The structure of methylthiolate and ethylthiolate monolayers on Au(111): Absence of the (√3 × √3)R30° phase

Surface structures of self-assembled methylthiolate and ethylthiolate monolayers on Au(111) have been imaged with STM. For saturation coverage of 0.33 ML at room temperature, the well-known (√3 × √3)R30° phase routinely observed for longer chain alkanethiolates does not appear under any conditions for adsorbed methylthiolate and ethylthiolate. Instead, both thiolate species organize themselves into a well-ordered 3 × 4 structure. We thus conclude that the stable structure for saturation coverage of methylthiolate/ethylthiolate on Au(111) at RT is 3 × 4, not (√3 × √3)R30° as generally believed. For coverage less than 0.33 ML, a striped-phase with short-range order is observed for methylthiolate. Fourier transform of the STM image from the striped-phase produces a clear (√3 × √3)R30° “diffraction” pattern. This strongly indicates that the (√3 × √3)R30° diffraction pattern for methylthiolate monolayers reported in literature is likely from the striped-phase, rather than from a true (√3 × √3)R30° lattice in real space. Consequently, theoretical modeling that reproduces the (√3 × √3)R30° structure for methylthiolate monolayers should be re-examined.     

Fabrication and luminescent properties of Al2O3:Cr3 + microspheres via a microwave solvothermal route followed by heat treatment

AlOOH:Cr^3 + powders were synthesized via a microwave solvothermal route at 433 K for 30 min and were used as the precursor and template for the preparation of γ-Al₂O₃:Cr^3 + by thermal transformation at 773 K for 2 h in air. The obtained γ-Al₂O₃ based powders were microspheres with an average diameter about 1.9 μm. Photoluminescence (PL) spectra showed that the Al₂O₃:Cr^3 + particles presented a symmetric broad R band at 696 nm without appreciable splitting when excited at 462 nm. It is shown that the 0.04 mol% of doping concentration of Cr^3 + ions in γ-Al₂O₃:Cr^3 + is optimum. According to Dexter's theory, the critical distance between Cr^3 + ions for energy transfer was determined to be 47.54 Å. Based on the corresponding PL spectrum, full width at half maximum (FWHM) of Al₂O₃:Cr^3 + (0.04 mol%) was calculated to be 3.35 nm.     

Clinical feasibility of 3D-QALAS – Single breath-hold 3D myocardial T1- and T2-mapping

PurposeTo investigate the in-vivo precision and clinical feasibility of 3D-QALAS - a novel method for simultaneous three-dimensional myocardial T1- and T2-mapping.MethodsTen healthy subjects and 23 patients with different cardiac pathologies underwent cardiovascular 3 T MRI examinations including 3D-QALAS, MOLLI and T2-GraSE acquisitions. Precision was investigated in the healthy subjects between independent scans, between dependent scans and as standard deviation of consecutive scans. Clinical feasibility of 3D-QALAS was investigated for native and contrast enhanced myocardium in patients. Data were analyzed using mean value and 95% confidence interval, Pearson correlation, Paired t-tests, intraclass correlation and Bland-Altman analysis.ResultsAverage myocardial relaxation time values and SD from eight repeated acquisitions within the group of healthy subjects were 1178 ± 18.5 ms (1.6%) for T1 with 3D-QALAS, 52.7 ± 1.2 ms (2.3%) for T2 with 3D-QALAS, 1145 ± 10.0 ms (0.9%) for T1 with MOLLI and 49.2 ± 0.8 ms (1.6%) for T2 with GraSE.Myocardial T1 and T2 relaxation times obtained with 3D-QALAS correlated very well with reference methods; MOLLI for T1 (r = 0.994) and T2-GraSE for T2 (r = 0.818) in the 23 patients. Average native/post-contrast myocardial T1 values from the patients were 1166.2 ms/411.8 ms for 3D-QALAS and 1174.4 ms/438.9 ms for MOLLI. Average native myocardial T2 values from the patients were 53.2 ms for 3D-QALAS and 54.4 ms for T2-GraSE.ConclusionsRepeated independent and dependent scans together with the intra-scan repeatability, demonstrated all a very good precision for the 3D-QALAS method in healthy volunteers. This study shows that 3D T1 and T2 mapping in the left ventricle is feasible in one breath hold for patients with different cardiac pathologies using 3D-QALAS.     

Adsorption of chlorine on Ru(0001)—A combined density functional theory and quantitative low energy electron diffraction study

Chlorine adsorption on Ru(0001) surface has been studied by a combined density functional theory (DFT) and quantitative low energy electron diffraction (LEED) approach. The (√3 × √3)R30°-Cl phase with Θ_Cl = 1/3 ML and chlorine sitting in fcc sites has been identified by DFT calculations as the most stable chlorine adsorbate structure on Ru(0001) with an adsorption energy of ? 220 kJ/mol. The atomic geometry of (√3 × √3)R30°-Cl was determined by quantitative LEED. The achieved agreement between experimental and simulated LEED data is quantified by a Pendry factor of r_P = 0.19 for a fcc adsorption site with a Cl-Ru bond length of 2.52 Å. At chlorine coverages beyond 1/3 ML LEED reveals diffuse diffraction rings, indicating a continuous compression of the hexagonal Cl overlayer with a preferred average Cl–Cl distance of 4.7 Å in the (√3 × √3)R30°-Cl, Θ_Cl = 1/3 ML phase towards 3.9 Å at saturation coverage of 0.48 ML.     

An STM study of desorption-induced thallium structures on the Si(111) surface

The scanning tunneling microscopy is used to study morphology of a Tl adlayer in various stages of Tl desorption from the Si(111) surface. Transition from the Si(111)/(1 × 1)-Tl structure through the (√3 × √3)R30° mosaic phase to domains of metastable Si reconstructions is observed. Silicon substitutional atoms are found to be intrinsic to the (√3 × √3)R30° structure. The temperature dependence of the amount of residual Tl atoms on the surface is successfully fitted by a model using the first order desorption. The same desorption energy of (2.1 ± 0.3) eV and frequency prefactor 5 × 10^14 ± 2 s^? 1 during all stages of the desorption are sufficient for the fitting. It is concluded that bonding of Tl in both (1 × 1) and (√3 × √3) configurations is of the same nature.     

Crystallographic orientation-dependent optical properties of GaInSb mid-infrared quantum well laser

The optical properties of compressively strained GaInSb/GaInAlSb quantum well (QW) laser are numerically studied in different crystal orientations solving envelope function equation using finite difference method. The simulation results demonstrate that there is a strong correlation between the optical gain and its emission wavelength with crystal orientation of the QW. The maximum and minimum optical gains are evaluated in the (1 1 3) and (1 1 1) crystal orientations, respectively, due to band mixing effects. The peak emission wavelength can be tuned from 2.4 μm to 2.25 μm by changing the crystal orientation from (1 1 0) to (1 1 1). Typical optical gains are evaluated 3115, 3080, 2790, 3415, and 2940 cm^?1 in (0 0 1), (1 1 0), (1 1 1), (1 1 3), and (1 3 1) crystal orientations, respectively, when the injection carrier density is 3.5 × 10¹⁸ cm^?3. The highest optical power and lower threshold current are obtained in (1 1 3) orientation for the number of quantum wells three.     

Ga induced 2D superstructural phase diagram on trenched Si(5 5 12) surface

The high index Si(5 5 12) surface offers morphological trenches, which can be interesting for epitaxial growth. In this study, the evolution of Ga adsorption at a very low flux rate of 0.03 ML/min on high index trenched Si(5 5 12) ? 2 × 1 reconstructed surface at various substrate temperatures ranging from room temperature (RT) to 600 °C has been investigated using in-situ AES, LEED and EELS. The Auger uptake curves, which plot the Ga(LMM)/Si(LVV) Auger intensity ratio with Ga adsorption time, show that Ga grows in layer plus islands mode for substrate temperatures in the RT to 350 °C range, while it grows in Volmer–Weber (3D islands) for higher substrate temperatures (> 350 °C). We also arrive at a complete 2D superstructural phase diagram for Ga/Si(5 5 12) interfacial system that shows the pathways to attain the different superstructural phases. The formation of Ga nanowires as (2 2 5), (3 3 7) phase and Ga 3D islands in the (1 1 2) ? 6 × 1, (1 1 2) ? 6 × 2 phases and other Ga induced superstructural phases like (7 7 17) + 2x(1 1 3), (2 2 5) + (3 3 7), 1 × 1 has been carefully followed. The electronic structures of each of the observed phases have been probed by EELS and each of them is shown to have characteristic features.     

Optical temperature sensor through infrared excited blue upconversion emission in Tm3 +/Yb3 + codoped Y2O3

An analysis of the intense blue upconversion emission at 476 and 488 nm in Tm^3 +/Yb^3 + codoped Y₂O₃ under excitation power density of 86.7 W/cm² available from a diode laser emitting at 976 nm, has been undertaken. Fluorescence intensity ratio (FIR) variation of temperature-sensitive blue upconversion emission at 476 and 488 nm in this material was recorded in the temperature range from 303 to 753 K. The maximum sensitivity derived from the FIR technique of the blue upconversion emission is approximately 0.0035 K^? 1. The results imply that Tm^3 +/Yb^3 + codoped Y₂O₃ is a potential candidate for the optical temperature sensor.     

Blue upconversion luminescence in 12 CaO·7 Al2O3:Tm3 +/Yb3 + polycrystals

The effect of Yb^3 + concentration on the fluorescence of 12 CaO·7 Al₂O₃:Tm^3 +/Yb^3 + polycrystals is investigated. Under the excitation of 980 nm laser, the strong blue (477 nm) emission band is observed and attributed to ¹G₄ → ³H₆ of Tm^3 +. The ratio of blue to red emission increases with the increasing of Yb^3 + and remains constant at 10 mol% Yb^3 +. The pump dependence and upconversion mechanisms show that the two-photon cooperative upconversion process is responsible for the enhancement of the blue upconversion emission. The Commission Internationale de l'eclairage chromaticity coordinates (x, y) illustrate that the 12 CaO·7 Al₂O₃:1 mol% Tm^3 +/10 mol% Yb^3 + can emit high-purity blue light.     

Dissociation of dimethyl ether at high temperatures

The decomposition of dimethyl ether (CH₃OCH₃) has been investigated behind incident shock waves in a diaphragmless shock tube using laser schlieren densitometry, LS (T = 1500–2450 K, P = 57 ± 4, 125 ± 5 and 253 ± 12 Torr). The LS density gradient profiles were simulated and excellent agreement was found between the simulations and experimental profiles. Rate coefficients for CH₃OCH₃ → CH₃O + CH₃ were obtained. They showed strong fall-off, and at the lower end of the experimental temperature range are close to the low pressure limit. First order rate coefficient expressions were determined over 1500 < T < 2450 K. k_57Torr = (3.10 ± 1.0) × 10⁷⁹T^?19.03 exp(?54417/T) s^?1, k_125Torr = (1.12 ± 0.3) × 10⁸³T^?19.94 exp(?55554/T) s^?1and k_253Torr = (1.02 ± 0.3) × 10⁷³T^?17.09 exp(?51500/T) s^?1. The effect of a roaming channel for decomposition of dimethyl ether was assessed and the best agreement was obtained with 1% dissociation of DME via the roaming path.     

Surface structure of γ-Fe2O3(111)

The surface structure of γ-Fe₂O₃(111) has been investigated with a range of surface techniques. Two different surface structures were discovered depending upon surface preparation techniques. Sputtering followed by annealing in vacuum produced a reduced surface characterised by a (2 × 2) LEED pattern, whereas sputtering followed by annealing in 1 × 10^? 6 mbar oxygen produced a surface characterised by a (√3 × √3)-R30° LEED pattern. The latter appears to be a very low conductivity surface, whereas the former has the band gap expected for maghemite (~ 2.0 eV). We propose that the reduced surface is a magnetite-like layer, whereas the oxidised surface is an Fe₂O₃-like layer.     

Preparation and characterization of Fe3O4(1 1 1) nanoparticles and thin films on Au(1 1 1)

Fe₃O₄ nanoparticles and thin films were prepared on the Au(1 1 1) surface and characterized using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Fe₃O₄ was formed by annealing α-Fe₂O₃(0 0 0 1) structures on Au(1 1 1) at 750 K in ultrahigh vacuum (UHV) for 60 min. Transformation of the α-Fe₂O₃(0 0 0 1) structures into Fe₃O₄ nanoparticles and thin films was supported by XPS. STM images show that during the growth procedure used, Fe₃O₄ initially appears as nanoparticles at low coverages, and forms thin films at ～2 monolayer equivalents (MLE) of iron. Two types of ordered superstructures were observed on the Fe₃O₄ particles with periodicities of ～50 and ～42 Å, respectively. As the Fe₃O₄ particles form more continuous films, the ～50 Å feature was the predominant superstructure observed. The Fe₃O₄ structures at all coverages show a hexagonal unit cell with a ～3 Å periodicity in the atomically resolved STM images.     

A two-dimensional alloy of immiscible Bi and Sn atoms on Rh(111)

We studied the atomic arrangements and the phase diagram of two-dimensional (2D) Bi–Sn binary films on Rh(111) with low-energy electron diffraction and scanning tunneling microscopy (STM). The 2D binary films exhibited (“2” × √3)-(Bi,Sn), (√7 × √7)R19°-(Bi,Sn), and (7 × 3√3)-(Bi,Sn) structures, depending on the compositional ratio of Bi and Sn. Atomically resolved STM images revealed that the binary films formed a BiSn₃ ordered alloy for the (√7 × √7)R19°-(Bi,Sn) structure and a solid solution alloy for the (“2” × √3)-(Bi,Sn) structure. The atomic configuration for the (7 × 3√3)-(Bi,Sn) structure was closely related to that of (√7 × √7) R19°-(Bi,Sn).     

Intensified depolymerization of aqueous polyacrylamide solution using combined processes based on hydrodynamic cavitation,ozone, ultraviolet light and hydrogen peroxide

The present work deals with intensification of depolymerization of polyacrylamide (PAM) solution using hydrodynamic cavitation (HC) reactors based on a combination with hydrogen peroxide (H₂O₂), ozone (O₃) and ultraviolet (UV) irradiation. Effect of inlet pressure in hydrodynamic cavitation reactor and power dissipation in the case of UV irradiation on the extent of viscosity reduction has been investigated. The combined approaches such as HC + UV, HC + O₃, HC + H₂O₂, UV + H₂O₂ and UV + O₃ have been subsequently investigated and found to be more efficient as compared to individual approaches. For the approach based on HC + UV + H₂O₂, the extent of viscosity reduction under the optimized conditions of HC (3 bar inlet pressure) + UV (8 W power) + H₂O₂ (0.2% loading) was 97.27% in 180 min whereas individual operations of HC (3 bar inlet pressure) and UV (8 W power) resulted in about 35.38% and 40.83% intrinsic viscosity reduction in 180 min respectively. In the case of HC (3 bar inlet pressure) + UV (8 W power) + ozone (400 mg/h flow rate) approach, the extent of viscosity reduction was 89.06% whereas individual processes of only ozone (400 mg/h flow rate), ozone (400 mg/h flow rate) + HC (3 bar inlet pressure) and ozone (400 mg/h flow rate) + UV (8 W power) resulted in lower extent of viscosity reduction as 50.34%, 60.65% and 75.31% respectively. The chemical structure of the treated PAM by all approaches was also characterized using FTIR (Fourier transform infrared) spectra and it was established that no significant chemical structure changes were obtained during the treatment. Overall, it can be said that the combination of HC + UV + H₂O₂ is an efficient approach for the depolymerization of PAM solution.     

Rapid acquisition of magnetic resonance imaging of the shoulder using three-dimensional fast spin echo sequence with compressed sensing

PurposeTo evaluate the feasibility of 3D fast spin-echo (FSE) imaging with compressed sensing (CS) for the assessment of shoulder.Materials and methodsTwenty-nine patients who underwent shoulder MRI including image sets of axial 3D-FSE sequence without CS and with CS, using an acceleration factor of 1.5, were included. Quantitative assessment was performed by calculating the root mean square error (RMSE) and structural similarity index (SSIM). Two musculoskeletal radiologists compared image quality of 3D-FSE sequences without CS and with CS, and scored the qualitative agreement between sequences, using a five-point scale. Diagnostic agreement for pathologic shoulder lesions between the two sequences was evaluated.ResultsThe acquisition time of 3D-FSE MRI was reduced using CS (3 min 23 s vs. 2 min 22 s). Quantitative evaluations showed a significant correlation between the two sequences (r = 0.872–0.993, p < 0.05) and SSIM was in an acceptable range (0.940–0.993; mean ± standard deviation, 0.968 ± 0.018). Qualitative image quality showed good to excellent agreement between 3D-FSE images without CS and with CS. Diagnostic agreement for pathologic shoulder lesions between the two sequences was very good (κ = 0.915–1).ConclusionsThe 3D-FSE sequence with CS is feasible in evaluating the shoulder joint with reduced scan time compared to 3D-FSE without CS.     

Comparison of 7 T and 3 T MRI in patients with moyamoya disease

Magnetic resonance imaging and magnetic resonance angiography (MRI/MRA) are widely used for evaluating the moyamoya disease (MMD). This study compared the diagnostic accuracy of 7 Tesla (T) and 3 T MRI/MRA in MMD. In this case control study, 12 patients [median age: 34 years; range (10–66 years)] with MMD and 12 healthy controls [median age: 25 years; range (22–59 years)] underwent both 7 T and 3 T MRI/MRA. To evaluate the accuracy of MRI/MRA in MMD, five criteria were compared between imaging systems of 7 T and 3 T: Suzuki grading system, internal carotid artery (ICA) diameter, ivy sign, flow void of the basal ganglia on T2-weighted images, and high signal intensity areas of the basal ganglia on time-of-flight (TOF) source images. No difference was observed between 7 T and 3 T MRI/MRA in Suzuki stage, ICA diameter, and ivy sign score; while, 7 T MRI/MRA showed a higher detection rate in the flow void on T2-weighted images and TOF source images (p < 0.001). Receiver operating characteristic curves of both T2 and TOF criteria showed that 7 T MRI/MRA had higher sensitivity and specificity than 3 T MRI/MRA. Our findings indicate that 7 T MRI/MRA is superior to 3 T MRI/MRA for the diagnosis of MMD in point of detecting the flow void in basal ganglia by T2-weighted and TOF images.     

Sonocatalyzed decolorization of synthetic textile wastewater using sonochemically synthesized MgO nanostructures

The present study focused on the synthesis of nanostructured MgO via sonochemical method and its application as sonocatalyst for the decolorization of Basic Red 46 (BR46) dye under ultrasonic irradiation. The sonocatalyst was characterized using X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) equipped with energy dispersive X-ray microanalysis (EDX). In the following, the sonocatalytic removal of the dye under different operational conditions was evaluated kinetically on the basis of pseudo first-order kinetic model. The reaction rate of sonocatalyzed decolorization using MgO nanostructures (12.7 × 10⁻³ min⁻¹) was more efficient than that of ultrasound alone (2.0 × 10⁻³ min⁻¹). The increased sonocatalyst dosage showed better sonocatalytic activity but the application of excessive dosage should be avoided. The presence of periodate ions substantially increased the decolorization rate from 14.76 × 10⁻³ to 33.4 × 10⁻³ min⁻¹. Although the application of aeration favored the decolorization rate (17.8 × 10⁻³ min⁻¹), the addition of hydrogen peroxide resulted in a considerable decrease in the decolorization rate (9.5 × 10⁻³ min⁻¹) due to its scavenging effects at specific concentrations. Unlike alcoholic compounds, the addition of phenol had an insignificant scavenging effect on the sonocatalysis. A mineralization rate of 7.4 × 10⁻³ min⁻¹ was obtained within 120 min. The intermediate byproducts were also detected using GC–MS analysis.     

Red,green and infrared three-wavelength lasers generated from LD side-pumped Nd3+:YAG crystal

To obtain 1064 nm/532 nm/660 nm three wavelength lasers operating simultaneously or singly, a novel LD side-pumped Nd³⁺:YAG laser system with acousto-optic Q-switched and nonlinear frequency conversion technologies was investigated. When the three wavelength lasers output singly and the Pumping power was 103 W, 1064 nm laser was 14.5 W and the green and red lasers reached 4.7 W and 1.6 W, respectively, at the repetition rate of 10.5 kHz and 11.5 kHz. When they worked simultaneously, the red, green and infrared lasers were obtained with the output power distribution of 1.0 W at 660 nm, 4.3 W at 532 nm and 10.1 W at 1064 nm, and the instability was less than 2% within 3 h.     

Microwave sol–gel derived NaCaGd(MoO4)3:Er3+/Yb3+ phosphors and their upconversion photoluminescence properties

Ternary molybdate NaCaGd_1−x(MoO₄)₃:Er³⁺/Yb³⁺ phosphors with the proper doping concentrations of Er³⁺ and Yb³⁺ (x = Er³⁺ + Yb³⁺, Er³⁺ = 0, 0.05, 0.1, 0.2 and Yb³⁺ = 0, 0.2, 0.45) were successfully synthesized by microwave sol–gel method for the first time. Well-crystallized particles formed after heat-treatment at 900 °C for 16 h showed a fine and homogeneous morphology with particle sizes of 3–5 μm. The optical properties were examined comparatively using photoluminescence emission and Raman spectroscopy. Under excitation at 980 nm, the doped particles exhibited a strong 525-nm emission band, a weak 550-nm emission band in the green region, which correspond to the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions, and a very weak 655-nm emission band in the red region, which corresponds to the ⁴F_9/2 → ⁴I_15/2 transition. The optimal Yb³⁺:Er³⁺ ratio was obtained to be 9:1, as indicated by the composition-dependent quenching effect of Er³⁺ ions. The pump power dependence of upconversion emission intensity and Commission Internationale de L’Eclairage chromaticity coordinates of the phosphors were evaluated in detail.