Selectively colorimetric detection of cysteine with triangular silver nanoprisms

Triangular silver nanoprisms were prepared and applied to make colorimetric detection of cysteine based on our findings that cysteine could lead to the blue shift of the dipole plasmon resonance absorption,but other 19 kinds of natural amino acids could not.Cysteine with a concentration 160 nmol/L can result in a color change that can be discerned with naked eyes.     

Bending contours in silver nanoprisms

A detailed electron microscopy analysis is reported on the structure of silver nanoprisms synthesized by controlled photoinduced aggregation of Ag nanoparticles. Bending of the nanoprism (111) face is directly revealed in the presence of fringes in both bright and dark field TEM images, which are unequivocally assigned to bending contours. Such contours can be individually imaged through shifting of the objective aperture and selectively allowing transmission of the corresponding diffraction spot. The assignment of a bent structure is supported by images of the lateral sides of the prisms, and high-resolution images where apparent changes in the lattice constant are observed.     

Synthesis of uniform gold nanoparticles using non-pathogenic bio-control agent: evolution of morphology from nano-spheres to triangular nanoprisms

Green synthesis of gold nanospheres with uniform diameter and triangular nanoprisms with optically flat surface was carried out using a non-pathogenic bio-control agent Trichoderma asperellum for reduction of HAuCl(4). Kinetics of the reaction was monitored by UV-Vis absorption spectroscopy. No additional capping/complexing agent was used for stabilizing the gold nanoparticles. Evolution of morphology from pseudospherical nanoparticles to triangular nanoprisms was studied by transmission electron microscopy (TEM). It revealed that three or more pseudospheres fused to form nanoprisms of different shapes and sizes. Slow rate of reduction of HAuCl(4) by constituents of cell-free fungal extract was instrumental in producing such exotic morphologies. Isolation of gold nanotriangles from the reacting masses was achieved by differential centrifugation.     

Synthesis of silver nanoprisms in formamide

Polygonal (mainly triangular) silver nanoprisms were prepared by reducing silver perchlorate in formamide in the presence of polyethylene glycol (PEG) at room temperature. The reduction of silver ions by formamide leads to the deposition of arrays of triangular shaped silver nanoparticles on the glass walls of the container, accompanied by evolution of CO2 gas. In the presence of poly(N-vinyl-2-pyrrolidone) (PVP) and PEG (1:1), both nanospheres and nanoprisms are formed.     

Anisotropic assembly of Ag nanoprisms

The Ag nanoprisms with controlled arrangements show distinct optical, crystallographic, and surface-enhanced Raman scattering properties depending on their orientation in the assemblies, demonstrating that the controlled assembly of anisotropic nanostructures can be utilized as a powerful tool for studying their physicochemical properties and for the creation of new classes of functional materials.     

Three-dimensional self-organization of supramolecular self-assembled porphyrin hollow hexagonal nanoprisms

A self-assembly technique assisted with surfactant is developed to fabricate one-dimensional (1D) nanostructure of zinc meso-tetra (4-pyridyl) porphyrin. The so-prepared nanostructure appears in a shape of hollow hexagonal nanoprism with uniform size. The length and aspect ratio of the nanoprisms is easily tunable by controlling the stoichiometric ratio of porphyrin over surfactant. The internal structure of the nanoprisms is well described by XRD. Furthermore, as a result of dispersivity and regular geometric shape, these nanoprisms can readily self-organize into an ordered, smectic three-dimensional (3D) architecture through simple evaporation of the solvent. The results should be significant in porphyrin crystallization and porphyrin application in optoelectronic device, catalysis, drug delivery, and molecular filtration.     

Multipolar surface plasmon peaks on gold nanotriangles

In this paper, we report on the observation of multipolar surface plasmon excitation in lithographically designed gold nanotriangles, investigated by means of far-field extinction microspectroscopy in the wavelength range of 400-1000 nm. Several bands are observed in the visible and near infrared regions when increasing the side length of the triangles. The assignment of these peaks to successive in-plane multipolar plasmon modes is supported by calculations using the discrete dipole approximation method. We show that the lowest three multipolar excitations are clearly resolved in the visible and near infrared range. These new spectral features could be very promising in nanooptics or for chemosensing and biosensing applications.     

One pot synthesis of polymer protected gold nanoparticles and nanoprisms in glycerol

Uniform and stable polymer protected spherical gold nanoparticles were synthesized using glycerol as reducing agent. Further it was observed that the morphology of the particles varied from spherical to triangular prismatic gold nanoparticles when the reaction was changed from normal mode of reflux condition to microwave mode (MW) of heating. Further a brief mechanism relating the formation of prisms with the orientation of polymer and nucleation period has been discussed. Formation of triangular prismatic and spherical gold nanoparticles were characterised using UV–vis spectroscopy, transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis.     

Multipolar Porphyrin-Triazatruxene Arrays for Two-Photon Fluorescence Cell Imaging

Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP) _n (n=1–3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40–0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT-ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δ_TPA values of TAT-(ZnP)₂ and TAT-(ZnP)₃ further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π-conjugated quadrapole/octupole molecules and the extension of D -π-A-D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin-based TPEF materials by the construction and extension of D -π-A-D multipolar array.     

Tailoring the synthesis and heating ability of gold nanoprisms for bioapplications

The paper describes a novel and straightforward wet-chemical synthetic route to produce biocompatible single-crystalline gold tabular nanoparticles, herein called nanoprisms (NPRs) due to their characteristic shape. Besides the novelty of the method to produce NPRs with an unprecedented high yield, the synthesis avoids the use of highly toxic cetyltrimethylammonium bromide (CTAB), the most widely used surfactant for the synthesis of gold anisotropic nanoparticles such as nanorods or nanoprisms. The method presented here allows for tuning the edge length of NPRs in the range of 100-170 nm by adjusting the final concentration/molar ratio of gold salt and reducing agent (thiosulfate), while the thickness of NPRs remained constant (9 nm). Thus, the surface plasmon band of NPRs can be set along the near-infrared (NIR) range. The resulting NPRs were derivatized with heterobifunctional polyethylene glycol (PEG) and 4-aminophenyl β-D-glucopyranoside (glucose) chains to improve their stability and cellular uptake, respectively. The heating properties of colloidal solutions of NPRs upon 1064 nm light illumination were evaluated. As a proof of concept, the biocompatibility and suitability of functional NPRs as photothermal agents were studied in cell cultures. Due to their biocompatibility (avoiding CTAB), ease of production, ease of functionalization, and remarkable heating features, the NPRs discussed herein represent a significant advance in the biocompatibility of nanoparticles and serve as an attractive alternative to those currently in use as plasmonic photothermal agents.     

Ultrasonically induced Au nanoprisms and their size manipulation based on aging

A simple sonochemical approach was developed for the synthesis of single-crystal Au nanoprisms with triangular or hexagonal shape, 30-40 nm planar dimension, and 6-10 nm thickness in an ethylene glycol solution. It has been shown that ethylene glycol, the surfactant poly(vinylpyrrolidone), and ultrasonic irradiation play important roles in the formation of Au nanoprisms. The subsequent aging induces the growth of Au nanoprisms, which is attributed to the existence of residual reduced Au degrees atoms and Au clusters in the solution. Further growth of Au nanoprisms could be realized by adding a given amount of HAuCl4 to the irradiated and aged Au nanodisk colloidal solution, which provides a simple and an effective method to synthesize Au nanoprisms with different sizes. Au nanoprisms with planar sizes from 70 to 400 nm have been successfully synthesized based on this strategy.     

SERS-based DNA detection in aqueous solutions using oligonucleotide-modified Ag nanoprisms and gold nanoparticles

Oligonucleotide-modified nanoparticle conjugates show highly promising potential for SERS-based DNA detection. However, it remains challenging to carry out the SERS-based DNA detection in aqueous solutions directly using oligonucleotide-modified nanoparticles, because the Raman reporters would exhibit lower signals when they are dispersed in aqueous solutions than laid on “dry” metal nanoparticles. Here, we synthesized stable oligonucleotide-modified Ag nanoprism conjugates, and performed SERS-based DNA detection in aqueous solution directly by using such conjugates in combination with Raman reporter-labeled, oligonucleotide-modified gold nanoparticles. The experimental results indicate that this SERS-based DNA detection approach exhibited a good linear correlation between SERS signal intensity and the logarithm of target DNA concentration ranging from 10^?11～10^?8 M. This sensitivity is comparable to those SERS-based DNA detection approaches with the “dry” process. Additionally, a similar correlation could also be observed in duplex target DNA detection by SERS hybrid probes. Our results suggest that the oligonucleotide-modified Ag nanoprisms may be developed as a powerful SERS-based DNA detection tool.

Multipolar symmetric squaraines with large two-photon absorption cross-sections in the NIR region

The two-photon absorption (TPA) properties of two extended symmetric squaraine dyes are thoroughly characterized from the experimental and quantum-chemical point of view. The two molecules are specially engineered to have a multipolar structure with increasing complexity, D-π-A-π-D and A'-π-D-π-A-π-D-π-A', respectively. The experimental TPA spectra, measured by means of the Z-scan technique in the femtoseconds regime, display considerably high values of TPA cross sections (σ(TPA)) for both molecules. In particular, the squaraine with the more extended structure shows the highest value of σ(TPA) ever reported for this class of molecules. CIS and TDDFT calculations of the one and two-photon absorption properties are carried out to clarify the origin of the observed TPA properties and fully characterize the electronic properties of these compounds. The calculations, in good agreement with the experimental data, suggest that the origin of this exceptionally high σ(TPA) can be ascribed to the presence of a peripheral A' group, that increases the density of excited states involved in the TPA process.     

Multipolar electrostatics for proteins: Atom–atom electrostatic energies in crambin

Accurate electrostatics necessitates the use of multipole moments centered on nuclei or extra point charges centered away from the nuclei. Here, we follow the former alternative and investigate the convergence behavior of atom‐atom electrostatic interactions in the pilot protein crambin. Amino acids are cut out from a Protein Data Bank structure of crambin, as single amino acids, di, or tripeptides, and are then capped with a peptide bond at each side. The atoms in the amino acids are defined through Quantum Chemical Topology (QCT) as finite volume electron density fragments. Atom‐atom electrostatic energies are computed by means of a multipole expansion with regular spherical harmonics, up to a total interaction rank of L = ?_A+ ?_B + 1 = 10. The minimum internuclear distance in the convergent region of all the 15 possible types of atom‐atom interactions in crambin that were calculated based on single amino acids are close to the values calculated from di and tripeptides. Values obtained at B3LYP/aug‐cc‐pVTZ and MP2/aug‐cc‐pVTZ levels are only slightly larger than those calculated at HF/6‐31G(d,p) level. This convergence behavior is transferable to the well‐known amyloid beta polypeptide Aβ_1–42. Moreover, for a selected central atom, the influence of its neighbors on its multipole moments is investigated, and how far away this influence can be ignored is also determined. Finally, the convergence behavior of AMBER becomes closer to that of QCT with increasing internuclear distance. © 2013 Wiley Periodicals, Inc.     

用于合成气高选择性直接制备低碳烯烃的碳化钴纳米棱柱结构

低碳烯烃(乙烯、丙烯、丁烯)是十分重要的有机化工原料,在传统工业中,主要通过石脑油,石油气和凝析油裂解得到.由于石油资源的日益减少和C1化学的迅速发展,为缓解对石油资源的依赖,急需寻找一种烯烃制备的工艺过程替代石油路线.主流的非石油路线主要是指利用煤炭、天然气、生物质等含碳资源通过合成气直接或间接制备烯烃.间接过程是由合成气转化制得甲醇,然后通过甲醇转化路线(包括甲醇制烯烃的MTO工艺和甲醇制丙烯的MTP工艺)生产烯烃产品.无疑,如能减少反应步骤,将合成气直接高选择性合成低碳烯烃,将体现出流程更短能耗更低的优势,有较强的竞争力.国内外的研究学者一直致力于制备含两种组元的双功能催化剂,试图将甲醇合成及脱水制备烯烃两步耦合在一起,合并为一步法,从而简化工业过程.由于低温下MTO反应几乎无活性,目前该类双功能复合催化剂多采用较高的反应温度.鉴于传统的Cu-Zn-Al催化剂在高温下极低的甲醇选择性,而Zn与其它过渡金属复合氧化物(如ZnZr及ZnCr)可在高温下高选择性合成甲醇,故经常被考虑作为耦合催化剂进行研究.基于上述理念,大化所包信和等提出了全新的OX-ZEO过程,OX(复合氧化物)用来活化CO分子并形成相应中间体,这些中间体可以在ZEO(分子筛)的酸性位上形成相应的烯烃.他们报道的ZnCrOx/MSAPO催化剂,在较高的CO转化率(17%)下,低碳烯烃选择性高达80%.与此同时,厦门大学王野等采用ZnZr二元氧化物与SAPO-34分子筛物理混合的双功能催化剂,也可实现很高的低碳烯烃选择性(74%).合成气经费托路线直接制烯烃(FTO)反应与费托(FT)反应类似,传统FT催化剂均可用于FTO的改性研究.由于Fe基催化剂的加氢能力相对较弱,产物中烯/烷比较高,所以被广泛用于FTO反应的研究中.de Jong研究小组采用惰性载体负载的Fe基催化剂,并浸渍Na,S元素作为助剂进行FTO反应的研究,实现了61%的低碳烯烃的选择性,但由于反应温度较高(300–350℃),催化剂容易失活,稳定性不佳.此外,由于产物受到ASF分布的限制,甲烷选择性很高.目前FTO研究的挑战在于开发全新的催化活性位结构新方法,摆脱ASF分布的限制,在较温和的反应条件下同时呈现低甲烷选择性及高烯烃选择性.一般认为,金属Co纳米颗粒是Co基费托催化剂的活性相,主要产物为C5+长链饱和烷烃,而Co2C则被视为Co基FT催化剂失活的主要原因之一,即在合成气转化过程中Co2C活性很低且CH4选择性很高.但是,最近中国科学院上海高等研究院低碳转化科学与工程重点实验室的钟良枢及孙予罕领导的研究小组发现,暴露(020)及(101)晶面的Co2C纳米棱柱结构对合成气转化具有异乎寻常的催化性能.该催化剂在温和的反应条件(250℃和0.1–0.5 MPa)下可实现合成气高选择性直接制备烯烃,甲烷选择性可低至5%,低碳烯烃选择性能够达到60%,而总烯烃选择性高达80%以上(以上所谈到的选择性都是去除了CO2产物),同时烯/烷比大于30,产物分布完全不服从经典的ASF规律,并且该催化剂具有良好的稳定性,反应600 h仍未出现明显失活.他们通过深入的构效关系研究并结合DFT理论计算,揭示了Co2C存在显著的晶面效应,相比于其它暴露面,(101)晶面非常有利于烯烃的生成,同时(101)和(020)晶面可有效抑制甲烷的形成.     

Multipolar polarizabilities of the sodium atom by a variationally stable procedure

We present a formalism that combines a semiempirical model potential with a second-order energy correction variationally stable method to evaluate the multipolar dynamic polarizabilities of the sodium atom. In this framework, the alpha(L)(omega) up to L=4 were calculated achieving good precision including the resonance domains of omega.     

Observation of a quadrupole plasmon mode for a colloidal solution of gold nanoprisms

The synthesis and optical properties of single crystalline gold nanoprisms have been investigated. A three-step mediated seed growth process in an aqueous solution generated gold nanoprisms with a relatively homogeneous size distribution. The purity of these nanostructures has allowed us to observe a weak quadrupole resonance in addition to a strong dipole resonance associated with these novel structures. The experimental optical spectra agree with discrete dipole approximation calculations that have been modeled from the dimensions of gold nanoprisms produced in this synthesis.     

A mild liquid reduction route toward uniform blue-emitting EuCl2 nanoprisms and nanorods

In this work, for the first time, uniform blue-emitting EuCl(2) nanoprisms and nanorods were synthesized from Eu(CCl(3)COO)(3)·2H(2)O [or Eu(CH(3)COO)(3)·H(2)O] by a novel mild liquid reduction route, using acetamidine hydrochloride (or picolinamidine hydrochloride) as the reductant in oleylamine. The synthetic reaction even can take place under an atmosphere in the absence of inert gas at around 300 °C. The EuCl(2) nanoprism dispersion in n-hexane showed an intense blue emission when excited by UV light.