Engineering Efficient Self-Assembled Plasmonic Nanostructures by Configuring Metallic Nanoparticle’s Morphology

We reveal the significance of plasmonic nanoparticle’s (NP) shape and its surface morphology en route to an efficient self-assembled plasmonic nanoparticle cluster. A simplified model is simulated in the form of free-space dimer and trimer nanostructures (NPs in the shape of a sphere, cube, and disk). A ~200% to ~125% rise in near-field strength (gap mode enhancement) is observed for spherical NPs in comparison with cubical NPs (from 2 nm to 8 nm gap sizes). Full-width three-quarter maximum reveals better broad-spectral optical performance in a range of ~100 nm (dimer) and ~170 nm (trimer) from spherical NPs as compared to a cube (~60 nm for dimer and trimer). These excellent properties for sphere-based nanostructures are merited from its dipole mode characteristics.     

A negative resist for KrF excimer laser lithography

The design and preparation of a series of negative resists for KrF excimer laser lithography are described. Each resist is composed of poly(hydroxystyrene) and an aromatic azide. The base resin shows high transmittance of 62%/μm at 248 nm, when p-ethylphenyl p-azidophenylsulfonate. 4-azido-4α-methoxy-chalcone, 1-(4 azidobenzylidene)-3-(α-hydroxy-4-azidobenzyl)-indene, 4,4α-diazido-3,3α-dimethoxybiphenyl, or 1-(4-azidostyryl)-5, 5-dimethyl-2-cyclohexen-1-one is employed as a sensitizer. These azides are obtained by red-shifting the absorption maxima to lower energy regions than the exposing wavelength of 248 nm. Transmittance of resists can be controlled from 10 to 30%. The resist is exposed with a KrF excimer laser stepper and developed in an alkaline solution. Sensitivities of about 15 mJ/cm² are observed. A good, subhalf-micron resist profile is achieved. The photochemical reaction mechanisms of poly(hydroxystyrene) and 4,4α-diazido-3,3α-dimethoxybiphenyl were studied at 248 nm and 313 nm exposure. Quantum yield for photodecomposition at 248 nm is seven times larger than that at 313 nm, but dissolution-inhibition effects are larger at 313 nm exposure. Consequently, the resist shows higher sensitivity at 313 nm than at 248 nm.     

Nanostructure of Nafion membrane material as a function of mechanical load studied by SAXS

The nanostructure of a perfluorinated membrane material (Nafion 117 by DuPont) is investigated as a function of strain and load by small-angle X-ray scattering (SAXS) at a synchrotron source. Two-dimensional SAXS patterns are evaluated utilizing the multi-dimensional chord distribution function (CDF). Anisotropy of the extruded material is considered. Both the ionomer domain and matrix polymer nanostructure are studied. For the neat material the classical ionomer domain model (domains as inverted micellae interconnected by channels) is confirmed and refined. Matching the plastic deformation behavior of the material, the domain structure in the relaxed and in the elongated state are found to be very similar.During elongation, ionomer channels open to form hollow ionomer layers(‘slits’) that are oriented parallel to the strain with a thickness of 1.9 nm and a long period of 3.8 nm. The slit height increases from 3 nm at elongation ε=0.5 to 6 nm at ε=1.25, whereas the slit width decreases to 1.5 nm. The ultimate structure is characterized by ensembles of not more than three slits that are in good lateral register.In the polymer matrix during elongation, cylindrical crystallites with a thickness of 2.5 nm and a most probable height of 7 nm are disrupted and parallelized with respect to the straining direction. The ultimate structure before sample failure is characterized by a broad domain height distribution ranging from a most probable domain height of 4 nm with a corresponding ultimate inclination of 40° to some perfectly parallelized domains of 20 nm height.     

Online Nanoparticle Mass Measurement by Combined Aerosol Particle Mass Analyzer and Differential Mobility Analyzer: Comparison of Theory and Measurements

A combination of a differential mobility analyzer (DMA) and aerosol particle mass analyzer (APM) is used to measure the mass of NIST Standard Reference Materials (SRM®) PSL spheres with 60 and 100 nm nominal diameter, and NIST traceable 300 nm PSL spheres. The calibration PSL spheres were previously characterized by modal diameter and spread in particle size. We used the DMA to separate the particles with modal diameter in a narrow mobility diameter range. The mass of the separated particles is measured using the APM. The measured mass is converted to diameter using a specific density of 1.05. We found that there was good agreement between our measurements and calibration modal diameter. The measured average modal diameters are 59.23 and 101.2 nm for nominal diameters of 60 and 100 nm (calibration modal diameter: 60.39 and 100.7 nm) PSL spheres, respectively. The repeatability uncertainty of these measurements is reported. For 300 nm, the measured diameter was 305.5 nm, which is an agreement with calibration diameter within 1.8%.

The effect of spread in particle size on the APM transfer function is investigated. Two sources of the spread in “mono-dispersed” particle size distributions are discussed: (a) spread due to the triangular DMA transfer function, and (b) spread in the calibration particle size. The APM response function is calculated numerically with parabolic flow through the APM and diffusion broadening. As expected from theory, the calculated APM response function and measured data followed a similar trend with respect to APM voltage. However, the theoretical APM transfer function is narrower than the measured APM response.     

Reduced charge recombination in a co-sensitized quantum dot solar cell with two different sizes of CdSe quantum dot

An efficient photoelectrode is fabricated by sequentially assembling 2.5 nm and 3.5 nm CdSe quantum dots (QDs) onto a TiO2 film. As revealed by UV-vis absorption spectroscopy, two sizes of CdSe QD can be effectively adsorbed on the TiO2 film. With a broader light absorption range and better coverage of CdSe QDs on the TiO2 film, a power conversion efficiency of 1.26% has been achieved for the TiO2/CdSe QD (2.5 nm)/CdSe QD (3.5 nm) cell under the illumination of one Sun (AM 1.5G, 100 mW cm(-2)). Electrochemical impedance spectroscopy shows that the electron lifetime for the device based on TiO2/CdSe QD (2.5 nm)/CdSe QD (3.5 nm) is longer than that for devices based on TiO2/CdSe QD (2.5 nm) and TiO2/CdSe QD (3.5 nm), indicating that the charge recombination at the interface is reduced by sensitizing with two kinds of CdSe QDs.     

Synthesis of brushite particles in reverse microemulsions of the biosurfactant surfactin

In this study the "green chemistry" use of the biosurfactant surfactin for the synthesis of calcium phosphate using the reverse microemulsion technique was demonstrated. Calcium phosphates are bioactive materials that are a major constituent of human teeth and bone tissue. A reverse microemulsion technique with surfactin was used to produce nanocrystalline brushite particles. Structural diversity (analyzed by SEM and TEM) resulted from different water to surfactin ratios (W/S; 250, 500, 1000 and 40,000). The particle sizes were found to be in the 16-200 nm range. Morphological variety was observed in the as-synthesized microemulsions, which consisted of nanospheres (~16 nm in diameter) and needle-like (8-14 nm in diameter and 80-100 nm in length) noncalcinated particles. However, the calcinated products included nanospheres (50-200 nm in diameter), oval (~300 nm in diameter) and nanorod (200-400 nm in length) particles. FTIR and XRD analysis confirmed the formation of brushite nanoparticles in the as-synthesized products, while calcium pyrophosphate was produced after calcination. These results indicate that the reverse microemulsion technique using surfactin is a green process suitable for the synthesis of nanoparticles.     

钨酸钆镉单晶的光致发光性能

采用提拉法生长了钨酸钆镉[CdGd2(WO4)4, CGW]单晶.在室温下测试和研究了CGW单晶的光致发光谱和X射线能量色散谱.结果表明:样品中有Gd,Cd,W和O元素,未见其他杂质元素;样品的发光性质随激发波长的不同而有所变化.在313 nm波长光激发下,有3个发光带,分别为447 nm蓝光,487 nm蓝绿光和545 nm绿光;在353 nm波长光激发下,不仅有蓝光、蓝绿光和绿光出现,另外出现了575 nm黄光发光峰;在367 nm波长的光激发下,出现775 nm红光发光峰.对发光机制分析认为:蓝光和蓝绿光为本征发射,起源于WO42-离子团的内部电子跃迁;绿光起源于"WO42- Oi";黄光和红光起源于WO3内部跃迁.     

Potential aspect of rice husk biomass in Australia for nanocrystalline cellulose production

Nanocrystalline cellulose(NCC) was produced from rice husk biomass(Oryza sativa) by a chemical extraction process to explore the potential aspect of agro-waste biomass in Australia. In this work, the delignified rice husk pulp(D-RHP) was produced by alkaline delignification of raw rice husk biomass(R-RHB) using 4 mol·L~(-1) alkali solutions(Na OH) in a jacketed glass reactor under specific experimental conditions. D-RHP was bleached using 15% sodium hypochlorite, and the bleached rice husk pulp was coded as B-RHP. Finally,raw suspension of NCC was produced by the acid hydrolysis of B-RHP using 4 mol·L~(-1) sulphuric acid. The raw suspension of NCC was neutralized by a buffer solution and analyzed by TAPPI, FT-IR, XRD, SEM, AFM, and TEM. FT-IR spectra of NCC are different to R-RHB but similar with B-RHP and D-RHP. From XRD results, the crystallinity of NCC was found to be approximately 65%. In AFM analysis particle thicknesses have been confirmed to be in the range of(25 ± 15.14) nm or(27 ± 15.14) nm which is almost the same. From TEM analysis particle dimensions have been confirmed to be in the range of(50 ± 29.38) nm width and(550 ± 302.75) nm length with the aspect ratio ~ 11:1(length/diameter) at a 500 nm scale bar. On the other hand, at a 200 nm scale bar the particle dimensions have been confirmed to be in the range of(35 ± 17) nm width and(275 ± 151.38)nm length with the aspect ratio ~ 8:1. The aspect ratio of individual crystalline domain was determined in TEM analysis which is 10:1(100/10). Therefore the aspect ratios and dimensions of nanoparticles in NCC suspension are almost the same and in nano-meter scale, as confirmed from both AFM and TEM results. The yield of NCC from B-RHP was found to be approximately 95%, and the recovery of cellulose from R-RHB is about 90%.     

Novel multi-wavelength excitable single-component phosphor system for application in white-LEDs

A novel color-tunable phosphor of BaZnO₂:xEu³⁺ (x = 0–20 mol%) has been successfully prepared via high-temperature calcination method using alkaline earth metal as the charge compensator. Uncommonly, BaZnO₂:Eu³⁺ is a multi-wavelength excitable phosphor due to its wide absorption spectrum ranging 250–550 nm. It shows broad white (400–700 nm), orange (∼580 nm) and red (∼611 nm) photoluminescence (PL) under 370 nm, 395 nm and 467 nm excitations, respectively and were assigned to one or more ⁵D₀→⁷F_J (J = 1 to 4) transitions of Eu³⁺ ion. An efficient energy transfer between Zn²⁺ and Eu³⁺ has been observed upon systematically increasing the concentration of Eu³⁺ ion. Scanning Electron Microscopy images indicated elongated rod-like structures with an average diameter of ∼20 nm. The chromaticity coordinates (x, y) were found to be positioned at white (0.33, 0.42), orange (0.51, 0.42) and red (0.65, 0.34) regions correspond to 370 nm, 395 nm and 467 nm excitations, respectively. The temperature-dependent luminescence spectrum of BaZnO₂:Eu³⁺ under the excitation of 467 nm was also studied. It exhibited good thermal stability and a marginal drop in photoluminescence intensity by 4.29% at 150 °C was observed. The mathematical calculation of the activation energy was approximately 0.20 eV. The results indicate the suitability of the phosphor for LEDs applications, which is otherwise difficult to obtain in single-component system.     

Light scattering evidence of selective protein fouling on biocompatible block copolymer micelles

Selective protein fouling on block copolymer micelles with well-known potential for tumour-targeting drug delivery was evidenced by using dynamic light scattering measurements. The stability and interaction of block copolymer micelles with model proteins (BSA, IgG, lysozyme and CytC) is reported for systems featuring a hydrophobic (poly[2-(diisopropylamino)-ethyl methacrylate]) (PDPA) core and hydrophilic coronas comprising poly(ethylene oxide)/poly(glycerol monomethacrylate) (PEO-b-PG2MA) or poly[2-(methacryloyloxy)ethyl phosphorylcholine] (PMPC). The results revealed that protein size and hydrophilic chain density play important roles in the observed interactions. The PEO(113)-b-PG2MA(30)-b-PDPA(50) nanoparticles are stable and protein adsorption is prevented at all investigated protein environments. The successful protein-repellent characteristic of these nanoparticles is attributed to a high hydrophilic surface chain density (>0.1 chains per nm(2)) and to the length of the hydrophilic chains. On the other hand, although PMPC also has protein-repellent characteristics, the low surface chain density of the hydrophilic shell is supposed to enable interactions with small proteins. The PMPC(40)-b-PDPA(70) micelles are stable in BSA and IgG environments due to weak repulsion forces between PMPC and the proteins, to the hydration layer, and particularly to a size-effect where the large BSA (R(H) = 4.2 nm) and IgG (R(H) = 7.0 nm) do not easily diffuse within the PMPC shell. Conversely, a clear interaction was observed with the 2.1 nm radius lysozyme. The lysozyme protein can diffuse within the PMPC micellar shell towards the PDPA hydrophobic core in a process favored by its smaller size and the low hydrophilic PMPC surface chain density (～0.049 chains per nm(2)) as compared to PEO-b-PG2MA (～0.110 chains per nm(2)). The same behavior was not evidenced with the 2.3 nm radius positively charged CytC, probably due to its higher surface hydrophilicity and the consequent chemical incompatibility with PDPA.     

Laser from the dimer state of a conjugated polymer (PFO) in solution

The spectral and laser properties of the conjugated polymer poly (9,9-dioctylfluorenyl-2, 7-diyl) (PFO) in benzene have been studied and presented in this paper. The absorption spectra of PFO in benzene under low concentration showed that there was only one peak at 390 nm. When the concentration was increased, a new peak at 437 nm appeared additionally, indicating dimer formation at higher concentration of PFO in benzene. The fluorescence spectra for low concentration showed two peaks at 422 nm and 444 nm, which could be attributed to the monomer and the excimer. At the longer wavelength side of these spectra, there was a hump at 465 nm. This hump became dominant for higher concentrations and in low temperatures, while the other peaks became weaker. So, this new peak at 465 nm may be due to the dimer. For still higher concentrations, the peaks at 422 nm and 444 nm vanished and there was a dominant peak only at 465 nm. Under suitable concentration and pump power excitation of Nd: YAG laser (355 nm) the amplified spontaneous emission (ASE) spectra were obtained. It could be seen that there were three ASE peaks at 422, 444 and 470 nm. These peaks could be attributed to the monomer, excimer and dimer respectively. This is perhaps the first report on ASE from dimers of the conjugated polymer, PFO in liquid solution.     

超分子化合物(C10H10N2)Co（SCN）4的合成、晶体结构和热稳定性

在室温下合成了一个新的超分子配合物(C10H10N2)Co(SCN)4,通过元素分析、红外和单晶X-射线进行了表征。标题化合物属于正交晶系,P 21 21 2空间群,a=1.283 32(11)nm、b=1.297 53(12)nm、c=0.544 12(5)nm、V=0.906 04(14)nm3、Z=2。在化合物中,每个Co2+离子与4个SCN-的4个N原子形成变形的四面体几何构型、4,4’-联吡啶的两个氮原子双质子化,并与SCN-的S原子形成N—H…S氢键,构成一维氢键超分子链。通过热重分析研究该化合物的热稳定性。     

Synthesis and crystal structure of bis(morpholino dithiocarbamato) Cd(II) complex and its use as precursor for CdS quantum dots using different capping agents

ABSTRACT

Cadmium(II) morpholine dithiocarbamate complex [Cd(morphdtc)₂] was synthesized and characterized by single crystal X-ray crystallography. The molecular structure of the complex showed Cd(II) ion in a distorted 4?+?2 octahedral geometry, in which the two morpholine dithiocarbamates act as bidentate chelating and the central Cd ion bond the sulfur atoms of adjacent morpholine acting as bridging ligands to form centrosymmetric five coordinate dimeric molecules. The Cd(II) complex was thermolysed at 180°C to prepare CdS nanoparticles using three different capping agents. The pXRD patterns revealed a mixture of hexagonal and cubic crystalline phases of CdS nanocrystals. TEM images revealed semi-spherical and spherical nanoparticles, with the size range of 4.50–5.70?nm for OLM-CdS, 3.33–5.96?nm for HDA-CdS, and 3.00–5.83?nm for ODA-CdS. The particle size distribution of the CdS nanocrystallite is within the range 1.06?nm (SD?±?0.73) for OLM-CdS, 0.68?nm, (SD?±0.73) for HDA-CdS and 1.18?nm, (SD?±?0.60) for ODA-CdS. The lattice fringes showed that the particles are almost in the same environment with the interplanar of 0.32?nm for OLM-CdS, 0.34?nm for HDA-CdS, and 0.32?nm ODA-CdS. The band gaps energy were confirmed to be 1.59?eV for OLM-CdS, 1.65?eV for HDA-CdS, and 1.62?eV for ODA-CdS nanoparticles, respectively.     

Effect of surface microstructure of TiO₂ film from micro-arc oxidation on its photocatalytic activity: a HRTEM study

Photocatalysis is a reaction that happens on the surface of catalysts around only several atomic layers. Therefore, the microstructure beneath the surface plays a key role for the improvement of photocatalytic property. In this paper, the microstructural variation of the TiO(2) film from micro-arc oxidation (MAO) was characterized by using a high resolution transmission electron microscopy (HRTEM), and the relationship between microstructures and photocatalytic activity was studied. The results revealed that: 1) The microstructural variation from the surface to the interior in the as-prepared film is as follows: an amorphous layer with thickness around 10-20 nm, an intermediate zone consisting of amorphous, anatase and few rutile TiO(2) phases with grain size about 12 nm, then the main structure consisting of anatase and few rutile TiO(2) phases with grain size around 20 nm. This variation was formed due to temperature gradient during MAO. 2) When the TiO(2) film was annealed at 450 °C for 12 h, the amorphous layer disappeared and crystallized into fine anatase grains, and, simultaneously, the grain size in the intermediate layer grew obviously from 12 nm into 18 nm, and the interior portion from 20 nm into 30 nm. 3) The photocatalysis experiments exhibited that photocatalytic activity of the post-annealed TiO(2) film was enhanced to more than twice that of the as-prepared TiO(2) film. Therefore, we propose that the crystallization of amorphous phase beneath the surface plays a key role for the improvement of its photocatalytic property.     

Oberflächenstrukturierung polymerer Fasern durch UV-Laserbestrahlung, 15. Beschreibung des Temperaturfeldes in PETP-Polymeren während und nach der Laserbestrahlung mit einem gepulsten UV-Laser

For understanding the generation of UV laser induced surface structures of PETP polymers the temperature field within the irradiated surface is calculated in dependence on the laser irradiation wavelength (193 nm, 248 nm, 308 nm), pulse time, pulse form, the irradiation intensity and depth, using temperature-independent material data of PETP polymers known from literature. For this purpose the solution function of the one-dimensional heat differential equation is used. Depending on the order of magnitude of the absorption coefficient of the polymer for UV light of different wavelengths, surface temperatures of approx. 16 000°C (193 nm), 11 000°C (248 nm) and 500°C (308 nm) are calculated at the end of the laser pulse. The temperature input within the polymer layer is limited to only a very small penetration depth. For the irradiation with the two laser wavelengths of 193 nm and 248 nm this is less then 0.4 μm. The cooling process is considerably slower, reaching the initial temperature after approx. 4 μs.     

烷基葡糖苷微乳液中苯乙烯聚合的研究

在烷基聚葡糖苷(APG0810)/苯乙烯/水三元体系O/W微乳液中,选用水溶性K2S2O8作为引发剂,制得小粒径(46.6nm)、单分散(P=0.106<0.2)聚苯乙烯颗粒。着重研究了表面活性剂浓度、引发剂浓度以及无机盐浓度对产物粒径和多分散度的影响。最后得出随表面活性剂浓度的增加胶束数目增多,聚合所得颗粒粒径变小(44.3nm),单分散性变差;而随盐浓度的增加聚合物颗粒粒径变小(45.2nm),超过一定浓度时颗粒粒径有增大的趋势;随引发剂浓度的增加聚合物粒径变小(41.2nm)。     

Measurements of Particle Loss Functions in a Differential Mobility Analyzer (TSI,Model 3071) for Different Flow Rates

Particle losses in a differential mobility analyzer (TSI, Model 3071) caused by diffusive deposition and Brownian diffusion are measured for particles in the diameter size range between 3 and 100 nm. For small sampling and aerosol flow rates (0.3 liters/min) at 20 nm, nearly 50% of the primary particles are lost; and for 2 liters/min, the particle losses have to be considered in the diameter size range below 30 nm (50% at 7 nm). From the measured penetration values, an effective tube length is derived which is useful to calculate particle losses for other flow rates through the analyzer.     

Extension of dominant wavelength scale to the full hue cycle and evidence of fundamental color symmetry

Dominant wavelength is a psychophysical scale presently limited to the spectrum. It is extended into the nonspectrals to designate the hue cycle in a continuous wavelength-based scale. To omit the fading spectrum ends, the extended scale is based on the limited spectrum of optimum color stimuli (442–613 nm). The hue cycle interval is found by many methods in agreement, e.g., from the spacing of the ideal primaries (additive and subtractive). These were recently defined as the complementary maxima and minima of several visual functions (e.g., saturation/W, spectral sensitivity, λ discrimination, complementary efficiency). Five of these six primaries are spectral, uniformly spaced at (40 ± 4) nm intervals. Interpolating the sixth (531 c magenta) as similarly spaced between adjacent primaries (blue 447 nm and red 607 nm) gives it the dual designation 407/647 as both ends of the cycle, an interval equivalent to 240 nm. Nonspectral hues are numbered serially with wavelength by interpolating green–purple complementary pairs as sinusoidallike spectral pairs. Applying the extended scale to a color circle, the six primaries reveal a sextuple symmetry of (60 ± 2)°. Only these three pairs are both complements and opposites. In a graph (hue cycles as x and y axes) of x + y color-mixture, loci of constant λ center symmetrically on the RGB primaries near 607, 531, 447 nm. © 1993 John Wiley & Sons, Inc.     

介孔SBA-15的孔径尺寸对小牛血清蛋白和溶菌酶蛋白吸附的影响(英文)

In this paper,the effects of pore-size of SBA-15 on the adsorption kinetics and equilibrium of large protein molecules Bovine serum albumin(BSA)and lysozyme(LYS)have been investigated.The mesoporous molecular sieve SBA-15 with six different pore sizes were synthesized with P123 triblock copolymer as the template agent,and 1,3,5-trimethylbenzene(TMB)and isopropyl alcohol as the pore-expanding agent.The samples were characterized by N2 adsorption/desorption,Scanning Electron Microscopy(SEM),Transmission Electron Microscopy(TEM)and X-Ray Diffraction(XRD).It is found that BSA and LYS were adsorbed rapidly on SBA-15 materials with large pores.The BSA adsorption capacity of sieve with the pore diameter of 21.4 nm reached 500 mg·g-1 within 25 minutes.However,if the pore diameter was smaller than 14 nm,the BSA adsorption capacity of the sieve was only about 220 mg·g-1.The adsorption equilibrium data fits in the Langmuir model,where the coefficient of effective use of specific area of mesoporous molecular sieve was found to be 0.03,0.18,0.37 and 0.48,corresponding to the pore diameter of 10.1 nm,13.2 nm,15.4 nm and 21.4 nm,respectively.The equilibrium loading amount of LYS on SBA-15 materials with pore size of 15.4 nm could be up to 1000 mg·g-1.The coefficient of effective use of surface area of mesoporous molecular sieve with diameter of 3.9 nm,7.4 nm,10.1 nm,13.2 nm and 15.4 nm was 0.10,0.47,0.56,0.71 and 0.79,respectively.It is also noted that greater pore size of mesoporous molecular sieve would lead to a higher coefficient of effective use of surface area.