength but also in a wide pH range. The functionalized AuNPs were tagged with PSA/ACT complex monoclonal antibody and goat PSA polyclonal antibody and served as the probes to induce aggregation of the colloidal particles. As a result, PSA/ACT complex was detected at concentrations as low as 1 ng/ml. This is the first time that a new aggregation sandwich-immunoassay technique using two gold probes has been used, and the results are generally applicable to other LSPR-based immunoassays.     

Relationship between structure and electroluminescence of oligo(p-phenylenevinylene)s

The preparation of LEDs with poly( p-phenylenevinylene) (PPV) as emitting material is well established. However, due to the presence of a distribution of conjugated chain lengths in the polymer, systematic investigations of the electroluminescence with polymeric materials are difficult, as far as the optical emission is concerned. We are studying the relationship between structural variation of substituted oligo(p-phenylenevinylene)s and their electroluminescent behaviour using a series of distyrylbenzenes with a variety of substituents in order to investigate their influence on the electroluminescence (EL). Furthermore, we synthesized a homologous series of monodisperse oligo(2,5-dipropoxy-1,4-phenylenevinylene)s with up to 11 repeating units. This series covers the spectrum from monomer to polymer. The influence on the EL can be investigated by preparing single layer LEDs using vapor deposition or spincoating of the oligomers in a polystyrene (PS) matrix. The comparison of photoluminescence (PL)- and EL-spectra shows that the photophysical properties of the oligomers are strongly altered by aggregation phenomena.     

Enhanced relative biological effectiveness of proton radiotherapy in tumor cells with internalized gold nanoparticles

The development and use of sensitizing agents to improve the effectiveness of radiotherapy have long been sought to improve our ability to treat cancer. In this letter, we have studied the relative biological effectiveness of proton beam radiotherapy on prostate tumor cells with and without internalized gold nanoparticles. The effectiveness of proton radiotherapy for the killing of prostate tumor cells was increased by approximately 15%-20% for those cells containing internalized gold nanoparticles.     

Enhanced dispersity of gold nanoparticles modified by omega-carboxyl alkanethiols under the impact of poly(ethylene glycol)s

The physisorption of nonionic surfactant poly(ethylene glycol) (PEG) series and the chemisorption of carboxyl-terminated alkanethiols on surface of gold nanoparticles (AuNPs) were investigated. The physical adsorption of oligo(ethylene glycol) moieties introduced a tiny red shift of surface plasmon resonance (SPR) of AuNPs, indicating the formation of a protective layer of PEG molecules around gold surface. The subsequent chemisorption of omega-carboxyl alkanethiols was performed under the protection of PEG molecules, and the aggregation of metal nanoparticles did not appear by TEM observation. The successful adsorption of omega-carboxyl alkanethiol on gold surface was demonstrated according to FT-IR spectrum and the prior adsorbed PEG molecules could be washed out by centrifugation. Furthermore, the presence of nonionic surfactant even displayed a protective role in centrifugal process. The dispersity of modified AuNPs with peripheral functional groups was enhanced under the protection of PEG molecules as an important advantage in further biological applications.     

Poly(acrylic acid)-stabilized colloidal gold nanoparticles: synthesis and properties

Combining the intriguing optical properties of gold nanoparticles with the inherent physical and dynamic properties of polymers can give rise to interesting hybrid nanomaterials. In this study, we report the synthesis of poly(acrylic acid) (PAA)-capped gold nanoparticles. The polyelectrolyte-wrapped gold nanoparticles were fully characterized and studied via a combination of techniques, i.e. UV-vis and infrared spectroscopy, dark field optical microscopy, SEM imaging, dynamic light scattering and zeta potential measurements. Although PAA-capped nanoparticles have been previously reported, this study revealed some interesting aspects of the colloidal stability and morphological change of the polymer coating on the nanoparticle surface in an electrolytic environment, at various pH values and at different temperatures.     

Concentrated colloids of silica-encapsulated gold nanoparticles: colloidal stability, cytotoxicity, and X-ray absorption

As an effort to develop a new, effective, nontoxic X-ray contrast agent, the concentrated colloids of silica-encapsulated gold nanoparticles (Au@SiO2 NPs) were fabricated and their colloidal stability, cytotoxicity, and X-ray absorption were investigated. The concentrated colloidal NPs were manufactured by forming a 4 nm-thick silica shell on the surface of each Au NP with 15 nm diameter, followed by enrichment to [Au] = 100 mM. They were very stable in water: the NPs were well separated each other without forming agglomerates and their optical property was very similar to that before enrichment. The colloidal stability of the NPs in biological environment was strongly dependent on their previous morphology in water. The NPs with minor shell damage were stable in phosphate buffered saline (PBS) solution: both in water and in PBS solution, they showed very similar morphology and optical property. However, the NPs with profound shell damage formed big agglomerates in PBS solution, resulting in the red-shift and broadening of the Au surface plasmon resonance peak. Cell viability and proliferation assessments revealed the biocompatibility of the Au@SiO2 NPs: no apparent cytotoxicity was observed even at 100 ppm NPs. The concentrated colloidal NPs showed very strong X-ray absorption. Their relative X-ray transmittance to water was comparable to that of a commercial agent. Considering these, the concentrated colloids of the Au@SiO2 NPs are suitable for an X-ray contrast agent.     

Amorphous phase-segregated copoly(ether)esterurethane thermoset networks with oligo(propylene glycol) and oligo[(rac-lactide)-co-glycolide] segments: synthesis and characterization

Completely amorphous copoly(ether)ester networks based on oligo(propylene glycol) and oligo[(rac-dilactide)-co-glycolide] segments were synthesized by crosslinking star-shaped hydroxyl-telechelic cooligomers using an aliphatic low-molecular weight diisocyanate. Two different network architectures were applied exhibiting differences in the phase-separation behavior. For networks from oligo(propylene glycol)-block-oligo[(rac-lactide)-co-glycolide] triols (G³OPG-bl-OLG) only one glass transition was obtained. However, networks from a mixture of oligo(propylene glycol) triols (G³OPG) and oligo[(rac-lactide)-co-glycolide] tetrols (P⁴OLG) with a ratio of components in a certain range show two glass transition temperatures (T _g) being attributed to two segregated amorphous phases. In this way a wide spectrum of mechanical properties can be realized and adjusted to the requirements of a specific application.     

A review of the biological synthesis of gold nanoparticles using fruit extracts: scientific potential and application

Gold nanoparticles (GNPs) are well-known nanomaterials that can be used for multiple biomedical applications. There are various methods for synthesis of GNPs using microorganisms and plants, particularly through the use of fruit extracts. Their use is due to the fact that fruit extracts are the natural concentrate of substances that possesses therapeutic properties. In this review, we aim to compare the recent studies concerning the methods for synthesis of GNPs from fruit extracts, the methods used to characterize the properties of GNPs and capping biomaterial and the potential applications of GNPs. The most frequently used methods to characterize GNPs and capping biomaterial are UV–visible spectroscopy, transmission or scanning electron microscopy, dynamic light scattering and Fourier transformation infrared spectroscopy techniques. Because of GNPs’ optoelectronic properties, biocompatibility, stability and oxidation resistance, they can be used in areas such as electronics, chemical and biological sensing, tumour imaging, drug delivery and phototherapy.     

Reducing HAuCl(4) by the C(60) dianion: C(60)-directed self-assembly of gold nanoparticles into novel fullerene bound gold nanoassemblies

The C(60) dianion is used to reduce tetrachloroauric acid (HAuCl(4)) for the first time; three-dimensional C(60) bound gold (Au-C(60)) nanoclusters are obtained from C(60)-directed self-assembly of gold nanoparticles due to the strong affinities of Au-C(60) and C(60)-C(60). The?process was monitored in situ by UV-vis-NIR spectroscopy. The resulting Au-C(60) nanoclusters were characterized using transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive spectroscopy (EDS), x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and FT-IR and Raman spectroscopies. TEM demonstrates the formation of 3D nanonetwork aggregates, which are composed of discrete gold nanocores covered with a C(60) monolayer. The SAED and XRD patterns indicate that the gold nanocores inside the capped C(60) molecules belong to the face-centred cubic crystal structure, while the C(60) molecules are amorphous. The EDS and XPS measurements validate that the Au-C(60) nanoclusters contain only Au and C elements and Au(3+) is reduced to Au(0). FT-IR spectroscopy shows the chemiadsorption of C(60) to the gold nanocores, while Raman spectroscopy demonstrates the electron transfer from the gold nanocores to the chemiadsorbed C(60) molecules. Au-C(60) nanoclusters embedded in tetraoctyl-n-ammonium bromide (TOAB) on glassy carbon electrodes (GCEs) have been fabricated and have shown stable and well-defined electrochemical responses in aqueous solution.     

Selective and sensitive fluorescent sensors for metal ions based on manipulation of side-chain compositions of poly(p-phenyleneethynylene)s

The syntheses and metal-responsive properties of poly(p-phenyleenethynylene)s with grafted new pseudo-crown-ether groups are reported. These polymers exhibit high sensitivities to alkali ions because of their collective optical properties, which are very sensitive to ion-induced conformational changes. The quenching of polymer fluorescence caused by the conformational changes is proportional to the ion concentration. The selectivity of the sensing materials toward Li(+) ions is significantly enhanced by controlling the size of the binding site via manipulation of the polymer side-chain compositions. The polymers are very stable for their six-month solid-state storage at room temperature.     

Limitations arising from two-photon absorption of solvent in pulsed-laser thermal lens detection: determination of the two-photon absorption coefficient of ethanol at 266 nm

Two-photon absorption of the solvent under pulsed-laser excitation at 266 nm produces a high background thermal lens signal interfering with the analyte signal. Discrimination of both solvent and analyte signals along with calibration of the photothermal response has allowed the determination of the two-photon absorption coefficient of ethanol. The obtained value, 3.0x10(-10) cm W-1, is close to the literature values obtained from transmittance measurements using picosecond or femtosecond laser pulses.     

Low voltage flexible nonvolatile memory with gold nanoparticles embedded in poly(methyl methacrylate)

We demonstrate air-stable low voltage flexible nonvolatile memory transistors by embedding gold nanoparticles (Au NPs) in poly(methyl methacrylate) (PMMA) as the charge storage element. The solution processability of the nanocomposite is suitable for low-cost large area processing on flexible substrates. The memory transistor exhibits a memory window of 2.1?V, long retention time (?>?10(5)?s) with low operating voltage (≤5?V). The memory behavior has been tuned via varying the composition of the fillers (Au NPs), which offers relatively easy processability for different flexible electronics applications. The electrical properties of the memory devices are found to be stable under bending. These findings will be of value for low cost and low voltage advanced flexible electronics.     

One-pot sonochemical synthesis of dendron-stabilized gold nanoparticles as promising nano-hybrid with potential impact in biological application

Dihydroxy fatty acid-based (DF) dendron-stabilized gold nanoparticles (AuNps) were synthesized without adding any external reducing or stabilizing agent. Each DHA base dendron (G1, G2, or G3) possesses a single thiol at the focal point and free -OH groups at the other terminal and as a result can be used to reduce AuCl₄⁻ to Au⁰ and stabilize the nascent AuNps by the thiol group. The size and distribution of the AuNp produced can also be correlated with the rate of Au (III) reduction. TEM images vividly demonstrate the specific morphology of gold nanoparticles with different sizes and shapes obtained by using different generations of DF dendrons.     

Surface plasmon resonance scattering and absorption of anti-EGFR antibody conjugated gold nanoparticles in cancer diagnostics: applications in oral cancer

Gold nanoparticles with unique optical properties may be useful as biosensors in living whole cells. Using a simple and inexpensive technique, we recorded surface plasmon resonance (SPR) scattering images and SPR absorption spectra from both colloidal gold nanoparticles and from gold nanoparticles conjugated to monoclonal anti-epidermal growth factor receptor (anti-EGFR) antibodies after incubation in cell cultures with a nonmalignant epithelial cell line (HaCaT) and two malignant oral epithelial cell lines (HOC 313 clone 8 and HSC 3). Colloidal gold nanoparticles are found in dispersed and aggregated forms within the cell cytoplasm and provide anatomic labeling information, but their uptake is nonspecific for malignant cells. The anti-EGFR antibody conjugated nanoparticles specifically and homogeneously bind to the surface of the cancer type cells with 600% greater affinity than to the noncancerous cells. This specific and homogeneous binding is found to give a relatively sharper SPR absorption band with a red shifted maximum compared to that observed when added to the noncancerous cells. These results suggest that SPR scattering imaging or SPR absorption spectroscopy generated from antibody conjugated gold nanoparticles can be useful in molecular biosensor techniques for the diagnosis and investigation of oral epithelial living cancer cells in vivo and in vitro.