Quantitative assessment of mobile protein levels in human knee synovial fluid: feasibility of chemical exchange saturation transfer (proteinCEST) MRI of osteoarthritis

Purpose

To establish the feasibility of chemical exchange saturation transfer (proteinCEST) MRI in the differentiation of osteoarthritis (OA) knee joints from non-OA joints by detecting mobile protein and peptide levels in synovial fluid by determining their relative distribution.

Materials and Methods

A total of 25 knees in 11 men and 12 women with knee injuries were imaged using whole knee joint proteinCEST MRI sequence at 3 T. The joint synovial fluid was segmented and the asymmetric magnetization transfer ratio at 3.5 ppm MTR_asym (3.5 ppm) was calculated to assess protein content in the synovial fluid. The 85th percentile of synovial fluid MTR_asym (3.5 ppm) distribution profile was compared using the independent Student's t test. The diagnostic performance of the 85th percentile of synovial fluid MTR_asym (3.5 ppm) in differentiating OA and non-OA knee joints was evaluated.

Results

The 85th percentile of synovial fluid MTR_asym (3.5 ppm) in knee joints with OA was 8.6%±3.4% and significantly higher than that in the knee joints without OA (6.3%±1.4%, P<.05). A knee joint with an 85th percentile of synovial fluid MTR_asym (3.5 ppm) greater than 7.7% was considered to be an OA knee joint. With the threshold, the sensitivity, specificity and overall accuracy for differentiating knee joints with OA from the joints without OA were 54% (7/13), 92% (11/12) and 72% (18/25), respectively.

Conclusion

proteinCEST MRI appears feasible as a quantitative methodology to determine mobile protein levels in synovial fluid and identify patterns characteristic for OA disease.     

Influence of temperature on structure as well as adhesion and friction and wear behavior of hydrogenated carbon nitride films prepared on silicon substrate

Hydrogenated-carbon nitride (CN_x:H) films were synthesized on silicon substrate in a large quantity by the pyrolysis of ethylenediamine in a temperature range of 700-950 °C. The influence of temperature on the morphology, structure, adhesion to substrate, and friction and wear behavior of CN_x:H films was investigated. It has been found that CN_x:H films obtained at 700 °C and 800 °C are amorphous, and those prepared at 900 °C and 950 °C consist of carbon nitride nanocrystal. Besides, CN_x:H film sample obtained at 700 °C has the maximum N content of 9.1 at.% but the poorest adhesion to Si substrate, while the one prepared at 900 °C has the lower N content and the highest adhesion to substrate. As a result, nanocrystalline CN_x:H (nc-CN_x:H) film synthesized at 900 °C possesses the best wear resistance when slides against stainless steel counterpart. N atom is incorporated into the graphitic network in three different bonding forms, and their relative content is closely related to temperature, corresponding to different adhesion as well as friction and wear behavior of the films obtained at different temperatures. Furthermore, the friction coefficient and antiwear life of as-deposited CN_x:H films vary with varying deposition temperature and thickness, and the film with thickness of 1.3 μm, obtained at 900 °C, has the longest antiwear life of over 180,000 s.     

In situ growth stresses during the phase separation of immiscible FeCu thin films

This paper addresses the in situ growth stress evolution and post-growth stress relaxation during the phase separation of immiscible Fe_0.51Cu_0.49 thin films at various in situ deposition temperatures. Each film was sputter-deposited onto a 10 nm Si₃N₄ underlayer that was grown on top of Si [0 0 1] substrate at 25 °C, 145 °C, 205 °C, 265 °C or 325 °C. The thin film stress was measured using a wafer curvature technique. The in situ growth stress increased in compression with increasing substrate temperature. The stress relaxation of the Fe_0.51Cu_0.49 was found to have a linear increase with the inverse grain size for films deposited at temperatures greater than 205 °C. The stress state was correlated to the films’ phase and morphology by X-ray diffraction, (scanning) transmission electron microscopy and atomic force microscopy techniques.     

Effects of thermo-hygro-mechanical densification on the surface characteristics of trembling aspen and hybrid poplar wood veneers

The effect of thermo-hygro-mechanical (THM) densification temperature on the surface color, roughness, wettability, and chemical composition of trembling aspen (Populus tremuloides) and hybrid poplar (Populus maximowiczii × P. balsamifera) veneers was investigated. Veneers were subjected to four THM densification temperatures (160 °C, 180 °C, 200 °C, and 220 °C). Veneer color darkened with increasing THM densification temperature. Surface roughness decreased between 160 °C and 200 °C. Wettability decreased after THM densification, but no significant difference was found between treated specimens. ATR-FTIR and XPS results confirmed that THM densification caused major chemical changes in veneer surfaces, and more pronounced at temperatures higher than 160 °C.     

Annealing and measurement temperature dependence of W2B5-based rectifying contacts to n-GaN

The thermal stability and measurement temperature dependence of Schottky contact characteristics on n-GaN using a W₂B₅/Ti/Au metallization scheme was studied using current-voltage (I-V), scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) measurements. The elemental profile obtained from samples annealed at 350 °C showed some titanium diffusion into the gold layer but little other difference from the as-deposited wafer. Annealing at 700 °C produced significant diffusion of titanium. The Schottky barrier height increased with anneal temperature up to 200 °C, reaching a maximum value of 0.65 eV, but decreased at higher annealing temperatures. The reverse breakdown voltage from diodes fabricated using the W₂B₅-based contacts showed a similar dependence. The reverse current magnitude was larger than predicted by thermionic emission alone. The barrier height showed only minor changes with measurement temperature up to 150 °C.     

Influence of the substrate position angle on the adhesion of ZnO thin films deposited on polyimide foil substrates

ZnO thin films, as polymer protection layers against ultraviolet radiation, were deposited on polyimide foil substrates using cathodic vacuum arc deposition technique. X-ray diffraction results showed that all the samples had (0 0 2) preferred orientation and the FWHM decreased as the position angle decreased. A fragmentation test was employed to investigate the influence of substrate position angle on the adhesion of ZnO thin films. It was found that the intrinsic adhesion between the ZnO film and the polyimide substrate is about 60 MPa at the substrate position angle of 0°. When the position angle increases to ±60°, the value of intrinsic adhesion decreases to about 30 MPa.     

Effect of annealing temperature on microstructure, hardness and adhesion properties of TiSixNy superhard coatings

A series of TiSi_xN_y superhard coatings with different Si contents were prepared on M42 steel substrates using two Ti and two Si targets by reactive magnetron sputtering at 500 °C. These samples were subsequently vacuum-annealed at 500, 600, 700, 800 and 900 °C, respectively. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), microindenter, Rockwell hardness tester and scratch tester were applied to investigate the microstructure, phase configuration, hardness and adhesion properties of as-deposited and annealed samples. The results indicated that there were two bonds, TiN and Si₃N₄, in all presently deposited TiSi_xN_y thin films, that structure was nanocomposite of nanocrystalline (nc-) TiN embedded into amorphous Si₃N₄ matrices. Annealing treatment below 900 °C played a little role in microstructure and hardness of the coatings although it greatly affected those of steel substrates. The film-substrate adhesion strength was slightly increased, followed by an abrupt decrease with increasing annealing temperature. Its value got to the maximum at 600 °C. Annealing had little effect on the friction coefficient with its value varying in the range of 0.39-0.40.     

Trace element changes during hibernation of Drosophila melanogaster by WDXRF analyses at chilling temperature

Fruit flies (Drosophila melanogaster) were exposed to low temperature (4 °C, 3d), after controlled acclimation (15 °C, 1d) and passed to artificial hibernation. The concentrations of elements in almost 1000 mature flies were measured by Wavelength-Dispersive X-ray Fluorescence (WDXRF) spectrometry. Concentration changes of Zn, K, S, Ca (33.5%, 11.2%, 10.3% and 7.5%, respectively) and especially Cr and Mn (99.90 and 99.60) were observed. Concentrations of Cr, Zn, S and Ca increased significantly, but concentrations of Mn and K decreased in with comparison to the control group.     

AFM investigation on surface evolution of amorphous carbon during ion-beam-assisted deposition

Hydrogen-free amorphous carbons (a-C) have been prepared on mirror-polished Si(1 1 1) wafers through thermally evaporated C₆₀ with simultaneous bombardments of Ne⁺ ions. The time evolution of film surfaces has been characterized by atomic force microscopy (AFM) at two temperatures of 400 and 700 °C, respectively. Based on the topography images and the root-mean-square (rms) roughness analysis, it is found that the a-C surfaces present roughening growth at the initial stage. With increasing growth time, the cooperative nucleation of the islands and pits appears on the surfaces, suggesting three-dimensional growth, and then they continue to evolve to irregular mounds at 400 °C, and elongated mounds at 700 °C. At the steady growth stage, these surfaces further develop to the structures of bamboo joints and ripples corresponding to these two temperatures, respectively. It is believed that besides ion sputtering effect, the chemical bonding configurations in the amorphous carbon films should be taken into considerations for elucidating the surface evolutions.     

Ultrasound assisted oxidative desulfurization of model diesel fuel

Very stringent environmental regulations have limited the level of sulfur in diesel, therefore deep desulfurization of fuels is required. For that purpose, the frequently used industrial process is hydrodesulfurization (HDS) which enables effective elimination of sulfur compounds such as mercaptanes, thiols, sulfides, disulfides from diesel oil, but removal of thiophene sulfur compounds (benzothiophene, dibenzothiophene, 4,6 dimethyldibenzothiophene) is insufficient. Ultrasound assisted oxidative desulfurization (UAOD) as one of several new technologies enables performance under mild conditions without use of explosive hydrogen. A higher reactivity of thiophene sulfur compounds during UAOD also provides conversion into highly polar sulfoxides and sulfones that are easily removed by adsorption or extraction. Nowadays, different catalyst/oxidants systems are being studied to improve oxidation reaction efficiency and enhance the mass transfer in the interfacial region. In this paper, the effect of reaction temperature (40–70 °C) and oxidation time (5–150 min) for UAOD of model diesel fuel with a catalyst/oxidants system (acetic acid/hydrogen peroxide) was investigated in a 70 ml batch reactor. Furthermore, the effects of different initial concentrations of dibenzothiophene (DBT) and of ultrasound amplitude were additionally examined to achieve efficient sulfur removal. The obtained results indicated that temperature and US amplitude of 70 °C and 80% respectively were efficient for conversion of DBT (sulfur concentration up to 3976.86 ppm). The results indicate a rise in the yield of sulfones at higher temperatures and subsequent extraction with N,N-dimethylformamide conducted after the process of oxidation at different solvent/oil ratio revealed sulfur removal efficiency of 98.35%.     

Manganese-enhanced magnetic resonance imaging investigation of the interferon-α model of depression in rats

Therapeutic effects of interferon-α (IFN-α) are known to be associated with CNS toxicity in humans, and in particular with depression symptoms. Animal models of IFN-α-induced depression (sickness behaviour) have been developed in rodents using various preparations, dosing schedules or routes of administrations. In this work, Manganese Enhanced MRI (MEMRI) has been applied to investigate an experimental model of sickness behaviour induced by administration of IFN-α in rats. IFN-α (3.10⁵ U/kg), or vehicle, was daily administered i.p., for 7 days in rats (n = 20 IFN-α treated and n = 20 controls). After treatment, animals were assigned to behavioural (n = 10 treated, n = 10 control) or MRI (n = 10 treated and n = 10 control) studies. Animals assigned to the MRI study received two repeated i.p. injections of MnCl₂, before image acquisition. Images were acquired at 4.7 T using T₁ mapping for determination of Mn concentration in brain. After co-registration of T₁ maps to a digital brain atlas, differences between brains of treated and untreated animals were assessed pixel-to-pixel by statistical analysis.     

The γ-Fe formation in epitaxial Cu(0 0 1)/Fe(0 0 1) thin films by the solid-state synthesis: Structural and magnetic features

The γ-Fe formation in epitaxial Cu(0 0 1)/Fe(0 0 1) bilayers with the annealing temperature increasing has been studied. Using Mössbauer spectroscopy, X-ray diffraction, and magnetic analysis, structural and chemical characterization of the interface between cooper and iron layers has been performed. After annealing at 850 °C and subsequent cooling to room temperature, paramagnetic γ-Fe(0 0 1) precipitates with an average size of 30 nm coherent to a Cu(0 0 1) matrix form. Conditions of intermixing and the γ-Fe formation at the Cu/Fe interface are explained in terms of the solid-state synthesis in thin films. Specific features of the martensitic transition γ↔α are discussed.     

Ultrasound treatment enhances cholesterol removal ability of lactobacilli

This study aimed to evaluate the effect of ultrasound treatment on the cholesterol removing ability of lactobacilli. Viability of lactobacilli cells was significantly increased (P < 0.05) immediately after treatment, but higher intensity of 100 W and longer duration of 3 min was detrimental on cellular viability (P < 0.05). This was attributed to the disruption of membrane lipid bilayer, cell lysis and membrane lipid peroxidation upon ultrasound treatment at higher intensity and duration. Nevertheless, the effect of ultrasound on membrane properties was reversible, as the viability of ultrasound-treated lactobacilli was increased (P < 0.05) after fermentation at 37 °C for 20 h. The removal of cholesterol by ultrasound-treated lactobacilli via assimilation and incorporation of cholesterol into the cellular membrane also increased significantly (P < 0.05) upon treatment, as observed from the increased ratio of membrane C:P. Results from fluorescence anisotropies showed that most of the incorporated cholesterol was saturated in the regions of phospholipids tails, upper phospholipids, and polar heads of the membrane bilayer.     

Characterization and catalytic performance of pure and Li2O-doped CuO/CeO2 catalysts

Pure and Li₂O-doped CuO/CeO₂ catalysts calcined at 500 °C were prepared by impregnation method. The catalysts are characterized by DTA, TG-DTG, XRD, IR, TEM, nitrogen adsorption at −196 °C and the catalytic decomposition of hydrogen peroxide at 30 °C.The effects of molar ratio, heat treatment time and the doping on the structural, surface and catalytic properties of nanocrystalline Cu/Ce-mixed oxides system have been studied. It was found that the catalytic activity of ceria-supported copper oxide catalysts increased by increasing both the heat treatment time and dopant content. However, the pure Cu/Ce-mixed oxide solids containing 10 wt.% CuO exhibited the best performance. The characterization results indicated that the higher surface area, the formation of solid solution between copper and cerium oxides, and the high dispersion of copper species on the ceria were responsible for the high catalytic activity of the CuO/CeO₂ catalysts.     

Structural, morphological, wettability and thermal resistance properties of hydro-oleophobic thin films prepared by a wet chemical process

The structural properties of fluorine containing polymer compounds make them highly attractive materials for hydro-oleophobic applications. However, most of these exhibit low surface energy and poor adhesion on the substrates. In the present investigation, crack free, smooth and uniform thin films of poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole]-co-tetrafluoroethylene (TFD-co-TFE) with good adhesion have been deposited by wet chemical spin-coating technique on polished AISI 440C steel substrates. The as-deposited films (xerogel films) have been subjected to annealing for 1 h at different temperatures ranging from 100 to 500 °C in an argon atmosphere. The size growth of the nano-hemispheres increased from 8 nm for xerogel film to 28 nm for film annealed at 400 °C. It was found that as the annealing temperature increased from 100 to 400 °C, nano-hemisphere-like structures were formed, which in turn have shown increase in the water contact angle from 122° to 147° and oil (peanut) contact angle from 85° to 96°. No change in the water contact angle (122°) has been observed when the films deposited at room temperature were heated in air from 30 to 80 °C as well as exposed to steam for 8 days for 8 h/day indicating thermal stability of the film.     

Equilibrium structure in the presence of internal rotation: A case study of cis-methyl formate

The Born-Oppenheimer (BO) equilibrium molecular structure () of cis-methyl formate has been determined at the CCSD(T) level of electronic structure theory using Gaussian basis sets of at least quadruple-ζ quality and a core correlation correction. The quadratic, cubic and semi-diagonal quartic force field in normal coordinates has also been computed at the MP2 level employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure () has been derived from experimental ground-state rotational constants and the lowest-order rovibrational interaction parameters calculated from the ab initio cubic force field. To determine structures, it is important to start from accurate ground-state rotational constants. Different spectroscopic methods, applicable in the presence of internal rotation and used in the literature to obtain “unperturbed” rotational constants from the analysis and fitting of the spectrum, are reviewed and compared. They are shown to be compatible though their precision may be different. The and structures are in good agreement showing that, in the particular case of cis-methyl formate, the methyl torsion can still be treated as a small-amplitude vibration. The best equilibrium structure obtained for cis-methyl formate is: r(C_m-O) = 1.434 Å, r(O-C_c) = 1.335 Å, r(C_m-H_s) = 1.083 Å, r(C_m-H_a) = 1.087 Å, r(C_c-H) = 1.093 Å, r(CO) = 1.201 Å, ∠(COC) = 114.4°, ∠(CCH_s) = 105.6°, ∠(CCH_a) = 110.2°, ∠(OCH) = 109.6°, ∠(OCO) = 125.5°, and τ(H_aCOC) = 60.3°. The accuracy is believed to be about 0.001 Å for the bond lengths and 0.1° for the angles.     

Correlation between ferromagnetism and defects in MgO nanocrystals studied by positron annihilation

High purity MgO nanopowders were pressed into pellets and annealed in air from 100 to 1400 °C. Variation of the microstructures was investigated by X-ray diffraction and positron annihilation spectroscopy. Annealing induces an increase in the MgO grain size from 27 to 60 nm with temperature increasing up to 1400 °C. Positron annihilation measurements reveal vacancy defects including Mg vacancies, vacancy clusters, microvoids and large pores in the grain boundary region. Rapid recovery of Mg monovacancies and vacancy clusters was observed after annealing above 1200 °C. Room temperature ferromagnetism was observed for MgO nanocrystals annealed at 100, 700, and 1000 °C. However, after 1400 °C annealing, MgO nanocrystals turn into diamagnetic. Our results suggest that the room temperature ferromagnetism in MgO nanocrystals might originate from the interfacial defects.     

Ni–Zn nanoferrite for radar-absorbing material

Nanoparticles of nickel–zinc ferrite have been prepared by using the citrate precursor method. According to scanning electron microscopy (SEM), the particle size is nanometric for the powder calcined at 350 °C/3.5 h. The phase formation has been studied by applying different calcining atmospheres, such as air and argon. Pure Ni–Zn ferrite has been observed when calcined in argon at the temperature of 350 °C. Hysteresis analyses have been done with magnetization of 53.01 emu/g at 350 °C and obtaining 84.62 emu/g at 1100 °C due to an optimization of domains formation at high temperature. Measures of reflectivity of Ni–Zn ferrite/epoxy composite have been obtained below 21% at 350 °C and above 96% at 1100 °C with a coercive field of 26.61 Oe. Low value of coercive field increased the mobilization of domains wall and increased the radiation absorption.     

The sterilization of Escherichia coli by dielectric-barrier discharge plasma at atmospheric pressure

The sterilization of E. coli (ATCC8099) using an atmospheric pressure, air DBD plasma driven by 100 Hz high-voltage power supply was investigated in this paper. The results showed that germicidal efficiency was closely related to the plasma treatment time, the gap spacing, the initial cell density and the surface characters of substrate materials. The germicidal efficiency was 99.999% under the conditions of 5-min plasma treatment, 3-cm gap spacing and on PET films. After plasma exposure for 5 min, the temperature was observed below 43 °C which could not lead to inactivate E. coli. The observation of protein leakage and cell morphology alteration by transmission electron microscopy (TEM) techniques revealed that the etching action on cell membrane by electrons, ions and radicals was primary reason of DBD air plasma sterilization.     

Dual N/Pb ion-implanted Si: Temperature dependence of the novel shift of the Pb peak under electron beam annealing

(1 0 0) Si was dual ion-implanted with 24 keV N and 7 keV Pb to peak concentrations ∼10 at.%. Implanted samples were then electron beam annealed (EBA) at a peak temperature T for 30 s with T ranging from 100 °C to 900 °C and for 15 s at 1000 °C. Pb profiles were measured using RBS and surfaces characterised by AFM. For T up to 500 °C there was no shift in the profile from the implanted depth ∼10 nm. For higher values of T a striking feature was the large movement of the Pb profile away from the surface without a significant change in width or Pb content. The profile depths were: ∼40 nm for 600 °C, ∼68 nm for 700-900 °C and ∼80 nm for 1000 °C. The response to EBA was found to be strongly dependent on both ion implantation order and Si starting structure. For (1 0 0) Si nanowhiskers formed on the treated surfaces for T = 900 °C and 1000 °C. A model is developed based on the restructuring of the amorphous implanted layer under EBA. It is proposed that a compaction starting at the surface sweeps the Pb before it via a stress interaction as it advances into the Si.