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ConspectusThe encapsulation of ions into macro(bi)cyclic hosts lies at the core of supramolecular chemistry. While chemically inert hosts such as crown ethers (synthesis) and cyclodextrins (Febreze) have enabled real-world applications, there is a wider and accelerating trend toward functional molecules and materials that are stimuli-responsive, degradable, or recyclable. To endow supramolecular hosts with these properties, a deviation from ether C-O bonds is required, and functional groups that engage in equilibrium reactions under relatively mild conditions are needed.In this Account, we describe our group's work on supramolecular hosts that comprise orthoester and trialkoxysilane bridgeheads. In their simplest structural realization, these compounds resemble both Cram's crown ethers (macrocycles with oxygen donor atoms) and Lehn's cryptands (macrobicycles with 3-fold symmetry). It is therefore not surprising that these new hosts were found to have a natural propensity to bind cations relatively strongly. In recent work, we were also able to create anion-binding hosts by placing disubstituted urea motifs at the center of the tripodal architecture. Structural modifications of either the terminal substituents (e.g., H vs CH 3 on the bridgehead), the diol (e.g., chiral), or the bridgehead atom itself (Si vs C) were found to have profound implications on the guest-binding properties.What makes orthoester/trialkoxysilane hosts truly unique is their dynamic covalent chemistry. The ability to conduct exchange reactions with alcohols at the bridgehead carbon or silicon atom is first and foremost an opportunity to develop highly efficient syntheses. Indeed, all hosts presented in this Account were prepared via templated self-assembly in yields of up to 90%. This efficiency is remarkable because the macrobicyclic architecture is established in one single step from at least five components. A second opportunity presented by dynamic bridgeheads is that suitable mixtures of orthoester hosts or their subcomponents can be adaptive, i.e. they respond to the presence of guests such that the addition of a certain guest can dictate the formation of a preferred host. In an extreme example of dynamic adaptivity, we found that ammonium ions can fulfill the dual role of catalyst for orthoester exchange and cationic template for efficient host formation, representing an unprecedented example of a fluxional supramolecular complex. The third implication of dynamic bridgeheads is due to the reaction of orthoesters and trialkoxysilanes with water instead of alcohols. We describe in detail how the hydrolysis rate differs strongly between O , O , O -orthoesters, S , S , S -trithioorthoesters, and trialkoxysilanes and how it is tunable by the choice of substituents and pH.We expect that the fundamental insights into exchange and degradation kinetics described in this Account will be useful far beyond supramolecular chemistry.

The dynamic covalent chemistry (DCvC) of the Si-O bond holds unique opportunities, but has rarely been employed to assemble discrete molecular architectures. This may be due to the harsh conditions required to initiate exchange reactions at silicon in aprotic solvents. Herein, we provide a comprehensive experimental and computational account on the reaction of trialkoxysilanes with alcohols and identify mild conditions for rapid exchange in aprotic solvents. Substituent, solvent and salt effects are uncovered, understood and exploited for the construction of sila-orthoester cryptates. A sharp, divergent pH-response of the obtained cages renders this substance class attractive for future applications well beyond host-guest chemistry, for instance, in drug delivery., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The increased importance of RNA-based therapeutics comes with a need to develop next-generation stimuli-responsive systems capable of binding, transporting and releasing RNA oligomers. In this work, we describe triazolium-based amphiphiles capable of siRNA binding and enzyme-responsive release of the nucleic acid payload. In aqueous medium, the amphiphile self-assembles into nanocarriers that can disintegrate upon the addition of esterase. Key to the molecular design is a self-immolative linker that is anchored to the triazolium moiety and acts as a positively-charged polar head group. We demonstrate that addition of esterase leads to a degradation cascade of the linker, leaving the neutral triazole compound unable to form complexes and therefore releasing the negatively-charged siRNA. The reported molecular design and overall approach may have broad utility beyond this proof-of-principle study, because the underlying CuAAC "click" chemistry allows bringing together three groups very efficiently as well as cleaving off one of the three groups under the mild action of an esterase enzyme., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

While supramolecular hosts capable of binding and transporting anions and ion pairs are now widely available, self-assembled architectures are still rare, even though they offer an inherent mechanism for the release of the guest ion(s). In this work, we report the dynamic covalent self-assembly of tripodal, urea-based anion cryptates that are held together by two orthoester bridgeheads. These hosts exhibit affinity for anions such as Cl - , Br - or I - in the moderate range that is typically advantageous for applications in membrane transport. In unprecedented experiments, we were able to dissociate the Cs⋅Cl ion pair by simultaneously assembling suitably sized orthoester hosts around the Cs + and the Cl - ion., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Although previous studies investigating the MALDI Biotyper database (matrix-assisted laser desorption/ionization time-of-flight mass spectrometry-based identification) have proven its high accuracy for bacterial identification, the studies differed in sample preparation, number of replicates, quantity of shots and target types used. In particular, the score cut-off values of special importance for reliable species identification varied. The aim of the present study was to identify species-specific differences in the mean score values for staphylococci. Cut-off values recommended by the manufacturer were adapted using the 20th percentile to rule out unknown score-modifying factors, even though the specificity was high and the lowest cut-off values would also yield an accurate result. Whilst correct species diagnosis was obtained in 97.32 % of samples (1382/1420), only 220 of all duplicates (15.49 %) revealed a score of ≥2.3, whilst 968 (68.17 %) had a score between 2.0 and 2.299, and 194 (13.66 %) had a score of <2.0. Ten of 21 species had a calculated 20th percentile of <2.0 and one species of <1.7. In conclusion, the use of species-specific cut-off values improves the relative sensitivity of species identification in staphylococci.

Objectives: The recently introduced ultrasonic osteotome procedure is an alternative to conventional methods of osteotomy. The aim of the present study was to establish the differences between five recently introduced ultrasonic osteotomes and to perform micromorphological and quantitative roughness analyses of osteotomized bone surfaces., Materials and Methods: Fresh, standard-sized bony samples were taken from a rabbit skull using the following ultrasonic osteotomes: the Piezosurgery 3 with insert tip OT7, Piezosurgery Medical with insert tip MT1-10, Piezon Master Surgery with insert tip SL1, VarioSurg with inert tip SG1, and Piezotome 2 with insert tip BS1 II. The required duration of time for each osteotomy was recorded. The prepared surfaces were examined via light microscopy, environmental surface electron microscopy (ESEM), and confocal laser scanning microscopy (CLSM)., Results: All of the investigated piezoelectric osteotomes preserved the anatomical structure of bone. The mean roughness values of the osteotomized bone edge obtained using the investigated piezoelectric osteotomes were as follows: 2.47 μm (Piezosurgery 3), 9.79 μm (Piezosurgery Medical), 4.66 μm (Piezon Master Surgery), 6.38 μm (VarioSurg), and 6.06 μm (Piezotome 2). Significantly higher roughness values were observed when using the Piezosurgery Medical in comparison with those achieved by the Piezosurgery 3 (P<0.0001) and Piezon Master Surgery (P=0.002). Different osteotomy durations were achieved using the different piezoelectric osteotomes: 144 s (Piezosurgery 3), 126 s (Piezosurgery Medical), 142 s (Piezon Master Surgery), 149 s (VarioSurg), and 137 s (Piezotome 2)., Conclusions: In the present study, micromorphological differences following the use of various ultrasonic devices were clearly identified. According to this study, it can be concluded that the power and the composition of the teeth of the insert tip might impact procedure duration and cutting qualities., (© 2011 John Wiley & Sons A/S.)

The head and neck region is the second most common site for the development of extranodal lymphomas. Richter's syndrome (RS) involves the transformation of B-cell chronic lymphocytic leukemia (B-CLL) to an aggressive lymphoma, most commonly, diffuse large B-cell lymphoma (DLBCL). We report the case of a 62-year-old man who developed DLBCL in the periorbital region 2 months after blunt trauma to the site. The patient lacked other physical symptoms at the time of presentation. Bone marrow biopsy and immunophenotypic analysis revealed a Richter transformation of unknown B-CLL. RS frequently arises in lymph nodes or bone marrow and rarely presents with extranodal involvement. Chemotherapy resulted in total remission of the lymphoma and no relapse was observed in the 6-month follow-up period. This case demonstrates that the clinician must recognize that unresolved soft tissue swelling after a trauma may be caused by NHL., (Copyright 2010 Mosby, Inc. All rights reserved.)