Photochemical Synthesis of Lactones, Cyclopropanes and ATRA Products: Revealing the Role of Sodium Ascorbate.

Light-mediated processes have received significant attention, since they have re-surfaced unconventional reactivity platforms, complementary to conventional polar chemistry. γ-Lactones and cyclopropanes are prevalent moieties, found in numerous natural products and pharmaceuticals. Among various methods for their synthesis, light-mediated protocols are coming to the spotlight, although these are contingent upon the use of photoorgano- or metal-based catalysts. Herein, we introduce a novel photochemical activation of iodo-reagents via the use of cheap sodium ascorbate or ascorbic acid to enable their homolytic scission and addition onto double bonds. The developed protocol was applied successfully to the formal [3+2] cycloaddition for the synthesis of γ-lactones, traditional atom transfer radical addition (ATRA) reactions and the one-pot two-step conversion of alkenes to cyclopropanes. In all cases, the desired products were obtained in good to high yields, while the reaction mechanism was thoroughly investigated. Depending on the nature of the iodo-reagent, a halogen or a hydrogen-bonded complex is formed, which initiates the process.

Photochemical Aminochlorination of Alkenes without the Use of an External Catalyst.

The niche field of photochemistry offers opportunities that are not found in "traditional" ground state chemical pathways. Aminochlorinated derivatives are an interesting family of 1,2-difunctionalised compounds that provide access to a variety of natural products and pharmaceutical active substances. A practical, catalyst-free chloroamination protocol is described herein, providing access to intermediates of great importance, utilising mild and photochemical reaction conditions (370 nm), where N-chlorosulfonamides are used as both nitrogen and chlorine sources. A wide variety of olefins, decorated with a plethora of functional groups, was tested providing excellent results (28 examples, 18-88 % yield). Mechanistic studies (UV-Vis, control experiments and quantum yield measurement) were also performed.

Light-accelerated "on-water" hydroacylation of dialkyl azodicarboxylates.

The hydroacylation of dialkyl azodicarboxylates has received a lot of attention lately due to the great importance of acyl hydrazides in organic chemistry. Herein, we report an inexpensive and green photochemical approach, where light irradiation (390 nm) significantly accelerates the reaction between dialkyl azodicarboxylates and aldehydes, while water is employed as the solvent. A variety of aromatic and aliphatic aldehydes were converted into their corresponding acyl hydrazides in good to excellent yields in really short reaction times (15-210 min) and the reaction mechanism was also studied. Applications of this reaction in the syntheses of Vorinostat and Moclobemide were demonstrated.

Slope stability analysis considering the strength anisotropy of c-φ soil.

In traditional slope stability analyses, soil is usually approximated as isotropic. However, naturally cohesive soil deposits are inherently anisotropic, primarily due to the directional arrangement of soil particles during their deposition process. In this paper, a generalized anisotropic constitutive model for c-φ soil is introduced to evaluate the influence of varying shear strength on slope stability. In this model, the initial strength anisotropy is defined by the variety of friction angles to the direction of the principle stress. This model is utilized by two approaches to estimate the slope stability. Firstly, the upper bound limit analysis solution for slope stability is developed, and the safety factor of the slopes is studied. Secondly, this model is coupled with the finite element method to get insight of the influence of anisotropy on slope stability. One typical slope case of slope is studied by numerical analyses. It is found that the slope stability is largely overestimated when the strength anisotropy is ignored, and the overestimation, in terms of safety factors, can reach up to 32.9%. The complex interrelations between the degree of anisotropy and evolution of the ensuing safety factor are revealed by a series of parametric studies in terms of different degrees of anisotropy.

A Unified Mechanism for the PhCOCOOH-mediated Photochemical Reactions: Revisiting its Action and Comparison to Known Photoinitiators.

Since 2014, we have introduced in literature the use of phenylglyoxylic acid (PhCOCOOH), a small and commercially available organic molecule, as a potent promoter in a variety of photochemical processes. Although PhCOCOOH has a broad scope of photochemical reactions that can promote, the understanding of its mode of action in our early contributions was moderate. Herein, we are restudying and revisiting the mechanism of action of PhCOCOOH in most of these early contributions, providing a unified mechanism of action. Furthermore, the understanding of its action as a photoinitiator opened a new comparison study with known and commercially available photoinitiators.

Hexafluoroisopropanol-Promoted or Brønsted Acid-Mediated Photochemical [2+2] Cycloadditions of Alkynes with Maleimides.

Although the use of light stimulating organic transformations has been known for more than a century, there is an increasing research interest on expanding the established knowledge. While [2+2] cycloadditions are promoted photochemically, literature precedent on the reaction between alkynes and maleimides is limited and only a handful of examples exist, focusing mainly on N-aliphatic maleimides. Herein, the differences in reactivity between N-alkyl and N-aryl maleimides were identified, and the use of hexafluoroisopropanol (HFIP) or trifluoroacetic acid (TFA) as viable solutions was proposed in order to achieve high yields. In the case of N-alkyl maleimides, both HFIP-mediated or TFA-promoted reactions were established using LED 370 nm irradiation, without the use of an external photocatalyst. In the case of N-aryl maleimides, thioxanthone (THX) was employed as the energy transfer photocatalyst along with LED 427 nm irradiation and HFIP. Mechanistic studies were performed, supporting the pivotal role of HFIP or TFA, in acquiring good to high yields in both classes of maleimides.

Thioxanthone: a powerful photocatalyst for organic reactions.

Photoorganocatalysis has been recognised by the organic chemistry community as an important part of photochemistry and catalysis. In general, aromatic ketones constitute key players in this type of catalysis as they are involved in a plethora of examples in the literature. Among the various aromatic ketones, thioxanthone (TX) seems to play a unique role in photochemistry. In comparison with other aromatic ketones, TX has a high triplet energy and a relatively long triplet lifetime, while it has the ability to participate successfully in merger reactions with metal complexes. In this review, we will discuss the photophysical properties of this small organic molecule, as well as the numerous examples of photochemical reactions, where it is employed as a mediator and more specifically in polymerisation reactions, and organic transformations.

Photochemical Activation of Aromatic Aldehydes: Synthesis of Amides, Hydroxamic Acids and Esters.

A cheap, facile and metal-free photochemical protocol for the activation of aromatic aldehydes has been developed. Utilizing thioxanthen-9-one as the photocatalyst and cheap household lamps as the light source, a variety of aromatic aldehydes have been activated and subsequently converted in a one-pot reaction into amides, hydroxamic acids and esters in good to high yields. The applicability of this method was highlighted in the synthesis of Moclobemide, a drug against depression and social anxiety. Extended and detailed mechanistic studies have been conducted, in order to determine a plausible mechanism for the reaction.

Performance of Optical Structural Vibration Monitoring Systems in Experimental Modal Analysis.

Image-based optical vibration measurement is an attractive alternative to the conventional measurement of structural dynamics predominantly relying on accelerometry. Although various optical vibration monitoring systems are now readily available, their performance is currently not well defined, especially in the context of experimental modal analysis. To this end, this study provides some of the first evidence of the capability of optical vibration monitoring systems in modal identification using input-output measurements. A comparative study is conducted on a scaled model of a 3D building frame set in a laboratory environment. The dynamic response of the model to an impulse excitation from an instrumented hammer, and an initial displacement, is measured by means of five optical motion capture systems. These include commercial and open-source systems based on laser Doppler velocimetry, fiducial markers and marker-less pattern recognition. The performance of these systems is analysed against the data obtained with a set of high-precision accelerometers. It is shown that the modal parameters identified from each system are not always equivalent, and that each system has limitations inherent to its design. Informed by these findings, a guidance for the deployment of the considered optical motion capture systems is given, aiding in their choice and implementation for structural vibration monitoring.

Phenylglyoxylic Acid: An Efficient Initiator for the Photochemical Hydrogen Atom Transfer C-H Functionalization of Heterocycles.

C-H functionalization at the α-position of heterocycles has become a rapidly growing area of research. Herein, a cheap and efficient photochemical method was developed for the C-H functionalization of heterocycles. Phenylglyoxylic acid (PhCOCOOH) could behave as an alternative to metal-based catalysts and organic dyes and provided a very general and wide array of photochemical C-H alkylation, alkenylation, and alkynylation, as well as C-N bond forming reaction methodologies. This novel, mild, and metal-free protocol was successfully employed in the functionalization of a wide range of C-H bonds, utilizing not only O- or N-heterocycles, but also the less studied S-heterocycles.

Aldehydes as powerful initiators for photochemical transformations.

Photochemistry, the use of light to promote organic transformations, has been known for more than a century but only recently has revolutionized the way modern chemists are thinking. Except from transition metal-based complexes, small organic molecules have been introduced as catalysts or initiators. In this review, we summarize the potential that (aromatic or aliphatic) aldehydes have as photoinitiators. The photophysical properties and photoreactivity of benzaldehyde are initially provided, followed by applications of aldehydes as initiators for polymerization reactions. Finally, the applications to date regarding aldehydes as photoinitiators in organic synthesis are presented.

Vibration annoyance assessment of train induced excitations from tunnels embedded in rock.

Train movements generate oscillations that are transmitted as waves through the track support system into its surroundings. The vibration waves propagate through the soil layers and reach to nearby buildings creating distractions for human activities and causing equipment malfunctioning. Not only the train components and the rails, but also the surrounding tunnel, soil and rock strata have dynamic characteristics that play significant roles in the vibration levels felt in a nearby structure. This paper presents a finite element study conducted to investigate the vibrations resulting from train movements in nearby subway tunnels. The subway line is located at an average horizontal distance of 50 ft (15.2 m) from the structure in assessment, which is a six-story office building. The main goal of the work is to assess the train-induced vibrations at the ground level of the building through a case study and sensitivity analysis. A plane strain finite element model is built to represent the railroad tunnel embedded in the rock and the soil stratum above it. The one train loading function is applied to the model as a point source at the track level and compared to the two-train scenario. Other simulations are undertaken for sensitivity analysis involving increased loading, decreased damping and decreased distance to tunnels. Even though there are several numerical studies on the propagation of train induced vibrations in the literature; a finite element model accompanied with a sensitivity analysis has not been discussed in detail in a technical publication before. The paper not only presents the finite element modeling but also compares the results with the criteria of Transit Noise and Vibration Impact Assessment Manual, which was published by the Federal Transit Administration (FTA) of the U.S. Department of Transportation.

Photocatalytic Atom Transfer Radical Addition to Olefins Utilizing Novel Photocatalysts.

Photocatalysis is a rapidly evolving area of research in modern organic synthesis. Among the traditional photocatalysts, metal-complexes based on ruthenium or iridium are the most common. Herein, we present the synthesis of two photoactive, ruthenium-based complexes bearing pyridine-quinoline or terpyridine ligands with extended aromatic conjugation. Our complexes were utilized in the atom transfer radical addition (ATRA) of haloalkanes to olefins, using bromoacetonitrile or bromotrichloromethane as the source of the alkyl group. The tailor-made ruthenium-based catalyst bearing the pyridine-quinoline bidentate ligand proved to be the best-performing photocatalyst, among a range of metal complexes and organocatalysts, efficiently catalyzing both reactions. These photocatalytic atom transfer protocols can be expanded into a broad scope of olefins. In both protocols, the photocatalytic reactions led to products in good to excellent isolated yields.