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814 result(s) for "mechanochemistry"
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Outstanding Advantages, Current Drawbacks, and Significant Recent Developments in Mechanochemistry: A Perspective View
Although known since antiquity, mechanochemistry has remained dormant for centuries. Nowadays, mechanochemistry is a flourishing research field at the simultaneous stages of gathering data and (often astonishing) observations, and scientific argumentation toward their analysis, for which the combination of interdisciplinary expertise is necessary. Mechanochemistry’s implementation as a synthetic method is constantly increasing, although it remains far from being fully exploited, or understood on the basis of fundamental principles. This review starts by describing many remarkable advantages of mechanochemical reactions, simplifying and “greening” chemistry in solutions. This description is followed by an overview of the current main weaknesses to be addressed in the near future toward the systematic study of its energetics and chemical mechanisms. This review finishes by describing recent breakthrough experimental advances, such as in situ kinetics monitoring using synchrotron X-ray powder diffraction and Raman spectroscopy, plus equally significant computational chemistry approaches, such as quantum mechanochemistry, used for the understanding of covalent or hydrogen bond ruptures in biomolecules or mechanophores in polymers at the single-molecule level. Combined with new technologies to control temperature and pressure in ball mills, these appealing new methods are promising tools for establishing the fundamental knowledge necessary for the understanding of mechanochemical reactivity and mechanisms.
Quantifying forces in cell biology
Physical forces influence the growth and development of all organisms. In the second Review in the Series on Mechanobiology, Trepat and co-authors describe techniques to measure forces generated by cells, and discuss their use and limitations. Cells exert, sense, and respond to physical forces through an astounding diversity of mechanisms. Here we review recently developed tools to quantify the forces generated by cells. We first review technologies based on sensors of known or assumed mechanical properties, and discuss their applicability and limitations. We then proceed to draw an analogy between these human-made sensors and force sensing in the cell. As mechanics is increasingly revealed to play a fundamental role in cell function we envisage that tools to quantify physical forces may soon become widely applied in life-sciences laboratories.
Enzymatic depolymerization of highly crystalline polyethylene terephthalate enabled in moist-solid reaction mixtures
Less than 9% of the plastic produced is recycled after use, contributing to the global plastic pollution problem. While polyethylene terephthalate (PET) is one of the most common plastics, its thermomechanical recycling generates a material of lesser quality. Enzymes are highly selective, renewable catalysts active at mild temperatures; however, they lack activity toward the more crystalline forms of PET commonly found in consumer plastics, requiring the energy-expensive melt-amorphization step of PET before enzymatic depolymerization. We report here that, when used in moist-solid reaction mixtures instead of the typical dilute aqueous solutions or slurries, the cutinase from Humicola insolens can directly depolymerize amorphous and crystalline regions of PET equally, without any pretreatment, with a 13-fold higher space-time yield and a 15-fold higher enzyme efficiency than reported in prior studies with high-crystallinity material. Further, this process shows a 26-fold selectivity for terephthalic acid over other hydrolysis products.
Mechanochemical Synthesis of MOF-303 and Its CO2 Adsorption at Ambient Conditions
Metal–organic structures have great potential for practical applications in many areas. However, their widespread use is often hindered by time-consuming and expensive synthesis procedures that often involve hazardous solvents and, therefore, generate wastes that need to be remediated and/or recycled. The development of cleaner, safer, and more sustainable synthesis methods is extremely important and is needed in the context of green chemistry. In this work, a facile mechanochemical method involving water-assisted ball milling was used for the synthesis of MOF-303. The obtained MOF-303 exhibited a high specific surface area of 1180 m2/g and showed an excellent CO2 adsorption capacity of 9.5 mmol/g at 0 °C and under 1 bar.
Thermocatalytic Decomposition of Methane Over NiO–MgO Catalysts Synthesized by the Mechanochemical Method
The reaction of methane decomposition is an endothermic process that produces hydrogen without any impurities as a gas product and carbon nanotubes/carbon nanofibers as a solid product. In this study, NiO–MgO catalysts with different nickel loadings (20, 30, 40, and 50 wt. %) were synthesized using the mechanochemical method. The Physicochemical features of the synthesized catalysts were characterized by various methods such as BET, XRD, SEM, TPO, and H2-TPR. The prepared samples were tested in the methane decomposition process at various temperatures under the GHSV value of 48,000 ml/(gcat h). Among the prepared samples, the 50wt.%NiO–MgO exhibited the best activity (40% methane conversion at 575 °C) in this process due to its higher concentration of active metal and better catalyst reducibility. Also, the effect of different parameters such as feed ratio, GHSV, and calcination temperature was studied on the activity of this catalyst. The results showed that with the increase of GHSV and feed ratio, the methane conversion decreased due to the lesser contact time and diminishing the proportion of accessible active sites per methane entrance molecules. Moreover, the results showed that with the rise of calcination temperature from 500 to 700 °C, the methane conversion decreased due to the sintering of nickel particles. The results also showed that the addition of 15 wt.% Cr2O3 to the catalyst formulation improved the catalytic performance and lifetime in the thermocatalytic decomposition of methane due to the higher reducibility and dispersion of the active species on the catalyst surface.
Mechanochemical synthesis of small organic molecules
With the growing interest in renewable energy and global warming, it is important to minimize the usage of hazardous chemicals in both academic and industrial research, elimination of waste, and possibly recycle them to obtain better results in greener fashion. The studies under the area of mechanochemistry which cover the grinding chemistry to ball milling, sonication, etc. are certainly of interest to the researchers working on the development of green methodologies. In this review, a collection of examples on recent developments in organic bond formation reactions like carbon–carbon (C–C), carbon–nitrogen (C–N), carbon–oxygen (C–O), carbon–halogen (C–X), etc. is documented. Mechanochemical syntheses of heterocyclic rings, multicomponent reactions and organometallic molecules including their catalytic applications are also highlighted.
Mechanochemical difluoromethylations of ketones
We present a mechanochemical synthesis of difluoromethyl enol ethers. Utilizing an in situ generation of difluorocarbenes, ketones are efficiently converted to the target products under solvent-free conditions. The reactions proceed at room temperature and are complete within 90 minutes, demonstrating both efficiency and experimental simplicity.
Methods for Exerting and Sensing Force in Polymer Materials Using Mechanophores
In recent years, polymer mechanochemistry has evolved as a methodology to provide insights into the action‐reaction relationships of polymers and polymer‐based materials and composites in terms of macroscopic force application (stress) and subsequent deformation (strain) through a mechanophore‐assisted coupling of mechanical and chemical phenomena. The perplexity of the process, however, from the viewpoint of mechanophore activation via a molecular‐scaled disruption of the structure that yields a macroscopically detectable optical signal, renders this otherwise rapidly evolving field challenging. Motivated by this, we highlight here recent advancements of polymer mechanochemistry with particular focus on the establishment of methodologies for the efficient activation and quantification of mechanophores and anticipate to aptly pinpoint unresolved matters and limitations of the respective approaches, thus highlighting possible developments. Polymer mechanochemistry facilitates an in‐depth investigation of the behavior of polymers and polymer‐based materials and composites, and provides insights into their action‐reaction relationships through the coupling of mechanical and chemical phenomena. The selective mechanochemical activation of mechanophores via a molecular‐scaled disruption of the structure yields macroscopically detectable optical signals upon force application expressed in different manifestations.
Mechanochemistry: A Green Approach in the Preparation of Pharmaceutical Cocrystals
Mechanochemistry is considered an alternative attractive greener approach to prepare diverse molecular compounds and has become an important synthetic tool in different fields (e.g., physics, chemistry, and material science) since is considered an ecofriendly procedure that can be carried out under solvent free conditions or in the presence of minimal quantities of solvent (catalytic amounts). Being able to substitute, in many cases, classical solution reactions often requiring significant amounts of solvents. These sustainable methods have had an enormous impact on a great variety of chemistry fields, including catalysis, organic synthesis, metal complexes formation, preparation of multicomponent pharmaceutical solid forms, etc. In this sense, we are interested in highlighting the advantages of mechanochemical methods on the obtaining of pharmaceutical cocrystals. Hence, in this review, we describe and discuss the relevance of mechanochemical procedures in the formation of multicomponent solid forms focusing on pharmaceutical cocrystals. Additionally, at the end of this paper, we collect a chronological survey of the most representative scientific papers reporting the mechanochemical synthesis of cocrystals.
Mechanisms of ZDDP—An Update
This paper describes how research over the last 20 years has advanced our understanding of the mechanisms of action of ZDDP, especially with respect to tribofilm formation. We now know that ZDDP tribofilm formation is promoted by applied shear stress and this explains many of the features of these films. We also now recognise that ZDDP tribofilms evolve during rubbing from relatively soft, long chain polyphosphate films to much more wear-resistant, short chain phosphates. Several disadvantages of ZDDPs as lubricant additives have emerged in recent years, in particular their tendency to increase friction in thin film rubbing conditions, their promotion of micropitting wear, and accelerated wear when present together with soot contaminants in engine oils. Research has revealed the origins of all these effects. Over the last 20 years there have been growing efforts to model ZDDP tribofilm formation, both at a macro- and molecular-scale, so far with limited success. Finally, this paper outlines some aspects of ZDDP behaviour that we still do not fully understand and where further research is needed. Graphical Abstract