Elemental analysis of particulate matter in a metal workshop and of biological samples from exposed workers

During metal welding and cutting, large amounts of particulate matter (PM) are produced that might represent a significant health risk for the exposed workers. In the present pilot study, we performed an elemental analysis of fine PM collected in a metal workshop. Also, elemental analysis of the hair and nail samples collected from workers exposed to the workshop dust and control group was done. Concentrations of 15 elements in PM were measured with X‐Ray Fluorescence (XRF) and Particle Induced X‐ray Emission (PIXE), whereas inductively coupled plasma mass spectrometry (ICP‐MS) was used to determine 12 elements in hair and nail samples. Mean 8‐hr concentrations of PM_2.5, Fe, and Mn in the vicinity of welders were up to 1803, 860, and 30 μg/m³, respectively, whereas in the nearby city, daily PM_2.5 concentrations are on average 11 μg/m³. We found that several elements, especially Fe and Mn, had substantially higher concentrations in hair and nail samples of exposed workers than in the control group, which indicates the accumulation of metals in workers' tissues, although limit values were not exceeded.     

Development of an improved divergence‐free‐condition compensated coupled framework to solve flow problems with time‐varying geometries

In this article a coupled version of the improved divergence‐free‐condition compensated method will be proposed to simulate time‐varying geometries by direct forcing immersed boundary method. The proposed method can be seen as a quasi‐multi‐moment framework due to the fact that the momentum equations are discretized by both cell‐centered and cell‐face velocity. For simulating time‐varying geometries, a semi‐implicit iterative method is proposed for calculating the direct forcing terms. Treatments for suppressing spurious force oscillations, calculating drag/lift forces, and evaluating velocity and pressure for freshly cells will also be addressed. In order to show the applicability and accuracy, analytical as well as benchmark problems will be investigated by the present framework and compared with other numerical and experimental results.     

Polymer 4D printing: Advanced shape-change and beyond

4D printing is an exciting branch of additive manufacturing. It relies on established 3D printing techniques to fabricate objects in much the same way. However, structures which fall into the 4D printed category have the ability to change with time, hence the “extra dimension.” The common perception of 4D printed objects is that of macroscopic single-material structures limited to point-to-point shape change only, in response to either heat or water. However, in the area of polymer 4D printing, recent advancements challenge this understanding. A host of new polymeric materials have been designed which display a variety of wonderful effects brought about by unconventional stimuli, and advanced additive manufacturing techniques have been developed to accommodate them. As a result, the horizons of polymer 4D printing have been broadened beyond what was initially thought possible. In this review, we showcase the many studies which evolve the very definition of polymer 4D printing, and reveal emerging areas of research integral to its advancement.     

Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

Finding any given 2‐factor in sparse pseudorandom graphs efficiently

Given an $n$‐vertex pseudorandom graph $G$ and an $n$‐vertex graph $H$ with maximum degree at most two, we wish to find a copy of $H$ in $G$, that is, an embedding $\phi :V\left(H\right)\to V\left(G\right)$ so that $\phi \left(u\right)\phi \left(v\right)\in E\left(G\right)$ for all $uv\in E\left(H\right)$. Particular instances of this problem include finding a triangle‐factor and finding a Hamilton cycle in $G$. Here, we provide a deterministic polynomial time algorithm that finds a given $H$ in any suitably pseudorandom graph $G$. The pseudorandom graphs we consider are $\left(p,\lambda \right)$‐bijumbled graphs of minimum degree which is a constant proportion of the average degree, that is, $\mathrm{\Omega }\left(pn\right)$. A $\left(p,\lambda \right)$‐bijumbled graph is characterised through the discrepancy property: $|e\left(A,B\right)?p|A||B||<\lambda \sqrt{|A||B|}$ for any two sets of vertices $A$ and $B$. Our condition $\lambda =O(p^{2}n/\log n)$ on bijumbledness is within a log factor from being tight and provides a positive answer to a recent question of Nenadov. We combine novel variants of the absorption‐reservoir method, a powerful tool from extremal graph theory and random graphs. Our approach builds on our previous work, incorporating the work of Nenadov, together with additional ideas and simplifications.     

Enantioselective C−H Activation with Earth‐Abundant 3d Transition Metals

Molecular syntheses largely rely on time‐ and labour‐intensive prefunctionalization strategies. In contrast, C?H activation represents an increasingly powerful approach that avoids lengthy syntheses of prefunctionalized substrates, with great potential for drug discovery, the pharmaceutical industry, material sciences, and crop protection, among others. The enantioselective functionalization of omnipresent C?H bonds has emerged as a transformative tool for the step‐ and atom‐economical generation of chiral molecular complexity. However, this rapidly growing research area remains dominated by noble transition metals, prominently featuring toxic palladium, iridium and rhodium catalysts. Indeed, despite significant achievements, the use of inexpensive and sustainable 3d metals in asymmetric C?H activations is still clearly in its infancy. Herein, we discuss the remarkable recent progress in enantioselective transformations via organometallic C?H activation by 3d base metals up to April 2019.     

Selective Decrosslinking in Liquid Crystal Polymer Actuators for Optical Reconfiguration of Origami and Light‐Fueled Locomotion

The ability to optically reconfigure an existing actuator of a liquid crystal polymer network (LCN) so that it can display a new actuation behavior or function is highly desired in developing materials for soft robotics applications. Demonstrated here is a powerful approach relying on selective polymer chain decrosslinking in a LCN actuator with uniaxial LC alignment. Using an anthracene‐containing LCN, spatially controlled optical decrosslinking can be realized through photocleavage of anthracene dimers under 254 nm UV light, which alters the distribution of actuation (crosslinked) and non‐actuation (decrosslinked) domains and thus determines the actuation behavior upon order‐disorder phase transitions. Based on this mechanism, a single actuator having a flat shape can be reconfigured in an on‐demand manner to exhibit reversible shape transformation such as self‐folding into origami three‐dimensional structures. Moreover, using a dye‐doped LCN actuator, a light‐fueled microwalker can be optically reconfigured to adopt different locomotion behaviors, changing from moving in the laser scanning direction to moving in the opposite direction.     

Recent advances and challenges in the recovery and purification of cellular exosomes

Exosomes are nanovesicles secreted by most cellular types that carry important biochemical compounds throughout the body with different purposes, playing a preponderant role in cellular communication. Because of their structure, physicochemical properties and stability, recent studies are focusing in their use as nanocarriers for different therapeutic compounds for the treatment of different diseases ranging from cancer to Parkinson's disease. However, current bioseparation protocols and methodologies are selected based on the final exosome application or intended use and present both advantages and disadvantages when compared among them. In this context, this review aims to present the most important technologies available for exosome isolation while discussing their advantages and disadvantages and the possibilities of being combined with other strategies. This is critical since the development of novel exosome‐based therapeutic strategies will be constrained to the effectiveness and yield of the selected downstream purification methodologies for which a thorough understanding of the available technological resources is needed.