A two-point calibration method for quantifying organic binary mixtures using secondary ion mass spectrometry in the presence of matrix effects

Quantification of the composition of binary mixtures in secondary ion mass spectrometry (SIMS) is required in the analyses of technological materials from organic electronics to drug delivery systems. In some instances, it is found that there is a linear dependence between the composition, expressed as a ratio of component volumes, and the secondary ion intensities, expressed as a ratio of intensities of ions from each component. However, this ideal relationship fails in the presence of matrix effects and linearity is observed only over small compositional ranges, particularly in the dilute limits. In this paper, we assess an empirical method, which introduces a power law dependence between the intensity ratio and the volume fraction ratio. A previously published physical model of the organic matrix effect is employed to test the limits of the method and a mixed system of 3,3′-bis(9-carbazolyl) biphenyl and tris(2-phenylpyridinato)iridium (III) is used to demonstrate the method. This paper introduces a two-point calibration, which determines both the exponent in the power law and the sensitivity factor for the conversion of ion intensity ratio into volume fraction ratio. We demonstrate that this provides significantly improved accuracy, compared with a one-point calibration, over a wide compositional range in SIMS quantification and with a weak dependence on matrix effects. Because the method enables the use of clearly identifiable secondary ions for quantitative purposes and mitigates commonly observed matrix effects in organic materials, the two-point calibration method could be of significant benefit to SIMS analysts.     

Spectral editing in solid-state MAS NMR of quadrupolar nuclei using selective satellite inversion

A sensitivity enhancement method based on selective adiabatic inversion of a satellite transition has been employed in a (pi/2)CT-(pi)ST1-(pi/2)CT spectral editing sequence to both enhance and resolve multisite NMR spectra of quadrupolar nuclei. In addition to a total enhancement of 2.5 times for spin 3/2 nuclei, enhancements up to 2.0 times is reported for the edited sites in a mixture of rubidium salts.     

Reliability of Speaking and Maximum Voice Range Measures in Screening for Dysphonia

Speech range profile (SRP) is a graphical display of frequency-intensity occurring interactions during functional speech activity. Few studies have suggested the potential clinical applications of SRP. However, these studies are limited to qualitative case comparisons and vocally healthy participants. The present study aimed to examine the effects of voice disorders on speaking and maximum voice ranges in a group of vocally untrained women. It also aimed to examine whether voice limit measures derived from SRP were as sensitive as those derived from voice range profile (VRP) in distinguishing dysphonic from healthy voices. Ninety dysphonic women with laryngeal pathologies and 35 women with normal voices, who served as controls, participated in this study. Each subject recorded a VRP for her physiological vocal limits. In addition, each subject read aloud the "North Wind and the Sun" passage to record SRP. All the recordings were captured and analyzed by Soundswell's computerized real-time phonetogram Phog 1.0 (Hitech Development AB, T?by, Sweden). The SRPs and the VRPs were compared between the two groups of subjects. Univariate analysis results demonstrated that individual SRP measures were less sensitive than the corresponding VRP measures in discriminating dysphonic from normal voices. However, stepwise logistic regression analyses revealed that the combination of only two SRP measures was almost as effective as a combination of three VRP measures in predicting the presence of dysphonia (overall prediction accuracy: 93.6% for SRP vs 96.0% for VRP). These results suggest that in a busy clinic where quick voice screening results are desirable, SRP can be an acceptable alternate procedure to VRP.     

Large-scale plasmonic-SERS templates by successive growth steps

This work presents the fabrication of large-scale tunable-plasmonic surface-enhanced Raman scattering (SERS) templates and investigates their Raman enhancement. Substrates for SERS were prepared by deposition of gold nanoparticles on a glass slide followed by their growth. A plasmon shift was observed upon growing due to the formation of elongated nanoparticles and their mutual coupling. The changes in particle size, shape and interparticle distances were indicated by SEM measurements. Surface-enhanced Raman spectra of Nile blue A at a very low concentration on top of a blocking layer were measured. The overall Raman enhancement is correlated with the number of growth steps. For excitation at 532 nm four growth steps lead to maximum enhancement. Better overlap of excitation laser and the plasmon resonances upon growing increased the enhancement until four steps while further growing decreased the enhancement. At longer wavelengths excitation (633 and 785 nm) the enhancement further increased beyond the fourth growth step. This enhancement is caused by the plasmon excitation of narrower gap sizes. The proposed procedure for the SERS substrates is simple, allows covering large surface areas and plasmon band tuning from 530 nm to the near infrared in order to increase overall Raman enhancement.     

Heteronuclear Cross‐Relaxation Effects in the NMR Spectroscopy of Hyperpolarized Targets

Dissolution dynamic nuclear polarization (DNP) enables high‐sensitivity solution‐phase NMR experiments on long‐lived nuclear spin species such as ¹⁵N and ¹³C. This report explores certain features arising in solution‐state ¹H NMR upon polarizing low‐γ nuclear species. Following solid‐state hyperpolarization of both ¹³C and ¹H, solution‐phase ¹H NMR experiments on dissolved samples revealed transient effects, whereby peaks arising from protons bonded to the naturally occurring ¹³C nuclei appeared larger than the typically dominant ¹²C‐bonded ¹H resonances. This enhancement of the satellite peaks was examined in detail with respect to a variety of mechanisms that could potentially explain this observation. Both two‐ and three‐spin phenomena active in the solid state could lead to this kind of effect; still, experimental observations revealed that the enhancement originates from ¹³C→¹H polarization‐transfer processes active in the liquid state. Kinetic equations based on modified heteronuclear cross‐relaxation models were examined, and found to well describe the distinct patterns of growth and decay shown by the ¹³C‐bound ¹H NMR satellite resonances. The dynamics of these novel cross‐relaxation phenomena were determined, and their potential usefulness as tools for investigating hyperpolarized ensembles and for obtaining enhanced‐sensitivity ¹H NMR traces was explored.     

纳米银对铕配合物荧光性质的影响(英文)

研究了纳米银对稀土铕-吡啶-2,6-二羧酸配合物(Eu(Ⅲ)C7H5NO4,Eu(Ⅲ)DPA)的荧光性质的影响。随着纳米银浓度增加,荧光强度先增强而后逐渐下降。较大粒径的纳米银使Eu(Ⅲ)DPA荧光增强效率较大,且达到最大荧光增强效率所需的纳米银浓度较低。在高浓度Eu(Ⅲ)DPA溶液体系中,纳米银导致荧光猝灭。电偶极子跃迁发射荧光增强效率大于磁偶极子跃迁发射荧光增强效率。分析认为,纳米银对Eu(Ⅲ)DPA荧光性质的影响与表面等离子体共振与激发态荧光中心强烈耦合以及表面等离子体再吸收有关。同时,纳米银对铕配合物的不对称率有影响,其影响因素与局域电磁场增强,折射率以及配位场有关。     

Ag/ZrO2-NT/Zr hybrid material: A new platform for SERS measurements

In this paper, we present recent results of our attempts to produce nanoporous zirconia, as well as our investigations of a hybrid material consisting of nanoporous zirconia loaded with Ag-nanoparticles, Ag-n/ZrO₂-NT/Zr, which could be used as an active SERS substrate. The Zr-based hybrid material, as our investigations have shown, is an active and stable substrate in SERS investigations aimed at detecting various organic molecules: mercaptobenzoic acid, pyridine and two different dyes – rodhanine derivatives. The SERS spectra for the probe molecules adsorbed on silver nanoparticles on a ZrO₂-NT/Zr platform display characteristic intensity ratios different from those measured on previously studied nanoporous substrates based on Ti and Al, which ensure a different (alternative) interaction between the investigated adsorbate and adsorbent. In order to characterize our new substrate we used high-resolution SEM and surface analytical techniques: XPS (X-ray photoelectron spectroscopy) and SERS (surface enhanced Raman spectroscopy).     

Pressure-Suppressed Carrier Trapping Leads to Enhanced Emission in Two-Dimensional Perovskite (HA)2(GA)Pb2I7

A remarkable PL enhancement by 12 fold is achieved using pressure to modulate the structure of a recently developed 2D perovskite (HA)₂(GA)Pb₂I₇ (HA=n-hexylammonium, GA=guanidinium). This structure features a previously unattainable, extremely large cage. In situ structural, spectroscopic, and theoretical analyses reveal that lattice compression under a mild pressure within 1.6 GPa considerably suppresses the carrier trapping, leading to significantly enhanced emission. Further pressurization induces a non-luminescent amorphous yellow phase, which is retained and exhibits a continuously increasing band gap during decompression. When the pressure is released to 1.5 GPa, emission can be triggered by above-band gap laser irradiation, accompanied by a color change from yellow to orange. The obtained orange phase could be retained at ambient conditions and exhibits two-fold higher PL emission compared with the pristine (HA)₂(GA)Pb₂I₇.     

Enhancing the performance of TFC nanofiltration membranes by adding organic acids in polysulfone support layer

Throughout this study, the effect of certain organic acids, methacrylic acid, lactic acid and tartaric acid, doped in polysulfone (PSF) casting solution onto the performance of nanofiltration (NF) membranes was investigated. Different NF membranes have been prepared from m-phenylenediamine and trimesoylchloride onto the top surface of the acid-modified PSF membranes through regulating the concentration and contact time of the conventional interfacial polymerization process. The study of scanning electron microscopy (SEM) was used to investigate the influence of acids on the morphology of membranes and cross-sectional structures. The functional groups, hydroxyl and carboxylic acid, of the acids have resulted in a significant increase in membrane thickness, porosity and hydrophilicity, with a decrease in macrovoid capacity of the PSF layer. The acid-modified PSF/TFC membranes showed higher rejection of salt, with an increment in water flux compared to the neat membrane. Water flux and salt rejection (R_s %) of the control membrane was 7.6 L/m² h and 65.4%, whereas polysulfone/methacrylic acid (PSF/MAAc), polysulfone/tartaric acid (PSF/TAc), and polysulfone/lactic acid (PSF/LAc) were 16.8, 18.5, and 20.2 L/m² h and 88, 88.2 and 94.1%, respectively. Efficiency of prepared NF membranes under various inlet pressures and specific salts was investigated with selectivity and salt rejection. The salt rejection of a mixed salt solution was found to meet the order of R_s % CaSO₄ ≥ R_s % Na₂SO₄ ˃ R_s % MgSO₄ ˃ R_s MgCl₂ ˃ Rs % NaCl.     

超高分子量聚乙烯烧结制品的链缠结调控及其对性能影响

利用新的单中心Ziegler-Natta(Z-N)催化剂,通过干预分子链的生长与聚集行为,可获得低缠结的超高分子量聚乙烯(UHMWPE)初生树脂.本研究利用这类低缠结UHMWPE,通过设置不同的烧结温度(Ts)来改变熔体缠结状态,并探讨了链缠结程度对烧结制品结构与性能的影响.实验结果表明TS=220℃下,UHMWPE样品发生显著的复缠,造成高缠结度;而Ts=170℃下,初始低缠结状态能够得以充分保留,从而获得了缠结度具有明显差别的不同样品.示差扫描量热法(DSC)测试表明,在Ts=170℃下,低缠结度有利于在随后等温及冷却结晶过程中生成高熔点(最高达141℃)晶体与高的结晶度(最高达65%).力学测试表明低缠结度制品的综合力学性能显著提升,其中屈服强度提高72%,拉伸断裂强度提升139%,弹性模量提升162%以及断裂伸长率提升36%,实现了同时增强增韧.这就提供了一种从调节链缠结温度实现UHMWPE烧结制品高性能化的新思路.