Thermodynamically controlled separation of polyvalent 2-nm gold nanoparticle-oligonucleotide conjugates

We describe the synthesis of small (2-nm diameter) gold nanoparticles densely functionalized with thiolated DNA (DNA-Au NPs) and a method to separate these particles from excess free DNA after synthesis. The separation method utilizes the thermodynamically enhanced binding properties of 2-nm DNA-Au NPs, compared to free excess DNA, to selectively hybridize these small particles to larger (15-nm diameter) DNA-Au NPs and form aggregates that can be isolated by simple centrifugation. These 2-nm DNA-Au NPs are obtained in a 46% overall yield, have a high surface coverage of DNA (64.8 +/- 6.4 pmol/cm2), and as a result, exhibit increased melting temperatures and cooperative melting properties.     

"Three-dimensional hybridization" with polyvalent DNA-gold nanoparticle conjugates

We have determined the minimum number of base pairings necessary to stabilize DNA-Au NP aggregates as a function of salt concentration for particles between 15 and 150 nm in diameter. Significantly, we find that sequences containing a single base pair interaction are capable of effecting hybridization between 150 nm DNA-Au NPs. While traditional DNA hybridization involves two strands interacting in one dimension (1D, Z), we propose that hybridization in the context of an aggregate of polyvalent DNA-Au NP conjugates occurs in three dimensions (many oligonucleotides oriented perpendicular to the X, Y plane engage in base pairing), making nanoparticle assembly possible with three or fewer base pairings per DNA strand. These studies enabled us to compare the stability of duplex DNA free in solution and bound to the nanoparticle surface. We estimate that 4-8, 6-19, or 8-33 additional DNA bases must be added to free duplex DNA to achieve melting temperatures equivalent to hybridized systems formed from 15, 60, or 150 nm DNA-Au NPs, respectively. In addition, we estimate that the equilibrium binding constant (K(eq)) for 15 nm DNA-Au NPs (3 base pairs) is approximately 3 orders of magnitude higher than the K(eq) for the corresponding nanoparticle free system.     

Gold nanoparticle-catalyzed environmentally benign deoxygenation of epoxides to alkenes

We have developed a highly efficient and green catalytic deoxygenation of epoxides to alkenes using gold nanoparticles (NPs) supported on hydrotalcite [HT: Mg(6)Al(2)CO(3)(OH)(16)] (Au/HT) with alcohols, CO/H(2)O or H(2) as the reducing reagent. Various epoxides were selectively converted to the corresponding alkenes. Among the novel metal NPs on HT, Au/HT was found to exhibit outstanding catalytic activity for the deoxygenation reaction. Moreover, Au/HT can be separated from the reaction mixture and reused with retention of its catalytic activity and selectivity. The high catalytic performance of Au/HT was attributed to the selective formation of Au-hydride species by the cooperative effect between Au NPs and HT.     

Detection of mercury(II) based on Hg2+ -DNA complexes inducing the aggregation of gold nanoparticles

A DNA-Au NP probe for sensing Hg2+ using the formation of DNA-Hg2+ complexes through thymidine (T)-Hg2+ -T coordination to control the negative charge density of the DNA strands-thereby varying their structures-adsorbed onto Au NPs.     

Direct detection of genomic DNA by enzymatically amplified SPR imaging measurements of RNA microarrays

A novel surface enzymatic reaction scheme that amplifies the optical response of RNA microarrays to the binding of complementary DNA is developed for the direct detection and analysis of genomic DNA. The enzyme RNase H is shown to selectively and repeatedly destroy RNA from DNA-RNA heteroduplexes on gold surfaces; when used in conjunction with the label-free technique of surface plasmon resonance (SPR) imaging, DNA oligonucleotides can be detected at a concentration of 1 fM. This enzymatically amplified SPR imaging methodology is then utilized to detect and identify the presence of the TSPY gene in human genomic DNA without PCR amplification.     

Intrinsic peroxidase-like activity and catalase-like activity of Co3O4 nanoparticles

We demonstrate that Co(3)O(4) nanoparticles (NPs) exhibit intrinsic peroxidase-like activity and catalase-like activity. The peroxidase-like activity of the Co(3)O(4) NPs originates from their ability of electron transfer between reducing substrates and H(2)O(2), not from ˙OH radical generated. As peroxidase mimetics, Co(3)O(4) NPs were used for colorimetric determination of H(2)O(2) and glucose.     

二氧化铈纳米微粒过氧化物酶活性及其在葡萄糖检测中的应用

合成了一种稳定和水溶性的聚丙烯酸修饰CeO2 NPs,利用动态光散射(DLS)、傅里叶变换红外光谱(FT-IR)和X射线光电子能谱(XPS)进行表征.结果表明,CeO2 NPs能够催化H2O2氧化3,3′,5,5′-四甲基联苯胺(TMB)发生显色反应,表现出过氧化物模拟酶催化活性.利用Raman和顺磁共振(EPR)光谱技术研究了其催化机理.基于CeO2 NPs催化TMB变色反应对H2O2浓度的依赖性和葡萄糖氧化酶能够催化溶解氧氧化葡萄糖产生H2O2的原理,构建了一种简单、灵敏、选择性高的测定血清中葡萄糖的检测方法.在优化条件下,测定葡萄糖的线性范围为0.5~10 mmol/L,检出限(3σ)为0.1 mmol/L.对1.0 mmol/L葡萄糖进行11次平行测定,其相对标准偏差为2.4%.该方法已成功用于血清样品中葡萄糖的测定.     

Stabilisation of water-soluble platinum nanoparticles by phosphonic acid derivatives

Sodium 2-(diphenylphosphino)ethyl phosphonate (1) was investigated as a stabilising agent for platinum nanoparticles (Pt-NPs) in aqueous solution. This phosphino phosphonate is known to stabilise rhodium nanoparticles (NPs) in water. Here we report that in the case of Pt-NPs this ligand is indirectly involved in the stabilisation mechanism and the actual stabilisation agent is the platinum complex Na(2)[Pt(1)(2)] (2). The reduction of platinum(II) salts in the presence of the phosphonates 1, 2, sodium 2-(diphenylphosphoryl)ethyl phosphonate (3) and 3,3,3-triphenylpropyl phosphonate (4) leads to stable platinum NPs with a remarkably narrow particle size distribution. These platinum NPs show high catalytic activity in the hydrogenation of 1-hexene and 1-chloro-3-nitrobenzene under biphasic as well as heterogeneous (supported on charcoal) conditions. The activity of the supported NPs was 30 times higher than the commercially available catalyst Pt(0) EnCat?. Furthermore, the single-crystal X-ray structures of (1)(MeOH)(2)(H(2)O)(2), (3)(H(2)O)(4), and (4)(2)(H(2)O)(17) have been determined.     

Synthesis of Chemically Asymmetric Silica Nanobottles and Their Application for Cargo Loading and as Nanoreactors and Nanomotors

We report the synthesis of chemically asymmetric silica nanobottles (NBs) with a hydrophobic exterior surface (capped with 3‐chloropropyl groups) and a hydrophilic interior surface for spatially selective cargo loading, and for application as nanoreactors and nanomotors. The silica NBs, which have a “flask bottle” shape with an average diameter of 350 nm and an opening of ca. 100 nm, are prepared by anisotropic sol–gel growth in a water/n‐pentanol emulsion. Due to their chemically asymmetric properties, nanoparticles (NPs) with hydrophilic or hydrophobic surface properties can be selectively loaded inside the NBs or on the outside of the NBs, respectively. A high‐performance nanomotor is constructed by selectively loading catalytically active hydrophilic Pt NPs inside the NBs. It is also demonstrated that these NBs can be used as vessels for various reactions, such as the in situ synthesis of Au NPs, and using Au NP‐loaded NBs as nanoreactors for catalytic reactions.     

Efficient RNase H-directed cleavage of RNA promoted by antisense DNA or 2'F-ANA constructs containing acyclic nucleotide inserts

The ability of modified antisense oligonucleotides (AONs) containing acyclic interresidue units to support RNase H-promoted cleavage of complementary RNA is described. Manipulation of the backbone and sugar geometries in these conformationally labile monomers shows great benefits in the enzymatic recognition of the nucleic acid hybrids, while highlighting the importance of local strand conformation on the hydrolytic efficiency of the enzyme more conclusively. Our results demonstrate that the duplexes support remarkably high levels of enzymatic degradation when treated with human RNase HII, making them efficient mimics of the native substrates. Furthermore, interesting linker-dependent modulation of enzymatic activity is observed during in vitro assays, suggesting a potential role for this AON class in an RNase H-dependent pathway of controlling RNA expression. Additionally, the butyl-modified 2'F-ANA AONs described in this work constitute the first examples of a nucleic acid species capable of eliciting high RNase H activity while possessing a highly flexible molecular architecture at predetermined sites along the AON.     

Superparamagnetic Fe3O4 nanoparticles-carbon nitride nanotube hybrids for highly efficient peroxidase mimetic catalysts

We report a facile route to synthesize size tunable Fe(3)O(4) nanoparticles (NPs)-carbon nitride nanotube (CNNT) hybrids. These hybrids showing the water-soluble property are proven to exhibit ultra high peroxidase mimetic activity compared to those of pure NPs, where a colorless peroxidase substrate 3,3,5,5-tetramethylbenzidine changes by H(2)O(2) to its blue colored oxidized state.     

A density functional theory approach to mushroom-like platinum clusters on palladium-shell over Au core nanoparticles for high electrocatalytic activity

Recently, it was found that Pt clusters deposited on Pd shell over Au core nanoparticles (Au@Pd@Pt NPs) exhibit unusually high electrocatalytic activity for the electro-oxidation of formic acid (P. P. Fang, S. Duan, et al., Chem. Sci., 2011, 2, 531-539). In an attempt to offer an explanation, we used here carbon monoxide (CO) as probed molecules, and applied density functional theory (DFT) to simulate the surface Raman spectra of CO at this core-shell-cluster NPs with a two monolayer thickness of Pd shell and various Pt cluster coverage. Our DFT results show that the calculated Pt coverage dependent spectra fit the experimental ones well only if the Pt clusters adopt a mushroom-like structure, while currently the island-like structure is the widely accepted model, which follows the Volmer-Weber growth mode. This result infers that there should be a new growth mode, i.e., the mushroom growth mode as proposed in the present work, for Au@Pd@Pt NPs. We suggest that such a mushroom-like structure may offer novel active sites, which accounts for the observed high electrocatalytic activity of Au@Pd@Pt NPs.     

A nanoscale DNA-Au dendrimer as a signal amplifier for the universal design of functional DNA-based SERS biosensors

The use of a nanoscale DNA-Au dendrimer as a signal amplifier was proposed for the universal design of functional DNA-based ultra-sensitive SERS biosensors. This novel design combines the high specificity of functional DNA with the high sensitivity of surface-enhanced Raman scattering (SERS) spectroscopy, resulting in sensitivity superior to that of previously reported sensors.     

Self-suspended Pure Polydiacetylene Nanoparticles with Selective Response to Lysine and Arginine

We demonstrate a very convenient access to self-suspended pure poly(10,12-pentacosadiynoic acid) (PDA) nanoparticles (NPs) simply by adding the ethanol solution of diacetylene monomer to water, followed by UV irradiation. The as-obtained PDA NPs are of high purity because no any initiator, catalyst or stabilizer was used during the whole process. The stabilizer-free PDA NPs are stable in the aqueous suspension. Due to the high purity and stability, the PDA NPs can respond sensitively and selectively to lysine and arginine among 18 kinds of water soluble natural amino acids; without the competitive interaction from the stabilizer, the sensitivity was enhanced.     

Delivery of ROS Generating Anthraquinones Using Reduction‐Responsive Peptide‐Based Nanoparticles

In order to limit the side effects associated with antitumor drugs such as doxorubicin, nanosized drug‐delivery systems capable of selectively delivering and releasing the drug in the diseased tissue are required. We describe nanoparticles (NPs), self‐assembled from a reduction responsive amphiphilic peptide, capable of entrapping high amounts of a redox active anticancer drug candidate and releasing it in presence of a reducing agent. This system shows a high entrapment efficiency with up to 15 mg drug per gram of peptide (5.8 mol‐%). Treatment of the NPs with reducing agent results in the disassembly of the NPs and release of the drug molecules. A reduction in cell viability is observed at drug concentrations above 250 nm in HEK293T and HeLa cell lines. This drug delivery system has potential for targeting tumor sites via the EPR effect while taking advantage of the increased reduction potential in tumor microenvironment.     

Identifying the active photocatalytic H2-production sites on TiO2-supported Pt nanoparticles by the in-situ infrared spectrum of CO

Identifying the active catalytic centers on catalyst surface is significant for exploring the catalytic reaction mechanism and further guiding the synthesis of high-performance catalysts.However,it remains a challange in developing the site-specific technology for the identification of the active catalytic centers.Herein,in-situ infrared spectroscopy of adsorbed CO,photocatalytic hydrogen evolution reaction(HER) test and theoretical simulation were used to distinguish and quantify the different surface sites and their H2-production catalytic activity on TiO_2-supported Pt nanoparticles(Pt NPs).Two different types of surface Pt sites,tip Pt(Pt_(tip)) and edge/terrace Pt_(edge/terrace),on TiO_2-supported Pt nanoparticles(Pt NPs) were identified.The photocatalytic H2-production activity of TiO_2-supported Pt NPs shows a linear functional relationship with the number of Pt_(tip) sites.However,the number of Pt_(edge/terracesites) produced little effect on the activity of TiO_2-supported Pt NPs.First-principle simulations confirmed that H2-evolution at the Pttipsites owns a lower energy barrier than that at Pt_(edge/terrace).This findings would be helpful for the fabrication of high-performance Pt catalysts.     

Preparation and enhanced visible-light photocatalytic H2-production activity of CdS-sensitized Pt/TiO2 nanosheets with exposed (001) facets

CdS-sensitized Pt/TiO(2) nanosheets with exposed (001) facets were prepared by hydrothermal treatment of a Ti(OC(4)H(9))(4)-HF-H(2)O mixed solution followed by photochemical reduction deposition of Pt nanoparticles (NPs) on TiO(2) nanosheets (TiO(2) NSs) and chemical bath deposition of CdS NPs on Pt/TiO(2) NSs, successively. The UV and visible-light driven photocatalytic activity of the as-prepared samples was evaluated by photocatalytic H(2) production from lactic acid aqueous solution under UV and visible-light (λ ≥ 420 nm) irradiation. It was shown that no photocatalytic H(2)-production activity was observed on the pure TiO(2) NSs under UV and/or visible-light irradiation. Deposition of CdS NPs on Pt/TiO(2) NSs caused significant enhancement of the UV and visible-light photocatalytic H(2)-production rates. The morphology of TiO(2) particles had also significant influence on the visible-light H(2)-production activity. Among TiO(2) NSs, P25 and the NPs studied, the CdS-sensitized Pt/TiO(2) NSs show the highest photocatalytic activity (13.9% apparent quantum efficiency obtained at 420 nm), exceeding that of CdS-sensitized Pt/P25 by 10.3% and that of Pt/NPs by 1.21%, which can be attributed to the combined effect of several factors including the presence of exposed (001) facets, surface fluorination and high specific surface area. After many replication experiments of the photocatalytic hydrogen production in the presence of lactic acid, the CdS-sensitized Pt/TiO(2) NSs did not show great loss in the photocatalytic activity, confirming that the CdS/Pt/TiO(2) NSs system is stable and not photocorroded.     

Inhibition of translation by small RNA-stabilized mRNA structures in human cells

RNA-mediated gene regulation and expression are critically dependent on both nucleic acid architecture and recognition. We present a novel mechanism for the regulation of gene expression through direct RNA-RNA interactions between small RNA and mRNA in human cells. Using mRNA reporters containing G-rich sequences in the 5'-untranslated region (5'-UTR), in the coding region, or both, we showed that G-rich small RNAs bind to the reporter mRNAs and form an intermolecular RNA G-quadruplex that can inhibit gene translation in living cells. Using a combination of circular dichroism (CD) and RNase footprinting in vitro, we found that the intermolecular G-quadruplexes show a parallel G-quadruplex structure. We next investigated whether the intermolecular G-quadruplex is present in living cells. Employing the fluorophore-labeled probes, we found that two G-rich RNA molecules form an intermolecular G-quadruplex structure in living cells. These results extend the concept of small RNA-mediated expression and suggest an important role for such RNA structures in the inhibition of mRNA translation.     

Novel high-sensitive fluorescent detection of deoxyribonuclease I based on DNA-templated gold/silver nanoclusters

Herein, fluorescent DNA-templated gold/silver nanoclusters (DNA-Au/Ag NCs) are presented as a novel probe for sensitive detection of deoxyribonuclease I (DNase I). The procedure is based on quenching fluorescence of DNA-Au/Ag NCs by DNase I digestion of the DNA (5′-CCCTTAATCCCC-3′) template. This decrease in fluorescence intensity permitted sensitive detection of DNase I in a linear range of 0.013–60 μg mL⁻¹, with a detection limit of 3 ng mL⁻¹ at a signal-to-noise ratio of 3. Furthermore, the practicality of this probe for detection of DNase I in human serum and saliva samples was validated, demonstrating its advantages of simplicity, selectivity, sensitivity and low cost. Importantly, satisfactory agreement between results obtained by the fluorescent method described here and high performance liquid chromatography (HPLC) further confirmed the reliability and accuracy of this approach.     

Oxidation Responsive PEGylated Polyamino Acid Bearing Thioether Pendants for Enhanced Anticancer Drug Delivery

Reactive oxygen species (ROS) in biological tissues are in a state of dynamic balance. However, many diseases such as cancer and inflammation, are accompanied by a long-term increase in ROS. This situation inspires researchers to use ROS-sensitive nanocarriers for a site-specific release of cargo in pathological areas. Polyamino acid materials with good biodegradability, biocompatibility, and regular secondary structure are widely used in the biomedical field. Herein, a new oxidation responsive PEGylated polyamino acid is synthesised for anticancer drug delivery by ring-opening polymerisation of N-carboxyanhydrides bearing thioether pendants. The obtained block copolymer mPEG-b-PMLG self-assembles into spherical nanoparticles (NPs) in water with diameter ≈68.3 nm. NMR measurement demonstrated that the hydrophobic thioether pendants in the NPs can be selectively oxidised to hydrophilic sulfoxide groups by H₂O₂, which will lead to the disassociation of NPs. In vitro drug release results indicated that the encapsulated Nile red is selectively released in the trigger of 10 mM H₂O₂ in PBS. Finally, anticancer drug doxorubicin (DOX) is encapsulated to the NPs, and the obtained NPs/DOX exhibits an improved antitumor efficacy in 4T1 tumour-bearing mice and lower cardiotoxicity than free DOX. These results indicates that the mPEG-b-PMLG NPs are promising for anticancer drug delivery.