X-ray photoelectron spectroscopy characterization of Cu compounds for the development of organic protection treatments dedicated to heritage Cu objects preservation

The preservation of bronze and copper heritage objects is challenging. Exposure to water or pollution in outdoor conditions leads to corrosion phenomena, which can highly degrade the objects or structures. We aim to develop an alternative nontoxic corrosion inhibiting treatment, based on the use of a carboxylate (HC₁₀) treatment. Electron spectroscopies (X-ray photoelectron spectroscopy and scanning Auger microscopy) are used to determine, from micrometric to nanometric scale, the composition and chemical environments (oxidation degrees) of the copper compounds commonly found in the corrosion product layer. In the present study, we focus on the evaluation of X-ray beam irradiation damage when performing surface analysis on cuprite, brochantite, and Cu decanoate reference samples. The reduction phenomenon has already been reported, especially for Cu(II) compounds, but not clearly explained. Different behavior has been observed depending on the X-ray source used, and the nature and hydration level of the compounds. The photoreduction issue is critical, as it guarantees the reliability of the chemical information obtained and sheds light on the best analysis pathway to adopt when multitechnique analyses are implemented. An analytical procedure is employed to track the reduction of Cu(II) reference samples during XPS analysis evidencing practically instantaneous modifications of the spectra and thus, the instability of these phases except for the dehydrated cuprite sample.     

Determination of hydroxybupropion in human serum for routine therapeutic drug monitoring in psychiatry: A tool for dose‐individualization in treatment with bupropion

Therapeutic drug monitoring (TDM) has become a clinical routine in psychiatry. Nevertheless, for bupropion there is only one method available that is suitable for routine use. However, it involves a complex sample clean‐up. Owing to the instability of bupropion in serum, the main and active metabolite hydroxybupropion was chosen as the target substance. Therefore, a simple and robust high‐performance liquid chromatography method for the quantification of hydroxybupropion in serum was developed and validated. A volume of 30 μL serum was used for easy sample clean‐up, based on protein precipitation with acetonitrile followed by online solid‐phase extraction. As hydroxybupropion was present in high serum concentrations, UV detection was possible. Owing to the commonly available instrumentation, the method could easily be integrated in routine TDM. The newly developed method was validated following the guidelines for bioanalytical method validation of the European Medicines Agency and US Food and Drug Administration. The lower limit of quantification was 100 ng/mL (0.391 μm ) and linearity was shown between 100 and 2500 ng/mL. Intraday and interday precision ranged from 1.17 to 6.79% and from 6.07 to 9.41%, respectively. Intraday and interday accuracy ranged from 89.97 to 110.86% and from 95.05 to 101.2%. The method was shown to be selective, accurate and precise. Additionally, the method was successfully implemented in the therapeutic drug monitoring laboratory of the Department of Psychiatry, Psychosomatics and Psychotherapy at the University Hospital of Würzburg, Germany. Six months of routine analysis showed a rather low correlation between applied dose and serum concentration and therefore the necessity of TDM for dose‐individualization in the treatment with bupropion.     

基于立体舒适度的立体图像感知距离估计

提出了一种基于立体舒适度的双目图像感知距离估计方法.首先,推导双目立体图像的立体深度;然后进行主观实验获取实际人眼感知到的深度,分析其与立体深度间的差异;最后,将立体舒适度作为生理因素,建立感知距离、立体深度与视觉舒适度之间的关联关系,并得出感知距离的计算模型.在IVY公共数据集上进行实验验证,结果表明:当视觉舒适度值较高时,模型预测值的平均绝对值误差与均方根误差较主观评测值分别减少了0.0049、0.0073;而当视觉舒适度值较低时,平均绝对值误差与均方根误差分别减少了0.0721、0.0594.本模型结果更接近人类主观感知到的深度.     

Affected depth approach to determine the fatigue strength of materials containing surface defects

This paper explains a novel methodology to determine the High Cycle Fatigue (HCF) reliability of materials with defects. A defect was represented by a semi-spherical void situated at a specimen surface subjected to periodic loading. Then, the Finite Element (FE) method was carried out to find out the stress distribution near the defects for diverse sizes and diverse loadings. The Crossland stress change is studied and interpolated by a mathematical function depending on fatigue limits, defect radius, and profundity from the defect tip. The HCF strength of defect material is computed by the “stress strength” approach via the Monte Carlo sampling. This approach leads to determine Kitagawa–Takahashi diagrams, for a definite reliability, of materials with defects. The calculated HCF reliabilities agree well with fatigue tests. Obtaining Kitagawa–Takahashi diagrams with reliability level permits the engineer to be engaged in an endurance problem to compute the defective fatigue lives in safe and efficient process. As a final point, we discuss the sensitivity effects of defect size, defect free fatigue limits, affected depth, and load amplitude to envisage the fatigue reliability of materials with defects.     

THE DEPTH AND THE BREADTH OF THEORETICAL MECHANICS IN THE TEACHING PRACTICE1)

理论力学是工科专业的基础课,要提升学业挑战度,增加课程难度,拓展课程深度,那么该门课程对于工科专业来说,是首先要进行打造的。专业基础课的深度和广度拓展后,才能支撑后续专业课的拓展。文中从理论力学的教学环节、教学内容、教学方法和手段,以及实践环节几方面,探讨理论力学课堂教学的深度和广度的拓展,力求能够为打造理论力学成为"金课"出一份力。     

Visible Light Cross‐Linking of Gelatin Hydrogels Offers an Enhanced Cell Microenvironment with Improved Light Penetration Depth

In this study, the cyto‐compatibility and cellular functionality of cell‐laden gelatin‐methacryloyl (Gel‐MA) hydrogels fabricated using a set of photo‐initiators which absorb in 400–450 nm of the visible light range are investigated. Gel‐MA hydrogels cross‐linked using ruthenium (Ru) and sodium persulfate (SPS), are characterized to have comparable physico‐mechanical properties as Gel‐MA gels photo‐polymerized using more conventionally adopted photo‐initiators, such as 1‐[4‐(2‐hydroxyethoxy)‐phenyl]‐2‐hydroxy‐2‐methyl‐1‐propan‐1‐one (Irgacure 2959) and lithium phenyl(2,4,6‐trimethylbenzoyl) phosphinate (LAP). It is demonstrated that the Ru/SPS system has a less adverse effect on the viability and metabolic activity of human articular chondrocytes encapsulated in Gel‐MA hydrogels for up to 35 days. Furthermore, cell‐laden constructs cross‐linked using the Ru/SPS system have significantly higher glycosaminoglycan content and re‐differentiation capacity as compared to cells encapsulated using I2959 and LAP. Moreover, the Ru/SPS system offers significantly greater light penetration depth as compared to the I2959 system, allowing thick (10 mm) Gel‐MA hydrogels to be fabricated with homogenous cross‐linking density throughout the construct. These results demonstrate the considerable advantages of the Ru/SPS system over traditional UV polymerizing systems in terms of clinical relevance and practicability for applications such as cell encapsulation, biofabrication, and in situ cross‐linking of injectable hydrogels.     

Characterization of polymeric surfaces and interfaces using time-of-flight secondary ion mass spectrometry

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used for chemical analysis of surfaces. ToF-SIMS is a powerful tool for polymer science because it detects a broad mass range with good mass resolution, thereby distinguishing between polymers that have similar elemental compositions and/or the same types of functional groups. Chemical labeling techniques that enhance contrast, such as deuterating or staining one constituent, are generally unnecessary. ToF-SIMS can generate both two-dimensional images and three-dimensional depth profiles, where each pixel in an image is associated with a complete mass spectrum. This Review begins by introducing the principles of ToF-SIMS measurements, including instrumentation, modes of operation, strategies for data analysis, and strengths/limitations when characterizing polymer surfaces. The sections that follow describe applications in polymer science that benefit from characterization by ToF-SIMS, including thin films and coatings, polymer blends, composites, and electronic materials. The examples selected for discussion showcase the three standard modes of operation (spectral analysis, imaging, and depth profiling) and highlight practical considerations that relate to experimental design and data processing. We conclude with brief comments about broader opportunities for ToF-SIMS in polymer science.     

On the relationships between resolution,dimensionless stability,pseudopotential well depth,acceptance, and transmission in mass filters

The relationships between resolution, stability, pseudopotential well depth, acceptance aperture, and transmission for sinusoidal quadrupole mass filters are examined graphically and mathematically. Simple linear or power relationships are revealed. Comparison of these quantities plotted against resolving power show that the pseudopotential well depth correlates well with the mass filter transmission. Pseudopotential well depth is directly proportional to the product of dimensionless stability well depth and the AC voltage. This relationship extends to all quadrupoles regardless of operational zone because it is rooted in stability. Ion transmission and sensitivity scale directly with the pseudopotential well depth. Resolving power and pseudopotential well depth increase when operating in higher stability zones for all types of mass filters. Unfortunately, for fixed frequency sine wave mass filters, the increased resolving power and pseudopotential well depth are accompanied by a significant reduction of the mass range and increased in fringe field effects. For these reasons, sine mass filter operation in higher stability zones has been reported but not commercially produced. In contrast, for rectangular wave mass filter operation, there is no mass range limitation in any stability zone. The fringe field does not increase because the AC voltage is constant and does not change within a single stability zone or between them. A DC voltage is also unnecessary to access any zone. The high resolution and sensitivity of rectangular wave mass filters that can be gained by operation in higher stability zones without mass limit and limited fringe field restrictions suggest a bright and expansive future for this technology.     

In Search of the Driving Factor for the Microwave Curing of Epoxy Adhesives and for the Protection of the Base Substrate against Thermal Damage

This study used controlled microwaves to elucidate the response of adhesive components to microwaves and examined the advantages of microwave radiation in curing epoxy adhesives. Curing of adhesives with microwaves proceeded very rapidly, even though each component of the adhesive was not efficiently heated by the microwaves. The reason the adhesive cured rapidly is that microwave heating was enhanced by the electrically charged (ionic) intermediates produced by the curing reaction. In contrast, the cured adhesive displayed lower microwave absorption and lower heating efficiency, suggesting that the cured adhesive stopped heating even if it continued to be exposed to microwaves. This is a definite advantage in the curing of adhesives with microwaves, as, for example, adhesives dropped onto polystyrene could be cured using microwave heating without degrading the polystyrene base substrate.