Probing Single Nanometer-scale Particles with Scanning Tunneling Microscopy and Spectroscopies

Scanning tunneling microscopy can be used to isolate single particles on surfaces for further study. Local optical and electronic properties coupled with topographic information collected by the scanning tunneling microscope (STM) give insight into the intrinsic properties of the species under study. Since each spectroscopic measurement is done on a single particle, each sample is monodisperse, regardless of the degree of heterogeneity of the original preparation. We illustrate this with three example systems – a metal cluster of known atomic structure, metal nanoparticles dispersed from colloid suspensions, and metallocarbohedrenes (Met-Cars) deposited with other reaction products. Au and Ag nanoparticles were imaged using a photon emission STM. The threshold voltage, the lowest bias voltage at which photons are produced, was determined for Au nanoparticles. Electronic spectra of small clusters of Ni atoms on MoS₂ were recorded. Preliminary images of Zr-based Met-Car-containing soot were obtained on Au and MoS₂ substrates and partial electronic spectra were recorded of these possible Met-Car particles.     

First-principles calculations of K-shell x-ray absorption spectra for warm dense ammonia

The x-ray absorption spectroscopy is a powerful tool for the detection of thermodynamic conditions and atomic structures on warm dense matter. Here, we perform first-principles molecular dynamics and x-ray absorption spectrum calculations for warm dense ammonia, which is one of the major constituents of Uranus and Neptune. The nitrogen K-shell x-ray absorption spectrum(XAS) is determined along the Hugoniot curve, and it is found that the XAS is a good indicator of the prevailing thermodynamic conditions. The atomic structures at these conditions are ascertained. Results indicate that the ammonia could dissociate to NH_x(x = 0, 1, or 2) fragments and form nitrogen clusters, and the ratios of these products change with varying conditions. The contributions to the XAS from these products show quite different characteristics,inducing the significant change of XAS along the Hugoniot curve. Further model simulations imply that the distribution of the peak position of atomic XAS is the dominant factor affecting the total XAS.     

Highly Water‐Dispersible,Highly Conductive,and Biocompatible Polypyrrole‐Coated Silica Particles Stabilized and Doped by Chondroitin Sulfate

Currently available methods to prepare conducting polymers‐coated colloidal substrates for biomedical applications need to be improved because they involve the use of toxic reagents and tend to result in aggregated products with diminished conductivity. The work herein describes for the first time a facile strategy for preparing highly water‐dispersible, highly conductive, and biocompatible polypyrrole‐coated silica core–shell (SiO₂@PPy) particles using only chondroitin sulfate (CS), a biologically derived polymer, as the stabilizer and dopant. The CS preadsorbed onto silica surface serves as a template to control the confined growth of the PPy shell and doping of in situ polymerized PPy shell. The thickness of the PPy shell can be tuned from 8 to 17 nm by varying the CS preadsorbed amount. Increasing the thickness of the adsorbed CS layer can control the deposition of thinner PPy shells on an SiO₂ core surface to provide highly water‐dispersible SiO₂@PPy particles. Moreover, CS‐doped SiO₂@PPy particles exhibit conductivities as high as 5.3 S cm^?1. The conductivity of the particles depends on the PPy mass loading and the doping level of the PPy shell. Furthermore, the SiO₂@PPy particles exhibit good biocompatibility and therefore have potential applications in biomedicine.     

具有优先权和准备时间的自由作业时间表问题

研究具有优先权和准备时间的自由作业时间表问题 ,在稠密时间表的情况下 ,给出一种启发式算法 ,猜想该算法的紧界是 2 -2 /( m +1 ) ,其中 m是机器台数 .对于只有两台机器的情况 ,即当 m =2 时 ,证明该算法的最坏性能比是 4/3 ,并通过实例证明上界是紧的 .     

Linear extensions of orderings

A construction is given which makes it possible to find all linear extensions of a given ordered set and, conversely, to find all orderings on a given set with a prescribed linear extension. Further, dense subsets of ordered sets are studied and a procedure is presented which extends a linear extension constructed on a dense subset to the whole set.     

电解法制备纳米溴化银溶胶及其SERS活性研究

将一定量的十六烷基三甲基溴化铵溶于500 mL去离子水中作为电解液,用直径为1.0 cm、长为10.0 cm银棒分别作为阴及阳电极,加上7 V直流电压,通电 3 h,用电解方法得到了乳白色的纳米溴化银溶胶。用吸收光谱、对该进行研究。其吸收峰为292.5 nm, 透射式电镜表明纳米溴化银粒径分布在一个较大的范围,既有大小不一的球形粒子,也有大小不一的椭球形粒子,部分粒子产生了凝聚。为测试该纳米溴化银溶胶是否具有表面增强拉曼散射(SERS)活性,选用了阳离子型分子甲基橙(Methyl orange)、中性分子苏丹红(Sudan red)及吡啶(Pyridine)作为测试分子,用二次去离子水配成适当浓度后,与纳米溴化银溶胶按1∶1的比例混合后,置入毛细管样品池中用Renishaw 2000测定,激发波长514.5 nm。结果发现电解法制备的纳米溴化银对这三种分子都具有较强的SERS活性,甲基橙中明显增强的峰是1 123,1 146,1 392,1 448,1 594 cm-1;苏丹红中明显增强的峰是1 141,1 179,1 433,1 590 cm-1;吡啶中明显增强的峰是1 003,1 034,1 121 cm-1。值得注意的是在该方法制备的纳米溴化银上,得到了在常规方法制备的黄银胶、灰银胶上得不到的甲基橙分子的SERS谱,对可能的原因进行了讨论。     

Densely Packed Hydrophobic Clustering: Encapsulated Valerates Form a High‐Temperature‐Stable {Mo132} Capsule System

Porous molecular nanocontainers of {Mo₁₃₂}‐type Keplerates offer unique opportunities to study a wide variety of relevant phenomena. An impressive example is provided by the highly reactive {Mo₁₃₂‐CO₃} capsule, the reaction of which with valeric acid results in the very easy release of carbon dioxide and the uptake of 24 valerate ions/ligands that are integrated as a densely packed aggregate, thus indicating the unique possibility of hydrophobic clustering inside the cavity. Two‐dimensional NMR techniques were used to demonstrate the presence of the 24 valerates and the stability of the capsule up to ca. 100 °C. Increasing the number of hydrophobic parts enhances the stability of the whole system. This situation also occurs in biological systems, such as globular proteins or protein pockets.     

Singular behavior of the density of states and the Lyapunov coefficient in binary random harmonic chains

We study the integrated density of statesH( ²) of a chain of harmonic oscillators with a binary random distribution of the masses. We show in particular that there is a dense set of values of the squared frequency for which the differenceH( ²+)-H( ²) has a singularity of the type ¦¦², multiplied by a periodic function of ln ¦¦, where the exponent and the period depend continuously on ². In the region where < 1/2,H is not differentiate on a dense set of points. The same type of singularities is also present in the Lyapunov coefficient.     

Interactions of thorium isotopes with colloidal organic matter in oceanic environments

The phase speciation of thorium and consequences for the residence times of colloids have been examined in seawater of the Middle Atlantic Bight (MAB) and the Gulf of Mexico. Two fractions of colloidal organic matter (COM), 0.2 μm > COM₁ > 1 kD and 0.2 μm > COM₁₀ > 10 kD, were sampled using cross-flow ultrafiltration techniques and measured for their ²³⁴Th activity and organic carbon concentration. The ratios of mass concentrations of COM₁ to those of suspended particulate matter were as high as 10 in the MAB and 6–34 in the Gulf of Mexico. Higher concentrations of colloids may be of great importance in the biogeochemical cycling of many particle-reactive nuclides or trace elements owing to their high specific surface area and complexation capacity. A significant fraction of ²³⁴Th in the traditionally defined “dissolved” pool was found to be associated with colloids. On average, about 10% of “dissolved” ²³⁴Th was in the colloidal fraction of sizes between 10 kDa and 0.2 μm, and 50% was in the 1 kDa-0.2 μm fraction. Values of the partition coefficients [K_c: (0.5−4) × 10⁶ ml g⁻¹ for K_c1 and (0.5−7) × 10⁶ ml g⁻¹ for K_c10] of ²³⁴Th between truly dissolved (<1 kDa) and colloidal fractions approximated those for Th-particle interactions [K_p: (0.3−10) × 10⁶ ml g⁻¹], indicating that colloid and suspended particle surface sites are similar. The distribution of ²³⁴Th between dissolved, colloidal, and particulate phases was broadly similar to that of organic carbon in these oceanic environments. Thus, thorium isotopes might be used as tracers of marine organic carbon cycling. Residence times of colloids derived from ²³⁴Th:²³⁸U disequilibria were consistently short, ranging from 1 to 14 days for COM₁₀ and from 5 to 65 days for COM₁, suggesting that marine colloids are highly reactive in marine biogeochemical processes. The discrepancy between apparent turnover times of colloids (1 kDa) derived from Th scavenging and ¹⁴C measurements suggest that ²³⁴Th and ¹⁴C may trace different geochemical pathways of colloids in the ocean.