Spectroscopic investigations of poly(propyleneimine)dendrimers using the solvatochromic probe phenol blue and comparisons to poly(amidoamine) dendrimers.

The physical and chemical properties of PPI dendrimers' interior were investigated using the fluorescent, solvatochromic probe phenol blue. In aqueous solutions of each generation studied, two discrete dye populations were clearly observed. PPI dendrimers were shown to form a tight, nonpolar association with the vast majority of available dye, within the dendrimer interior, near the core. In the steady-state fluorescence emission spectra, a microenvironment of decreasing polarity in increasingly larger-generation PPI dendrimers (up to G3) was seen for the associated probe. Each of the remaining larger-generation dendrimers provided a microenvironment of essentially equal polarity. Fluorescence anisotropy values for phenol blue in the PPI dendrimers demonstrated the dye's sensitivity to the changing molecular volumes of the dendrimer generations. Model compounds that mimicked PPI's surface groups and branching moieties were used to better define the associated dye's location. The mimics further confirmed that phenol blue was associated inside the dendrimer, where it did not interact with the dendrimer surface groups. The comparison of amine-terminated PPI and PAMAM dendrimers clearly demonstrated the effects of their structural differences and the ability of phenol blue to have sensed those differences, including the initiator core length, branching unit length, and branching unit chemical composition.     

微米铜粉/纳米TiO_2复合粒子的低温制备及光吸收性能

利用仿生合成的方法在温和条件下制备了微米铜粉/纳米TiO2复合粒子.选择有机胺对Cu粉进行表面处理,XPS分析表明有机胺通过N原子与表面Cu2+络合形成功能层,在Cu粉表面引入NH2和OH等功能基团,对比实验证实功能基团能够诱导无机氧化物的仿生沉积.XRD结果表明铜粉表面包覆的纳米TiO2呈现锐钛矿晶型,漫反射光谱(DRS)分析表明,Cu粉经过有机胺处理后在716.5nm处出现了由Cu2+离子与N配位产生的弱吸收.复合粒子的光吸收性能介于TiO2和Cu粉之间,Cu负载后样品的光吸收阀值从397.5nm红移至448.9nm,红移的原因可归于Cu负载后TiO2导带下出现新能级,光生电子经过这些中间能级发生跃迁,所需激发能量降低至可见光范围.448.9nm处吸收边的存在表明复合粒子具备可见光催化活性.     

Synthesis and properties of water-soluble core-shell-shell silica-CdSe/CdS-silica nanoparticles

This paper describes the synthesis of highly water-soluble and fluorescent core-shell-shell silica-CdSe/CdS-silica nanoparticles (CSS silica-QDs-silica NPs). We used cadmium nitrate and 1,1-dimethyl-2-selenourea precursors to synthesize CdSe quantum dots (QDs) in aqueous solution under simultaneous illumination with a diode-pumped solid state green laser and a Xe-Hg lamp. After passivation of the CdSe QDs with CdS, the CdSe/CdS QDs were then conjugated covalently to (3-mercaptopropyl)trimethoxysilane (MPS); we call these nanoparticles "MPS-QDs". We mixed the MPS-QDs with tetraethoxysilane (TEOS), ethanol, and NH3. By controlling the concentrations of the reagents, the stirring speed, and the reaction time, we synthesized CSS silica-QDs-silica NPs having sizes ranging from 75 to 190 nm. The incubation time for preparing the MPS-QDs and their concentrations are important parameters in determining the morphologies of the CSS silica-QDs-silica NPs. When we mixed 50 nM MPS-QDs, 1.1 mM TEOS, and 78 mM NH3 and reacted them at a stirring speed of 750 rpm, we obtained 85-nm-diameter CSS silica-QDs-silica NPs having a QD shell thickness of about 20 nm. The CSS silica-QDs-silica NPs provide a strong photoluminescence intensity (quantum yield 88%) and exhibit enhanced stability both photochemically and in high-conductivity media (e.g., 1.0 M NaCl).     

In-situ preparation of binary-phase silver nanoparticles at a high Ag+ concentration

Stable and monodisperse silver nanoparticles (NPs) have been synthesized using high metal salt concentration (up to 0.735 M) through a simple but novel technique. It is based on one-step procedure that uses glycerol for reducing Ag+ in the presence of o-phenylenediamine (o-PDA) resulting the nanoparticles are in two forms (one water-soluble, the other a precipitated). The water-soluble phase contains NPs that have a bimodal size distribution (2-3 and 5-6 nm); the other comprises precipitated NPs, having a unimodal size distribution (2-3 nm). The water-soluble NPs are covalently bonded to the aromatic amine molecules to form isolated units, while the precipitated nanoparticles are embedded in the networks formed by cross-linking between COOH groups of hydroxypyruvic acid (oxidized form of glycerol) and NH2 groups of o-PDA molecules. We used transmission electron microscopy (TEM), UV-Vis spectroscopy, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) to characterize the silver products obtained.     

HPLC separation of different generations of poly(amidoamine) dendrimers modified with various terminal groups

Polyamidoamine (PAMAM) dendrimers of different generations with various terminal groups were analyzed, for the first time, using a combination of high-performance liquid chromatography (HPLC), size exclusion chromatography (SEC), and matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) techniques. Separation of amine-terminated dendrimers from generation 1 through generation 9 (G1NH(2)-G9NH(2)) was achieved using reversed-phase HPLC with elution time increasing gradually as the density of terminal amine groups increases as a function of generation. Furthermore, separation of dendrimers with terminal amino, acetamide, hydroxyl, and carboxylate groups was obtained. It has also been shown that HPLC can be used to separate dendrimers based on some structural defects inherent during the syntheses of PAMAM dendrimers. MALDI-TOF mass spectra of G1NH(2) identify the major imperfections present during typical synthesis processes. The absolute molar masses (M(n)) and molar mass distributions of the dendrimers were measured using the SEC system equipped with multiangle laser light scattering and refractive-index detectors. Findings from this study suggest HPLC can be a vital tool for characterization and preparative separation of PAMAM dendrimers.     

Three‐Dimensional Gold Nanoparticle Clusters with Tunable Cores Templated by a Viral Protein Scaffold

Assembling nanoparticles (NPs) into ordered architectures remains a challenge in the field of nanotechnology. Templated strategies have been widely utilized for NP assembly. As typical biological nanostructures, virus‐based NPs (VNPs) have shown great promise in templating NP assembly. Here it is illustrated that the VNP of simian virus 40 (SV40) is a powerful scaffold in directing the assembly of 3D hybrid nanoarchitectures with one NP encapsulated inside as a core and a cluster of gold NPs (AuNPs) on the outer surface of the SV40 VNP as a shell, in which the core NPs can be CdSe/ZnS quantum dots (QDs), Ag₂S QDs, or AuNPs. The assembling of AuNPs onto the SV40 VNP surface is determined by the interactions between the AuNPs and the amine groups on the outer surface of SV40 VNPs. It is expected that the VNP guided 3D hybrid nanoarchitectures provide ideal models for NP interaction studies and open new opportunities for integrating various functionalities in NP assemblies.     

Desymmetrized Diiron Azadithiolato Carbonyls: A Step Toward Modeling the Iron-Only Hydrogenases

Condensation of Fe(2)(SH)(2)(CO)(6), acetaldehyde, and (NH(4))(2)CO(3) affords the methyl-substituted azadithiolate Fe(2)[(SCHMe)(2)NH](CO)(6) (1). The complex exists mainly (~95%) as the meso diastereomer, but the d,l diastereoisomers could be detected. DFT calculations predict that the meso isomer would be 2.5 kcal/mol more stable than the d,l isomer due to conventional nonbonding interactions between the methyl groups and the ring hydrogen atoms. Crystallographic analysis of meso-1 confirms that the two methyl groups are equatorial, constraining the diferraazadithiolate bicycle to a conformation that desymmetrizes the diiron center. The lowered symmetry is confirmed by the observation of two (13)C NMR signals in the FeCO region under conditions of fast turnstile rotation at the Fe(CO)(3) groups. The pK(a) value of the amine in 1 is 7.89 (all pK(a)'s determined in MeCN solution), which is similar to a redetermined value for Fe(2)[(SCH(2))(2)NH](CO)(6) (2, pK(a) = 7.98) and only slightly less basic than the tertiary amine Fe(2)[(SCH(2))(2)NMe](CO)(6) (pK(a) = 8.14). Substitution of 1 with PMe(3) proceeded via the intermediacy of two isomers of Fe(2)[(SCHMe)(2)NH](CO)(5)(PMe(3)), affording Fe(2)[(SCHMe)(2)NH](CO)(4)(PMe(3))(2) (3). (31)P NMR spectra confirm that the two PMe(3) ligands in 3 are nonequivalent, consistent with the desymmetrizing effect of the dithiolate. The pK(a) value of the amine in 3 was found to be 11.3. Using triphenylphosphine, we prepared Fe(2)[(SCHMe)(2)NH](CO)(5)(PPh(3)) as a single regioisomer.     

Fluorescent Polymer Nanoparticles Based on Dyes: Seeking Brighter Tools for Bioimaging

Speed, resolution and sensitivity of today's fluorescence bioimaging can be drastically improved by fluorescent nanoparticles (NPs) that are many‐fold brighter than organic dyes and fluorescent proteins. While the field is currently dominated by inorganic NPs, notably quantum dots (QDs), fluorescent polymer NPs encapsulating large quantities of dyes (dye‐loaded NPs) have emerged recently as an attractive alternative. These new nanomaterials, inspired from the fields of polymeric drug delivery vehicles and advanced fluorophores, can combine superior brightness with biodegradability and low toxicity. Here, we describe the strategies for synthesis of dye‐loaded polymer NPs by emulsion polymerization and assembly of pre‐formed polymers. Superior brightness requires strong dye loading without aggregation‐caused quenching (ACQ). Only recently several strategies of dye design were proposed to overcome ACQ in polymer NPs: aggregation induced emission (AIE), dye modification with bulky side groups and use of bulky hydrophobic counterions. The resulting NPs now surpass the brightness of QDs by ≈10‐fold for a comparable size, and have started reaching the level of the brightest conjugated polymer NPs. Other properties, notably photostability, color, blinking, as well as particle size and surface chemistry are also systematically analyzed. Finally, major and emerging applications of dye‐loaded NPs for in vitro and in vivo imaging are reviewed.     

Synthesis of highly environmental stable copper–silver core–shell nanoparticles for direct writing flexible electronics

In this study, Cu@Ag core–shell nanoparticles (NPs) with highly environmental stability were synthesized successfully by combining the NaBH₄ reduction method with the transmetallation reaction, and the Cu@Ag nano-ink was prepared for direct writing flexible electronics. The structure, component, thermal stability and oxidation resistance of Cu NPs and Cu@Ag core–shell nanoparticles were characterized and discussed systematically. The results showed that Cu NPs could be obtained via the reduction of Cu²⁺ ions by using cetyltrimethylammonium bromide (CTAB) as a dispersing agent under an excess of sodium hydroxide (NaOH) and sodium borohydride (NaBH₄) in aqueous solution. And the Cu@Ag core–shell nanoparticles with uniform Ag shell and Cu core can be fabricated with the transmetallation reaction that Ag⁺ ions were reduced by the copper atoms on the surface of Cu NPs at pH 7, and the Cu core were kept from oxidation from the Ag shell. Besides, Cu@Ag nano ink were fabricated by dispersing Cu@Ag core–shell nanoparticles in ethylene glycol, and Cu@Ag conductive pattern were directly drawn on ordinary photo paper using a roller pen filled with 30 wt% Cu@Ag nano ink. The electrical resistivity of the conductive Cu@Ag pattern obtained from the nano ink was as low as 13.8 μΩ cm^?1 due to the continuous interconnections between the nanoparticles established when thermal sintered at 150?°C for 1 h under N₂. When the conductive wires of a lamp were connected to the two ends of the written conductive line, the lamp was illuminated immediately. It demonstrated that the complicated Cu@Ag nano-ink pattern had very good conductivity and applicability. This work provides an effective approach to prepare Cu@Ag core–shell nano-ink for direct writing flexible electronics.     

Tannic acid stabilized antioxidation copper nanoparticles in aqueous solution for application in conductive ink

Water-dispersible copper nanoparticles (Cu NPs) with good antioxidation properties are facilely synthesized in aqueous solution without inert gas protection employing tannic acid (TA) as the stabilizer and protectant. The sizes of as-prepared tannic acid capped copper nanoparticles (TA-Cu NPs) are in the range of 20–40 nm with a narrow size distribution. Owing to the protection of TA layer, TA-Cu NPs exhibit excellent anti-oxidation power and no oxidation was observed even after being stored under ambient conditions for 90 days. In addition, homogenous Cu NPs inks could be synthesized via the simple dispersion of TA-Cu NPs in water, which can be inkjet-printed onto flexible substrates into conductive patterns using a common color printer.     

Immobilization of dendrimers on Si-C linked carboxylic acid-terminated monolayers on silicon(111)

Poly(amidoamine) dendrimers were attached to activated undecanoic acid monolayers, covalently linked to smooth silicon surfaces via Si-C bonds. The resulting ultra-thin dendrimer films were characterized by X-ray photoelectron spectroscopy (XPS), X-ray reflectometry (XR) and atomic force microscopy (AFM). XPS results suggested amide bond formation between the dendrimer and the surface carboxylic acid groups. XR yielded thicknesses of 10 Å for the alkyl region of the undecanoic acid monolayer and 12 Å for the dendrimer layer, considerably smaller than the diameter of these spherical macromolecules in solution. This was consistent with AFM images showing collapsed dendrimers on the surface. It was concluded that the deformation arose from a large number of amine groups on the surface of each dendrimer reacting efficiently with the activated surface, whereby the dendrimers can deform to fill voids while spreading over the activated surface to form a homogeneous macromolecular layer.     

Biocompatibility of Amine‐Functionalized Silica Nanoparticles: The Role of Surface Coverage

Here, amorphous silica nanoparticles (NPs), one of the most abundant nanomaterials, are used as an example to illustrate the utmost importance of surface coverage by functional groups which critically determines biocompatibility. Silica NPs are functionalized with increasing amounts of amino groups, and the number of surface exposed groups is quantified and characterized by detailed NMR and fluorescamine binding studies. Subsequent biocompatibility studies in the absence of serum demonstrate that, irrespective of surface modification, both plain and amine‐modified silica NPs trigger cell death in RAW 264.7 macrophages. The in vitro results can be confirmed in vivo and are predictive for the inflammatory potential in murine lungs. In the presence of serum proteins, on the other hand, a replacement of only 10% of surface‐active silanol groups by amines is sufficient to suppress cytotoxicity, emphasizing the relevance of exposure conditions. Mechanistic investigations identify a key role of lysosomal injury for cytotoxicity only in the presence, but not in the absence, of serum proteins. In conclusion, this work shows the critical need to rigorously characterize the surface coverage of NPs by their constituent functional groups, as well as the impact of serum, to reliably establish quantitative nanostructure activity relationships and develop safe nanomaterials.     

Synthesis and characterization of functionalized rhodamine B-doped silica nanoparticles

In this paper, we have prepared the fluorescent silica nanoparticles (FSNPs) covalently doped with rhodamine B (RB) dye molecules via 3-aminopropyltriethoxysilane (APTES) in reverse microemulsion method. Then by the cohydrolysis and polymerization of tetraethoxysilane (TEOS) and APTES, the surface of the FSNPs formed another thin silica shell with the functionalized amino groups. The resulting nanoparticles were characterized by infrared (IR) spectrum, transmission electron microscopy (TEM), and spectrofluorimetry. TEM showed that the particles with diameters in the range of 70–500 nm were obtained, with core and shell sizes controlled by varying component content. At the same time, the effect of RB content on the fluorescent properties of the FSNPs was studied, and the results indicated that the fluorescence intensity of the FSNPs could be precisely tuned by varying the doping amount of RB dyes. Finally, the dye leakage was also tested, displaying that RB molecules would not leak out from the silica nanoparticles after dispersing in the aqueous solution.     

TiO2-UV photocatalytic oxidation of Reactive Yellow 14: effect of operational parameters

The photocatalytic decolourisation and degradation of an azo dye Reactive Yellow (RY14) in aqueous solution with TiO(2) as photocatalyst in slurry form has been carried out using UV-A radiation (365 nm). The effect of various parameters such as catalyst loading, radiation intensity and initial dye concentration on the dye removal was investigated to find optimum conditions. The decolourisation and degradation kinetics have been analysed. Both follow modified Langmuir-Hinshelwood kinetic (L-H) model. A study on the effect of electron acceptors on photooxidation reveals that both decolourisation and degradation increase in the presence of H(2)O(2), (NH(4))(2)S(2)O(8), KBrO(3), to certain dosage beyond which the enhancement effect is negligible. But negative effects are observed in the presence of NaCl or Na(2)CO(3).     

Semiconductor-mediated photocatalysed degradation of two selected azo dye derivatives, amaranth and bismarck brown in aqueous suspension

Semiconductor-mediated photocatalysed degradation of two selected azo dye derivatives such as amaranth (1) and bismarck brown (2) has been investigated in aqueous suspension by monitoring the change in substrate concentration employing UV spectroscopic analysis technique as a function of irradiation time. The degradation was studied under different conditions such as types of TiO(2), pH, substrate concentration, catalyst concentration, and in the presence of electron acceptors such as hydrogen peroxide (H(2)O(2)), potassium bromate (KBrO(3)) and ammonium persulphate (NH(4))(2)S(2)O(8) besides air. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 showed comparatively highest photocatalytic activity. The dye derivative, bismarck brown (2) was found to degrade faster than amaranth dye (1).     

Cu nanoparticle preparation in a tube-in-tube microchannel reactor and encapsulation by silica

An approach to fabricate Cu@SiO₂ nanostructured materials was presented by using Cu nanoparticles (NPs) produced in a tube-in-tube microchannel reactor (TMR) as the core. Due to the excellent micromixing efficiency of the TMR, monodisperse Cu NPs of sub-5 nm were easily obtained. A combination of the direct silica-coating technique with the remarkable ability of the TMR for mass production of nanoparticles may open an economic pathway for producing core-shell nanomaterials.     

Direct electrochemistry of laccase immobilized on au nanoparticles encapsulated-dendrimer bonded conducting polymer: application for a catechin sensor

The direct electrochemistry of laccase was promoted by Au nanoparticle (AuNP)-encapsulated dendrimers (Den), which was applied for the detection of catechin. To increase the electrical properties, AuNPs were captured in the interiors of the dendrimer (Den-AuNPs) as opposed to attachment at the periphery of dendrimer. To prepare Den-AuNPs, the Au(III) ions were first coordinated in the interior of dendrimer with nitrogen ligands and then reduced to form AuNPs. The size of AuNPs encapsulated within the interior of the dendrimer was determined to be 1.7 +/- 0.4 nm. AuNPs-encapsulated dendrimers were then used to covalently immobilize laccase (PDATT/ Den(AuNPs)/laccase) through the formation of amide bonds between carboxylic acid groups of the dendrimer and the amine groups of laccase. Each layer of the PDATT/Den(AuNPs)/laccase probe was characterized using CV, EIS, QCM, XPS, SEM, and TEM. The PDATT/Den(AuNPs)/laccase probe displayed a well-defined direct electron-transfer (DET) process of laccase. The quasi-reversible redox peak of the Cu redox center of the laccase molecule was observed at -0.03/+0.13 V vs Ag/AgCl, and the electron-transfer rate constant was determined to be 1.28 s (-1). A catechin biosensor based on the electrocatalytic process by direct electrochemistry of laccase was developed. The linear range and the detection limit in the catechin analysis were determined to be 0.1-10 and 0.05 +/- 0.003 microM, respectively. Interference effects from various phenolic and polyphenolic compounds were also studied, and the general applicability of the biosensor was evaluated by selective analysis of real samples of catechin.     

Modifying the adsorption behavior of polyamidoamine dendrimers at silica surfaces investigated by total internal reflection fluorescence correlation spectroscopy

Polyamidoamine (PAMAM) dendrimers were modified and tested for use as solution-phase diffusion probes in silica nanostructures. In order for the successful application of dendrimers as solution-phase probes, their interactions with silica surfaces must be understood and controlled, so that the motion of the probe is not influenced by adsorption. Adsorption/desorption kinetics of PAMAM dendrimers and their diffusion in solution near silica surfaces were investigated with total internal reflection fluorescence correlation spectroscopy (TIR-FCS). Dendrimers of generations 3, 5, and 7 were dye-labeled with carboxyrhodamine 6G. Because PAMAM dendrimers are positively charged in solution (having primary amines as end groups), significant adsorption of these molecules to the negatively charged silica surface was observed. Adsorption/desorption rates and the equilibrium constant for adsorption were determined by fitting the autocorrelation functions to a kinetic model. The desorption rate decreases and the absorption equilibrium constant increases with higher dendrimer generation. To reduce the adsorption of these probes to silica surfaces, the labeled dendrimers were reacted with succinic anhydride, converting the primary amine end groups to negatively charged carboxylic acid groups. These carboxylated dendrimers did not detectably adsorb to silica from aqueous solution. TIR-FCS was used to determine their free-solution diffusion constants near silica surfaces, and the corresponding hydrodynamic radii compare favorably with values reported from forced Rayleigh scattering measurements.     

Molecular boxes on a molecular printboard: encapsulation of anionic dyes in immobilized dendrimers

Fifth-generation poly(propylene imine) dendrimers, modified with 64 apolar adamantyl groups, have been immobilized on cyclodextrin host monolayers ("molecular printboards") on glass by supramolecular microcontact printing. The immobilized dendrimers retain their guest-binding properties and function as "molecular boxes" that can be filled with fluorescent dye molecules from solution. Alternatively, part of the immobilized dendrimers were filled with dye molecules by cross-microcontact printing while the remaining, empty dendrimers were filled with a different dye from solution, resulting in alternating patterns of dye molecules. In addition, we demonstrate that encapsulation of dyes in immobilized dendrimers is reversible: immobilized molecular boxes can be filled with a dye, emptied, and subsequently refilled with a different dye.     

New photocatalysts based on MIL-53 metal-organic frameworks for the decolorization of methylene blue dye

The photocatalytic decolorization of methylene blue dye in aqueous solution using a novel photocatalyst MIL-53(Fe) metal-organic frameworks was investigated under UV-vis light and visible light irradiation. The effect of electron acceptor H(2)O(2), KBrO(3) and (NH(4))(2)S(2)O(8) addition on the photocatalytic performance of MIL-53(Fe) was also evaluated. The results show that MIL-53(Fe) photocatalyst exhibited photocatalytic activity for MB decolorization both under UV-vis light and visible light irradiation, and the MB decolorization over MIL-53(Fe) photocatalyst followed the first-order kinetics. The addition of different electron acceptors all enhances the photocatalytic performance of MIL-53(Fe) photocatalyst, and the enhanced rate follows the order of H(2)O(2)>(NH(4))(2)S(2)O(8)>KBrO(3) under UV-vis light irradiation, while in the order of (NH(4))(2)S(2)O(8)>H(2)O(2)>KBrO(3) under visible light irradiation. Moreover, MIL-53(Fe) did not exhibit any obvious loss of the activity for MB decolorization during five repeated usages. The photocatalytic activities over MIL-53(M) (M=Al, Fe), the isostructure to MIL-53(Fe), indicate that the metal centers show nil effect on the photocatalytic activity of MIL-53(M) photocatalysts.