Molecular tweezers in nitroaromatic sensing

Apart from their destructive force, nitroaromatic compounds also are toxic and harmful to humans and the environment. While a number of plants, bacteria and fungi produce nitroaromatic compounds, the largest part of these compounds found in the environment stems from industrial uses. Although nitroaromatic compounds can be detected in a laboratory, the corresponding equipment may be too delicate and/or not mobile enough to be used in the field where smaller devices are more suitable. Sensor-systems relying on the interaction or reaction of nitroaromatics with other molecules are of interest (notable for hand-held devices) because of ease of detection, simple material handling and short response time. Molecular tweezers constitute a promising class of molecules that could be able of molecular recognition of trace quantities of nitroaromatic compounds. In this thesis, the synthesis of different designed molecular tweezers is presented as well as their sensing properties in the presence of a guest, as determined from 1H-NMR titrations. The results are then interpreted in relation to molecular structure, with the aid of computational calculations

Determining Inversion Barriers in Atrop- isomers - A Tutorial for Organic Chemists

Dynamic behavior is a fascinating property of natural and artificial systems and its understanding has significantly impacted the transformation of molecular interchanges into controlled molecular motion. In this tutorial, the key descriptors of enantiomeric stability are examined in-depth. Enantiomerization and racemization are discussed and differentiated on a fundamental level proposing a unified and distinct nomenclature. Their mathematical meanings and relations are described and deduced cohesively in the context of atropisomerization. The calculation of inversion barriers from thermodynamic and kinetic data is demonstrated and the interdependences between the latter are explained mathematically. Using current examples from our group, the determination of rate constants and the thermodynamic parameters is shown in a step-by-step manner using the most common techniques. The tutorial is concluded with aspects and considerations concerning statistical data analysis and error determination of measurements including a practical guide to Monte-Carlo simulations

Bicyclic Phenyl–Ethynyl Architectures: Synthesis of a 1,4-Bis(phenylbuta-1,3-diyn-1-yl) Benzene Banister

The novel diacetylene bridged terphenylic macrocycle 1 is presented and discussed in the context of rotationally restricted “Geländer” oligomers. The 1,4‐bis(phenylbuta‐1,3‐diyn‐1‐yl) benzene bridge of diacetylene 1 is significantly longer than its terphenyl backbone, forcing the bridge to bend around the central pylon. The synthesis of molecule 1 is based to a large extent on acetylene scaffolding strategies, profiting from orthogonal alkyne protection groups to close both macrocyclic subunits by oxidative acetylene coupling sequentially. The spatial arrangement and the dynamic enantiomerization process of the bicyclic target structure 1 are analyzed. In‐depth NMR investigations not only reveal an unexpected spatial arrangement with both oligomer strands bent alongside the backbone, but also display the limited stability of the model compound in the presence of molecular oxygen

Bicyclic Phenyl-Ethynyl Architectures: Synthesis of a 1,4-Bis(phenylbuta-1,3-diyn-1-yl) Benzene Banister

The novel diacetylene bridged terphenylic macrocycle 1 is presented and discussed in the context of rotationally restricted "Gelander" oligomers. The 1,4-bis(phenylbuta-1,3-diyn-1-yl) benzene bridge of diacetylene 1 is significantly longer than its terphenyl backbone, forcing the bridge to bend around the central pylon. The synthesis of molecule 1 is based to a large extent on acetylene scaffolding strategies, profiting from orthogonal alkyne protection groups to close both macrocyclic subunits by oxidative acetylene coupling sequentially. The spatial arrangement and the dynamic enantiomerization process of the bicyclic target structure 1 are analyzed. In-depth NMR investigations not only reveal an unexpected spatial arrangement with both oligomer strands bent alongside the backbone, but also display the limited stability of the model compound in the presence of molecular oxygen

The Effect of Patellar Positioning on Femoral Component Rotation when Performing Flexion Gap Balancing Using a Tensioning Device for Total Knee Arthroplasty

There is an increasing interest in new devices such as tensiometers for flexion gap balancing during total knee arthroplasty (TKA). The purpose of this study was to determine the influence of patella positioning during flexion gap balancing on femoral component rotation. We prospectively evaluated 32 consecutive knees in 31 patients who underwent primary TKA for degenerative osteoarthritis and where soft tissue balancing was performed using the same tensiometer. Preoperative measurements included valgus/varus deformation, mechanical axis, epicondylar axis, and tibial slope. Intraoperatively, measurement of femoral component rotation in 90 degrees of knee flexion was conducted in three different positions of the patella: (1) patella reduced, (2) patella dislocated but not everted, and (3) patella dislocated and everted. The femoral component had significantly higher rotation when the patella was reduced compared with a dislocated patella (4.9 ± 2.1 degrees vs. 4.2 ± 2.2 degrees; p = 0.006) and compared with a dislocated and everted patella (4.9 ± 2.1 degrees vs. 4.1 ± 2.3 degrees; p = 0.006). Varus knees (n = 22) demonstrated significantly increased femoral component rotation if the patella was reduced (5.3 ± 2.2 degrees) compared with dislocated patella without eversion (4.7 ± 2.3 degrees; p = 0.037) and with eversion (4.4 ± 2.5 degrees; p = 0.019). As such, the measurement of the mediolateral flexion gap stability with a laterally dislocated patella leads to a statistically significant overestimation of the lateral ligament stability and an underestimation of the external rotation positioning of the femoral component of approximately 1 degree, which is aggravated in varus knees. This is a Level II, prospective consecutive series study

A Phenyl-Ethynyl-Macrocycle: A Model Compound for "Geländer" Oligomers Comprising Reactive Conjugated Banisters

Macrocycle 1 is assembled as smallest member of a series of “Geländer” oligomers with a conjugated banister comprising exclusively sp2‐ and sp‐hybridized carbon atoms. The synthesis of 1 is based on an acetylene scaffolding approach, comprising Sonogashira cross‐coupling reactions in combination with protection group strategies and a final cyclization based on an oxidative acetylene coupling using Eglinton‐Breslow reaction conditions. Macrocycle 1 serves as model compound for the investigation of the structural integrity of the strained 1,3‐diyne subunit. An enhanced reactivity of the strained 1,3‐diyne subunit is documented by its engagement in Huisgen's (2+3) cycloaddition when exposed to an azide at elevated temperature. Both structures, macrocycle 1 and cycloaddition‐product 2, are fully characterized including their solid‐state structure obtained by X‐ray diffraction analysis

Bicyclic Phenyl–Ethynyl Architectures: Synthesis of a 1,4‐Bis(phenylbuta‐1,3‐diyn‐1‐yl) Benzene Banister

The novel diacetylene bridged terphenylic macrocycle 1 is presented and discussed in the context of rotationally restricted “Geländer” oligomers. The 1,4‐bis(phenylbuta‐1,3‐diyn‐1‐yl) benzene bridge of diacetylene 1 is significantly longer than its terphenyl backbone, forcing the bridge to bend around the central pylon. The synthesis of molecule 1 is based to a large extent on acetylene scaffolding strategies, profiting from orthogonal alkyne protection groups to close both macrocyclic subunits by oxidative acetylene coupling sequentially. The spatial arrangement and the dynamic enantiomerization process of the bicyclic target structure 1 are analyzed. In‐depth NMR investigations not only reveal an unexpected spatial arrangement with both oligomer strands bent alongside the backbone, but also display the limited stability of the model compound in the presence of molecular oxygen