Tuning the Ground and Excited State Dynamics of Hemithioindigo Molecular Motors by Changing Substituents

Efficiency and performance of light triggered molecular motors are crucial features that need to be mechanistically understood to improve the performance and enable conscious property tailoring for specific applications. In this work, three different hemithioindigo-based molecular motors are investigated and all four steps in their complete unidirectional rotation are unraveled fully quantitatively. Transient absorption spectroscopy across twelve orders of magnitude in time is used to probe the fs nuclear motions up to the ms thermal kinetics, covering the timeframe of the whole motor rotation. The newly known full mechanisms allow simulation of the motor systems to scrutinize their performance at realistic illumination conditions. This highlights the importance of photoisomerization quantum yields for the rotation speed. The substitution pattern in close proximity to the rotation axle influences the excited and ground state properties. Reduction of electron donation and concomitant increase of steric hindrance leads to faster photoisomerization reactions with quasi-ballistic behavior, but also to a slight decrease in the quantum efficiency. The expected decelerating effects of increased sterics are primarily manifested in the ground state. A promising approach for next-generation hemithioindigo motors is to elevate electron donation at the rotor fragment followed by an increase of steric hindrance.     

3-Helix micelles stabilized by polymer springs

Despite increasing demands to employ amphiphilic micelles as nanocarriers and nanoreactors, it remains a significant challenge to simultaneously reduce the particle size and enhance the particle stability. Complementary to covalent chemical bonding and attractive intermolecular interactions, entropic repulsion can be incorporated by rational design in the headgroup of an amphiphile to generate small micelles with enhanced stability. A new family of amphiphilic peptide-polymer conjugates is presented where the hydrophilic headgroup is composed of a 3-helix coiled coil with poly(ethylene glycol) attached to the exterior of the helix bundle. When micelles form, the PEG chains are confined in close proximity and are compressed to act as a spring to generate lateral pressure. The formation of 3-helix bundles determines the location and the directionalities of the force vector of each PEG elastic spring so as to slow down amphiphile desorption. Since each component of the amphiphile can be readily tailored, these micelles provide numerous opportunities to meet current demands for organic nanocarriers with tunable stability in life science and energy science. Furthermore, present studies open new avenues to use energy arising from entropic polymer chain deformation to self-assemble energetically stable, single nanoscopic objects, much like repulsion that stabilizes bulk assemblies of colloidal particles.     

Application of open tubular electrochromatography for acidic and basic analytes

Summary The separation of charged analytes by electrochromatography has been examined on porous-layer open tubular capillaries prepared using the sol gel method. An electroosmotic flow of about 2.10×10⁴ cm²V¹s¹ was obtained using between 10 and 30% acetonitrile in the mobile phase. Acidic diuretic drug compounds were successfully separated at high pH as were theN-alkylanilines in their basic and neutral forms. The limitation of open tubular columns was observed on separating some basic pharmaceutical drugs. These components showed severe peak tailing and were not resolved on a 20 μm i.d. porous silica layer open tubular column. Strongly acidic components could not be detected on these columns due to their higher counter electromobilities. The successful separation of neutral aryl alkyl ketones with an efficiency of 101,533 plates m¹ for butyrophenone was an indication of the improved phase ratio on this type of open tubular columns.     

A Little More on Coz-Unique Frames

Coz-unique frames were defined and characterized by Banaschewski and Gilmour (J Pure Appl Algebra 157:1–22, 2001). In this note we give further characterizations of these frames along the lines of characterizations of absolutely z-embedded spaces obtained by Blair and Hager (Math Z 136:41–52, 1974) on the one hand, and by Hager and Johnson (Canad J Math 20:389–393, 1968) on the other. We also extend to frames certain characterizations of z-embedded spaces; namely, we give a characterization of coz-onto frame homomorphisms in terms of normal covers.      

On the sobriety of the inverse topology

An algebraic frame L with the finite intersection property (FIP) on compact elements is said to be polarised if every minimal prime element in it is complemented. In this note, we give a necessary and sufficient condition for the inverse topology on the set of minimal prime elements of such a frame to be sober. We also establish some sufficient conditions for sobriety when the polarisation condition is relaxed.     

Zur plasmachemischen Umsetzung von CO/H2-Gemischen zu leichten Kohlenwasserstoffen in einer Glimmentladung

Mixtures of CO und H₂ can be partially converted into hydrocarbons (Hc), especially methane, by nonthermal activation in a glow discharge. The degree of conversion α CO → Hc and the partial pressure of methane reached values of 12% and 3% resp. The CO-conversion depends on the discharge parameters, the discharge time the energy input resp., and the rate of CO/H₂-mixture. The Hc formed are intermediate products which react further to higher Hc including solid Hc. According to mass spectrometrical analysis of plasma ions a reaction scheme was developed which is considered to be valid for the Hc formation based on an ion as well on neutral particle reactions.     

Synthesis of functionalized nitroarylmagnesium halides via an iodine-magnesium exchange

[reaction: see text] Various nitro-substituted aryl and heteroaryl iodides undergo an iodine-magnesium exchange reaction when treated with PhMgCl leading to nitro-containing magnesium organometallics. These Grignard reagents display an excellent stability at temperatures below -40 degrees C and do not undergo electron-transfer reactions. They react as expected with various electrophiles.     

Notes on Pointfree Disconnectivity with a Ring-theoretic Slant

We give characterizations of extremally disconnected frames, basically disconnected frames and F-frames L in terms of ring-theoretic properties of the ring RLmathcal{R}L of continuous real-valued functions on L. Emanating from these are new (and purely ring-theoretic) proofs that a frame is extremally disconnected, basically disconnected or an F-frame iff the same holds for its Čech-Stone compactification.     

Transmission of Unidirectional Molecular Motor Rotation to a Remote Biaryl Axis

Molecular motors undergo repetitive directional motions upon external energy input. A profound challenge is the defined transfer of directional motor motions to remote entities at the molecular scale. Herein, we present a molecular setup that allows for the transfer of the directional rotation of a light‐powered motor unit onto a remote biaryl axis via an ethylene glycol chain link. Based on a combination of X‐ray crystallographic analysis, ECD, and NMR experiments as well as a comprehensive theoretical assessment, we provide evidence for the coupled stepwise directional motions of both molecular units. With the presented setup, facile integration of molecular motor units into larger functional frameworks and complex molecular machines can be explored consciously in the future.