Cemented vs. Cementless Fixation in Primary Knee Replacement: A Narrative Review.

Knee osteoarthritis (OA) is one of the leading causes of disability around the globe. Osteoarthritis is mainly considered a disease affecting the elderly. However, more and more studies show that sports overuse, obesity, or congenital disorders can initiate a pathologic cascade that leads to OA changes in the younger population. Nevertheless, OA mostly affects the elderly, and with increasing life expectancy, the disease will develop in more and more individuals. To date, the golden standard in the treatment of the end-stage of the disease is total joint replacement (TJR), which restores painless knee motion and function. One of the weakest elements in TJR is its bonding with the bone, which can be achieved by bonding material, such as poly methyl-methacrylate (PMMA), or by cementless fixation supported by bone ingrowth onto the endoprosthesis surface. Each technique has its advantages; however, the most important factor is the revision rate and survivor time. In the past, numerous articles were published regarding TJR revision rate, but no consensus has been established yet. In this review, we focused on a comparison of cemented and cementless total knee replacement surgeries. We introduced PICO rules, including population, intervention, comparison and outcomes of TJR in a PubMed search. We identified 783 articles published between 2010 and 2023, out of which we included 14 in our review. Our review reveals that there is no universally prescribed approach to fixate knee prostheses. The determination of the most suitable method necessitates an individualized decision-making process involving the active participation and informed consent of each patient.

Ammonium-tagged ruthenium-based catalysts for olefin metathesis in aqueous media under ultrasound and microwave irradiation.

The influence of microwave and ultrasonic irradiation on the performance of ammonium-tagged Ru-based catalysts in olefin metathesis transformations in aqueous media was studied. Differences in the catalytic activity in correlation with the nature of the present counter ion and the size of the N-heterocyclic carbene (NHC) ligand were revealed. The presented methodology allows for preparation of a variety of polar and non-polar metathesis products under environmentally friendly conditions.

The doping effect of fluorinated aromatic solvents on the rate of ruthenium-catalysed olefin metathesis.

A study concerning the effect of using a fluorinated aromatic solvent as the medium for olefin metathesis reactions catalysed by ruthenium complexes bearing N-heterocyclic carbene ligands is presented. The use of fluorinated aromatic hydrocarbons (FAH) as solvents for olefin metathesis reactions catalysed by standard commercially available ruthenium pre-catalysts allows substantially higher yields of the desired products to be obtained, especially in the case of demanding polyfunctional molecules, including natural and biologically active compounds. Interactions between the FAH and the second-generation ruthenium catalysts, which apparently improve the efficiency of the olefin metathesis transformation, have been studied by X-ray structure analysis and computations, as well as by carrying out a number of metathesis experiments. The optimisation of reaction conditions by using an FAH can be regarded as a complementary approach for the design of new improved ruthenium catalysts. Fluorinated aromatic solvents are an attractive alternative medium for promoting challenging olefin metathesis reactions.

The doping effect of fluorinated aromatic hydrocarbon solvents on the performance of common olefin metathesis catalysts: application in the preparation of biologically active compounds.

Aromatic fluorinated hydrocarbons, used as solvents for olefin metathesis reactions, catalysed by standard commercially available Ru precatalysts, allow substantially higher yields to be obtained, especially of challenging substrates, including natural and biologically active compounds.

In an attempt to provide a user's guide to the galaxy of benzylidene, alkoxybenzylidene, and indenylidene ruthenium olefin metathesis catalysts.

The data reported in this paper demonstrate that great care must be taken when choosing an appropriate catalyst for a given metathesis reaction. First-generation catalysts were found to be useful in the metathesis of sterically unhindered substrates. Second-generation catalysts (under optimised conditions) showed good to excellent activities toward sterically hindered and electron-withdrawing group (EWG)-substituted alkenes that do not react using the first-generation complexes. A strong temperature effect was noted on all of the reactions tested. Interestingly, attempts to force a reaction by increasing the catalyst loading were much less effective. Therefore, when possible, it is suggested that metathesis transformations should be carried out with a second-generation catalyst at 70 degrees C in toluene. However, different second-generation catalysts proved to be optimal for different applications and no single catalyst outperformed all others in all cases. Nevertheless, some empirical rules can be deduced from the model experiments, providing preliminary hints for the selection of the optimal catalysts.

A highly selective synthesis of dialkenyl sulfones via cross-metathesis of divinyl sulfone.

Catalytic cross-metathesis of commercial divinyl sulfone allowed direct access to novel (E)-alkenylvinyl sulfones and (E,E)-dialkenyl sulfones with excellent stereoselectivity. These compounds are useful building blocks, e.g., in the synthesis of substituted thiomorpholine 1,1-dioxide derivatives. [reaction: see text]

Advanced fine-tuning of grubbs/hoveyda olefin metathesis catalysts: a further step toward an optimum balance between antinomic properties.

A 95% yield in the cross metathesis of acrylonitrile with a model olefin is achieved at 25 degrees C with only 3 mol % of the new air-stable ruthenium catalyst 1f shown in the enclosed structural diagram. Even more remarkable are the performances of its boosted version 1g incorporating an electron-withdrawing group. Both these new enhanced versions of Hoveyda catalyst are readily available from Grubbs second generation precatalyst upon reaction with a styrenyl ether the end group of which has been functionalized by an ester function. The latter acts as a weakly coordinating ligand allowing to reach a desirable balance between antinomic properties such as the catalyst's stability, a high activity for challenging substrates, and a high initiation rate.

Catalysts for new tasks: preparation and applications of tunable ruthenium catalysts for olefin metathesis.

A continuous survey across structures, made over the past decades, has led to the development of highly active olefin metathesis catalysts for sophisticated synthetic tasks and for polymer technology. In this paper, our efforts toward novel and improved ruthenium complexes with even better performance in olefin metathesis are described. Oxygen ether derivatives 3, pioneered by Hoveyda, exhibit high activity and possess excellent functional group tolerance. We have successfully fine-tuned catalyst 3b to increase its activity and applicability by the introduction of electron-withdrawing groups to diminish the donor properties of the oxygen atom. As a result, the stable and easily accessible nitro-substituted catalyst 6 has found a number of successful applications in various research and industrial laboratories. We were intrigued by the possibility to further fine-tune the Hoveyda-type catalysts by combining two activating effects-steric and electronic-in a single catalyst. This was possible to achieve in so-called scorpio carbenes, which are currently under investigation in our laboratory. These modifications can be used not only to control the catalyst activity, but also to alter its physical-chemical properties, such as solubility in a given medium or an affinity to silica gel. An example of immobilization strategy based on this concept is presented.

Ortho- and para-substituted Hoveyda-Grubbs carbenes. An improved synthesis of highly efficient metathesis initiators.

A novel highly efficient and general route to various 3- and 5-substituted 2-alkoxystyrenes, required for the preparation of Hoveyda-Grubbs catalysts, is described.