Photochemically Induced Hydrogen Atom Transfer and Intramolecular Radical Cyclization Reactions with Oxazolones.

Photochemically induced intramolecular hydrogen atom transfer in oxazolones is reported. An acetal or thioacetal function at the side chain acts as a hydrogen donor while the photochemical exited oxazolone is the acceptor. A one-step process─the electron and the proton are simultaneously transferred─is productive, while electron transfer followed by proton transfer is inefficient. Radical combination then takes place, leading to the formation of a C-C or C-N bond. The regioselectivity of the reaction is explained by the diradical/zwitterion dichotomy of radical intermediates at the singlet state. In the present case, the zwitterion structure plays a central role, and intramolecular electron transfer favors spin-orbit coupling and thus the intersystem crossing to the singlet state. The reaction of corresponding thioacetal derivatives is less efficient. In this case, photochemical electron transfer is competitive. The photoproducts resulting from C-C bond formation easily undergo stepwise thermal decarboxylation in which zwitterionic and polar transition states are involved. A computational study of this step has also been performed.

Photocatalytic Transformation of Biomass and Biomass Derived Compounds-Application to Organic Synthesis.

Biomass and biomass-derived compounds have become an important alternative feedstock for chemical industry. They may replace fossil feedstocks such as mineral oil and related platform chemicals. These compounds may also be transformed conveniently into new innovative products for the medicinal or the agrochemical domain. The production of cosmetics or surfactants as well as materials for different applications are examples for other domains where new platform chemicals obtained from biomass can be used. Photochemical and especially photocatalytic reactions have recently been recognized as being important tools of organic chemistry as they make compounds or compound families available that cannot be or are difficultly synthesized with conventional methods of organic synthesis. The present review gives a short overview with selected examples on photocatalytic reactions of biopolymers, carbohydrates, fatty acids and some biomass-derived platform chemicals such as furans or levoglucosenone. In this article, the focus is on application to organic synthesis.

Surface similarity parameter: A new machine learning loss metric for oscillatory spatio-temporal data.

Supervised machine learning approaches require the formulation of a loss functional to be minimized in the training phase. Sequential data are ubiquitous across many fields of research, and are often treated with Euclidean distance-based loss functions that were designed for tabular data. For smooth oscillatory data, those conventional approaches lack the ability to penalize amplitude, frequency and phase prediction errors at the same time, and tend to be biased towards amplitude errors. We introduce the surface similarity parameter (SSP) as a novel loss function that is especially useful for training machine learning models on smooth oscillatory sequences. Our extensive experiments on chaotic spatio-temporal dynamical systems indicate that the SSP is beneficial for shaping gradients, thereby accelerating the training process, reducing the final prediction error, increasing weight initialization robustness, and implementing a stronger regularization effect compared to using classical loss functions. The results indicate the potential of the novel loss metric particularly for highly complex and chaotic data, such as data stemming from the nonlinear two-dimensional Kuramoto-Sivashinsky equation and the linear propagation of dispersive surface gravity waves in fluids.

A novel unknown-input and single-output approach to extract vibration patterns via a roving continuous random excitation.

Operating deflection shape analysis allows investigating the dynamic behaviour of a structure during operation. It normally requires simultaneous, multi-point measurements to capture the response from an unknown excitation source (unknown-input and multiple-output), which can complicate its usage for structures without ease of access. A novel vibration pattern testing method is proposed based on a roving continuous random excitation employing a small robotic Hexbug device and a single-point measurement. The Hexbug introduces a random excitation in consecutive locations while roaming over the structure. The resulting multi-modal, time and location dependent response of the system is captured in a single location, and then analysed with a newly developed method based on empirical wavelet transform, multiscale morphological filtering and optimization to extract the excited vibration patterns. The efficiency of the proposed method is experimentally demonstrated on a free-free and a cantilevered beam with comparison to mode shapes extracted by hammer test. The validation highlights its ability to extract several vibration patterns from a long slender structure with good accuracy and robustness, with the general ability to expand the usability of an operating deflecting shape analysis.

Enantioselective synthesis of heterocyclic compounds using photochemical reactions.

Different methods for the direct enantioselective photochemical synthesis of heterocycles are presented. Currently, asymmetric catalysis with templates involving hydrogen bonds or metal complexes is intensively investigated. Enzyme catalysis can be simplified under photochemical conditions. For example, in multi enzyme systems, one or more enzyme catalytic steps can be replaced by simple photochemical reactions. Chiral induction in photochemical reactions performed with homochiral crystals is highly efficient. Such reactions can also be carried out with crystalline inclusion complexes. Inclusion of a photochemical substrate and an enantiopure compound in zeolites also leads to enantioselective compounds. In all these methods, the conformational mobility of the photochemical substrates is reduced or controlled. Memory of chirality is a particular case in which a chiral information is temporally lost but the rigid conformations stabilize the molecular structure which leads to the formation of enantiopure compounds. Such studies allows a profound understanding on how particular conformations determine the configuration of the final products.Graphical abstract.

Photocycloadditions of Arenes Derived from Lignin.

Intramolecular photocycloaddition reactions of 3,4-alkoxybenzonitriles derived from vanillin with alkenes have been investigated. In contrast to previous reports on photochemical reactions with these compounds, mainly [2 + 3] cycloaddition has been observed. A competing [2 + 2] photocycloaddition plays a minor role. Most probably, these additions occur at the singlet state S1. In the case of a triplet reaction, a different regioselectivity of the [2 + 2] cycloaddition would be observed. Linear and angular [2 + 3] cycloadducts are formed as major products. The first isomer is transformed in the second one by a photochemical vinyl-cyclopropane rearrangement, which increases the selectivity of the reaction. The influence of the substitution pattern on the reactivity and the selectivity has also been investigated.

Studies on The Application of The Paternò-Büchi Reaction to The Synthesis of Novel Fluorinated Scaffolds.

In the context of new scaffolds obtained by photochemical reactions, Paternò-Büchi reactions between heteroaromatic, trifluoromethylphenyl ketone and electron rich alkenes to give oxetanes are described. A comprehensive study has then been carried out on the reaction of aromatic ketones with fluorinated alkenes. Depending on the substitution pattern at the oxetane ring, a metathesis reaction is described as a minor side process to give mono fluorinated alkenes. Overall, this last reaction corresponds to a photo-Wittig reaction and yield amid isosteres. In order to explain the uncommon regioselectivity of the Paternò-Büchi reaction with these alkenes, electrostatic-potential derived charges (ESP) have been determined. In a second computational study, the relative stabilities of the typical 1,4-diradical intermediates of the Paternò-Büchi reaction have been determined. The results well explain the regioselectivity. Further transformations of the oxetanes or previous functionalization of the fluoroalkenes open perspectives for oxetanes as core structures for biologically active compounds.

Photochemical radical cyclization reactions with imines, hydrazones, oximes and related compounds.

Photochemical reactions are a key method to generate radical intermediates. Often under these conditions no toxic reagents are necessary. During recent years, photo-redox catalytic reactions considerably push this research domain. These reaction conditions are particularly mild and safe which enables the transformation of poly-functional substrates into complex products. The synthesis of heterocyclic compounds is particularly important since they play an important role in the research of biologically active products. In this review, photochemical radical cyclization reactions of imines and related compounds such as oximes, hydrazones and chloroimines are presented. Reaction mechanisms are discussed and the structural diversity and complexity of the products are presented. Radical intermediates are mainly generated in two ways: (1) electronic excitation is achieved by light absorption of the substrates. (2) The application of photoredox catalysis is now systematically studied for these reactions. Recently, also excitation of charge transfer complexes has been studied in this context from many perspectives.

Directional soliton and breather beams.

Solitons and breathers are nonlinear modes that exist in a wide range of physical systems. They are fundamental solutions of a number of nonlinear wave evolution equations, including the unidirectional nonlinear Schrödinger equation (NLSE). We report the observation of slanted solitons and breathers propagating at an angle with respect to the direction of propagation of the wave field. As the coherence is diagonal, the scale in the crest direction becomes finite; consequently, beam dynamics form. Spatiotemporal measurements of the water surface elevation are obtained by stereo-reconstructing the positions of the floating markers placed on a regular lattice and recorded with two synchronized high-speed cameras. Experimental results, based on the predictions obtained from the (2D + 1) hyperbolic NLSE equation, are in excellent agreement with the theory. Our study proves the existence of such unique and coherent wave packets and has serious implications for practical applications in optical sciences and physical oceanography. Moreover, unstable wave fields in this geometry may explain the formation of directional large-amplitude rogue waves with a finite crest length within a wide range of nonlinear dispersive media, such as Bose-Einstein condensates, solids, plasma, hydrodynamics, and optics.

Photochemically Induced Intramolecular Radical Cyclization Reactions with Imines.

The photochemically induced intramolecular hydrogen abstraction or hydrogen atom transfer in cyclic imines 8a,b followed by a cyclization is investigated. Two types of products are observed, one resulting from the formation of a C-C bond, the other from the formation of a C-N bond. A computational study reveals that hydrogen is exclusively transferred to the imine nitrogen leading to a triplet diradical intermediate. After intersystem crossing, the resulting zwitterionic intermediate undergoes cyclization leading to the final product.

Load-separation curves for the contact of self-affine rough surfaces.

There are two main approximate theories in the contact of rough solids: Greenwood-Williamson asperity theories (GW) and Persson theories. Neither of them has been fully assessed so far with respect to load-separation curves. Focusing on the most important case of low fractal dimension (D f = 2.2) with extensive numerical studies we find that: (i) Persson's theory describes well the regime of intermediate pressures/contact area, but requires significant corrective factors: the latter depend also on upper wavevector cutoff of the roughness; hence, (ii) Persson's theory does not predict the correct functional dependence on magnification; (iii) asperity theories in the discrete version even neglecting interaction effects are more appropriate in the range of relatively large separations, also to take into consideration of the large scatter in actual realization of the surface.

Studies in organic and physical photochemistry - an interdisciplinary approach.

Traditionally, organic photochemistry when applied to synthesis strongly interacts with physical chemistry. The aim of this review is to illustrate this very fruitful interdisciplinary approach and cooperation. A profound understanding of the photochemical reactivity and reaction mechanisms is particularly helpful for optimization and application of these reactions. Some typical reactions and particular aspects are reported such as the Norrish-Type II reaction and the Yang cyclization and related transformations, the [2 + 2] photocycloadditions, particularly the Paternò-Büchi reaction, photochemical electron transfer induced transformations, different kinds of catalytic reactions such as photoredox catalysis for organic synthesis and photooxygenation are discussed. Particular aspects such as the structure and reactivity of aryl cations, photochemical reactions in the crystalline state, chiral memory, different mechanisms of hydrogen transfer in photochemical reactions or fundamental aspects of stereoselectivity are discussed. Photochemical reactions are also investigated in the context of chemical engineering. Particularly, continuous flow reactors are of interest. Novel reactor systems are developed and modeling of photochemical transformations and different reactors play a key role in such studies. This research domain builds a bridge between fundamental studies of organic photochemical reactions and their industrial application.

Photoorganocatalysed and visible light photoredox catalysed trifluoromethylation of olefins and (hetero)aromatics in batch and continuous flow.

Trifluoromethylation of olefins and (hetero)aromatics with sodium triflinate as CF3 source and readily accessible benzophenone derivatives as photosensitisers has been developed in batch and flow. The use of an iridium-based photocatalyst enables the trifluoromethylation to proceed under visible light irradiation.

Optical and photophysical properties of anisole- and cyanobenzene-substituted perylene diimides.

One- and two-photon absorption cross-sections and spectra and the photophysical properties of eight perylenetetracarboxy-3,4:9,10-diimide (PDI) derivatives are reported and analyzed. The investigated compounds are characterized by direct binding of the phenyl rings of the substituents to the bay positions of the perylene core. They have been designed to test the effects of differences in the electronic nature - electron donating (anisole) or accepting (cyanobenzene) - and binding topology (cis or trans, meta or para disubstitution or tetrasubstitution) of the bay substituents on the above optical and photophysical observables. (TD)DFT and Hückel MO calculations have provided theoretical information on the ground-state geometries, the MOs and the electronic spectra of several model compounds. For tetrasubstituted and cis disubstituted derivatives, strong steric interactions in the bay area determined the preferred conformations, with perylene cores distorted near the substituted bay(s) and a 42-44° twisting of the substituent rings relative to the core, quite irrespective of the electronic nature of the substituents. On the other hand, in trans-disubstituted PDI steric hindrance in the bay areas was much weaker and similar in the cyanobenzene and the anisole derivatives. So, the large differences found in the conformational preferences were completely attributable to electronic effects. With electron-accepting cyanobenzene, the substituent rings were found normal to the central planar perylene core, thus enabling the assignment of the moderate spectroscopic effects to inductive interactions. The DFT analysis of the PDI trans-disubstituted with electron-donating anisoles gave quite strongly distorted perylene-core geometries and less twisted (59°) substituent rings. The corresponding increased substituent/core conjugative interactions resulted in new CT allowed electronic transitions and an extremely pronounced solvent-polarity dependence of the emission spectra and intensities. All anisole substituted PDI feature a very fast radiationless decay path in polar solvents, likely related to a relaxation to a charge-separated configuration in the lowest excited-state.

The influence of stem design on critical squeaking friction with ceramic bearings.

Ceramic-on-ceramic hip joints have been reported to squeak, a phenomenon that may occur in compromised lubrication conditions. One factor related to the incidence of in vivo squeaking is the stem design. However, it has not yet been possible to relate stem design to squeaking in deteriorating lubrication conditions. The purpose of this study was to determine critical friction factors for different stem designs. A hip simulator was used to measure the friction factor of a ceramic bearing with different stem designs and gradually deteriorating lubrication represented by evaporation of a volatile fluid lubricant. The critical squeaking friction factor was measured at the onset of squeaking for each stem. Critical friction was higher for the long cobalt chrome (0.32 ± 0.02) and short titanium stems (0.39 ± 0.02) in comparison with a long titanium stem (0.29 ± 0.02). The onset of squeaking occurred at a friction factor lower than that measured for dry conditions, in which squeaking is usually investigated experimentally. The results suggest that shorter or heavier stems might limit the possibility of squeaking as lubrication deteriorates. The method developed can be used to investigate the influence of design parameters on squeaking probability.

Vibration transfer in the ball-stem contact interface of artificial hips.

Audible squeaking has put the reputation of ceramic bearings for total hip replacements into question. Inter-articular friction induces vibrations in the ceramic head which are transferred through the head-taper interface to the femoral stem. If excited to sufficient amplitudes, squeaking can be emitted by the stem. Hence, the damping and amplification properties of this interface have a crucial influence on stem vibrations. The aim of this study was to determine the vibration transfer behavior between the head and the taper of a femoral stem and its dependence on the assembly force, in order to assess its influence on the development of audible squeaking. A ceramic head was assembled on a titanium femoral stem taper with high and low forces. Frequency response functions characterizing the head-stem interface were determined experimentally. The interface demonstrated negligible influence on vibration transfer in the squeaking frequency range (1-5 kHz). However its damping effect in lower and higher frequency ranges was significant and some areas of amplification were also found. Although squeaking vibration was not influenced by the particular interface studied, the method established can be utilized to trace taper designs with dynamic properties that decrease the susceptibility to squeaking.

Parallel microflow photochemistry: process optimization, scale-up, and library synthesis.

A novel, multimicrocapillary flow reactor (MµCFR) was constructed and applied to a series of sensitized photoadditions involving 2(5H)-furanones. The reactor allowed for rapid and energy-, time-, and space-efficient sensitizer screening, process optimization, validation, scale-up, and library synthesis.

Photochemical reactions of aromatic compounds and the concept of the photon as a traceless reagent.

Electronic excitation significantly changes the reactivity of chemical compounds. Compared to ground state reactions, photochemical reactions considerably enlarge the application spectrum of a particular functional group in organic synthesis. Multistep syntheses may be simplified and perspectives for target oriented synthesis (TOS) and diversity oriented synthesis (DOS) are developed. New compound families become available or may be obtained more easily. In contrast to common chemical reagents, photons don't generate side products resulting from the transformation of a chemical reagent. Therefore, they are considered as a traceless reagent. Consequently, photochemical reactions play a central role in the methodology of sustainable chemistry. This aspect has been recognized since the beginning of the 20th century. As with many other photochemical transformations, photochemical reactions of aromatic, benzene-like compounds illustrate well the advantages in this context. Photochemical cycloadditions of aromatic compounds have been investigated for a long time. Currently, they are applied in various fields of organic synthesis. They are also studied in supramolecular structures. The phenomena of reactivity and stereoselectivity are investigated. During recent years, photochemical electron transfer mediated reactions are particularly focused. Such transformations have likewise been performed with aromatic compounds. Reactivity and selectivity as well as application to organic synthesis are studied.

Homogeneous photocatalytic reactions with organometallic and coordination compounds--perspectives for sustainable chemistry.

Since the time of Giacomo Ciamician at the beginning of the 20th century, photochemical transformations have been recognized as contributing to sustainable chemistry. Electronic excitation significantly changes the reactivity of chemical compounds. Thus, the application of activation reagents is frequently avoided and transformations can be performed under mild conditions. Catalysis plays a central role in sustainable chemistry. Stoichiometric amounts of activation reagents are often avoided. This fact and the milder catalytic reaction conditions diminish the formation of byproducts. In the case of homogeneous catalysis, organometallic compounds are often applied. The combination of both techniques develops synergistic effects in the sense of "Green Chemistry". Herein, metal carbonyl-mediated reactions are reported. These transformations are of considerable interest for the synthesis of complex polyfunctionalized compounds. Copper(I)-catalyzed [2+2] photocycloaddition gives access to a large variety of cyclobutane derivatives. Currently, a large number of publications deal with photochemical electron-transfer-induced reactions with organometallic and coordination compounds, particularly with ruthenium complexes. Several photochemically induced oxidations can easily be performed with air or molecular oxygen when they are catalyzed with organometallic complexes. Photochemical reaction conditions also play a certain role in C-H activation with organometallic catalysts, for instance, with alkanes, although such transformations are conveniently performed with a variety of other photochemical reactions.

Friction-induced whirl vibration: root cause of squeaking in total hip arthroplasty.

Squeaking is reported for ceramic-on-ceramic hip arthroplasty, and risk factors leading to this phenomenon have been investigated empirically in the past, this way giving hints to when this phenomenon occurs. The aim of this study is to present an experimentally validated explanation for the dynamical mechanism underlying the squeak, i.e. a description of what happens when noise is generated. First the kinematics of the ceramic bearing couple in relative motion are reconsidered. The relative motion at the contact zone can be understood as superposition of relative rotation and translation. The relative weight of both components depends substantially on the instantaneous load vector, which primarily determines the position of the contact area, and the instantaneous relative rotation vector. For the investigated gait scenarios, both load vector and rotation axis vary strongly during the gait cycle. Second, experimental vibration analysis during squeak is performed. A pronounced micrometer scale elliptical motion of the ball inside the liner is found. It is shown that the rotational component of the relative kinematics during gait indeed leads to friction induced vibrations. We show that a generic whirl type friction induced flutter instability, also known from similar (non bio-) mechanical systems, is the root cause of the emitted squeaking noise. Based on the identified mechanism, the role of THA system parameters (materials, design), patient risk factors, as well as the role of the gait cycle, will have to be reconsidered and linked in the future to develop effective measures against squeaking.