Ultrasound is widely used in medical imaging, and emerging photo-acoustic imaging is crucial for disease diagnosis. Currently, high-end photo-acoustic imaging systems rely on piezo-electric materials for detecting ultrasound waves, which come with sensitivity, noise, and bandwidth limitations. Advanced applications demand a large matrix of broadband, high-resolution, and scalable ultrasound sensors. Silicon photonic circuits have been introduced to meet these requirements by detecting ultrasound-induced deformation and stress in silicon waveguides. Although higher sensitivities could facilitate the exploration of new applications, the high stiffness of the waveguide materials constrains the intrinsic sensitivity of the silicon photonic circuits to ultrasound signals. Here, we explore the impact of the mechanical properties of a polymer cladding on the sensitivity of silicon photonic ultrasound sensors. Our model and experiments reveal that optimizing the polymer cladding's stiffness enhances the resonance wavelength sensitivity. Experimentally, we show a fourfold increase in the sensitivity compared to the sensors without a cladding polymer and, a twofold sensitivity increase compared to the sensors with a cladding polymer of saturated cross-linking density. Interestingly, comparing experiments with the optomechanical model suggests that the change in Young's Modulus alone cannot explain the sensitivity increase. In conclusion, polymer-coated silicon photonic ultrasound sensors exhibit potential for advanced photo-acoustic imaging applications. It offers the prospect of increasing the ultrasound detection sensitivity of silicon photonic ultrasound sensors while using CMOS-compatible processes. This paves the way to integrate the polymer-coated silicon photonic ultrasound sensors with electronics to utilize the sensors in advanced medical imaging applications.

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Many catalytic reactions suffer from product inhibition, which especially hard to control in homogeneous hydrogenation due to the scaling relation between the inhibited and active states of the catalyst. We recently reported one such pathway in Mn(I) hydrogenation and demonstrated that addition of alkoxide bases could affect the thermodynamic favorability of this reaction and selectively suppress the product inhibition. Since external reaction promotors are formally not involved in reaction thermodynamics, we set to investigate the explicit molecular interactions behind these apparently environmental effects. Herein, we reveal that the thermodynamic landscape of the inhibitory process exhibits a non-monotonic dependence on the base concentration. This study related this phenomenon to the presence of two dominant mechanisms operating at different base concentrations. Specifically, the base additives can enhance the ionic strength and lower the free energy of the inhibited state at low promotor concentration. At high base concentrations this study suggested the formation of highly labile alcohol-alkoxide clusters which stabilize the free alcohol and make its addition to the catalyst unfavourable, thereby suppressing the inhibition. While relatively weak, such noncovalent interactions between reactants and reaction environment can cause substantial perturbations to the free energy of catalytic process, ultimately deciding its fate.@en

Ultrasound is widely used in medical imaging, and photo-acoustics is an upcoming imaging modality for the diagnosis of diseases. Future applications require a large matrix of small, sensitive, and broadband ultrasound sensors. However, current high-end systems still use piezo-electric material to detect ultrasound, with limited sensitivity and bandwidth. Silicon photonic circuits can meet the requirements of size, bandwidth, and scalability when designed as ultrasound sensors. Namely, a silicon photonic waveguide deforms when the ultrasound pressure waves impinge on it, leading to a change in effective refractive index, n_e, due to geometrical and photo-elastic effects [1]. However, these effects are weak, which limits the intrinsic sensitivity of silicon photonic ultrasound sensors [2]. To significantly enhance sensitivity, silicon waveguides have been combined with acousto-mechanical structures, which achieved acoustomechanical-noise-limited sensing [3], but this is not compatible with standard photonic platforms. Besides that, recent demonstrations of waveguides coated with polymers also improved sensitivity of the silicon photonic ultrasound sensors significantly, but not sufficient to reach acoustomechnical-noise-limited sensing [4]. Here, we study the effect of mechanical and opto-mechanical properties of polymer claddings on the sensitivity of silicon photonic ultrasound sensors. Our aim is to enhance the sensitivity of these devices by implementing tailored polymer coatings. First, we model the refractive index sensitivity of these type of waveguides, i.e. the change in effective refractive index n_e due to the incident ultrasound plane-wave with a pressure P, and we (Equation presented) where n_c, p₁₂, E, and v are refractive index, elasto-optic coefficient, Young's modulus (stiffness), and Poisson's ratio of the cladding material, respectively. We assume the change in cladding index dominates sensitivity.

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Effective assessment of catalytic performance is the foundation for the rational design and development of new catalysts with superior performance. The ubiquitous screening/optimization studies use reaction yields as the sole performance metric in an approach that often neglects the complexity of the catalytic system and intrinsic reactivities of the catalysts. Using an example of hydrogenation catalysis, we examine the transient behavior of catalysts that are often encountered in activation, deactivation and catalytic turnover processes. Each of these processes and the reaction environment in which they take place are gradually shown to determine the real-time catalyst speciation and the resulting kinetics of the overall catalytic reaction. As a result, the catalyst performance becomes a complex and time-dependent metric defined by multiple descriptors apart from the reaction yield. This behaviour is not limited to hydrogenation catalysis and affects various catalytic transformations. In this feature article, we discuss these catalytically relevant descriptors in an attempt to arrive at a comprehensive depiction of catalytic performance.

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Mechanophores are powerful molecular tools used to track bond rupture and characterize mechanical damage in polymers. The majority of mechanophores are known to respond to external stresses, and we report in this study the first precedent of a mechanochemical response to internal, residual stresses that accumulate during polymer vitrification. While internal stress is intrinsic to polymers that can form solids, we demonstrate that it can dramatically affect the mechanochemistry of spiropyran probes and alter their intramolecular isomerization barriers by up to 70 kJ mol-1. This new behavior of spiropyrans (SPs) enables their application for analysis of internal stresses distribution and their mechanochemical characterization on the molecular level. Spectroscopy and imaging based on SP mechanochemistry showed high topological sensitivity and allowed us to discern different levels of internal stress impacting various locations along the polymer chain. The nature of the developed technique allows for wide-field imaging of stress heterogeneities in polymer samples of irregular shapes and dimensions, making it feasible to directly observe molecular-level manifestations of mechanical stresses that accompany the formation of a vast number of solid polymers.

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Automation and microfluidic tools potentially enable efficient, fast, and focused reaction development of complex chemistries, while minimizing resource- and material consumption. The introduction of automation-assisted workflows will contribute to the more sustainable development and scale-up of new and improved catalytic technologies. Herein, the application of automation and microfluidics to the development of a complex asymmetric hydrogenation reaction is described. Screening and optimization experiments were performed using an automated microfluidic platform, which enabled a drastic reduction in the material consumption compared to conventional laboratory practices. A suitable catalytic system was identified from a library of Ru^II-diamino precatalysts. In situ precatalyst activation was studied with ¹H/³¹P nuclear magnetic resonance (NMR), and the reaction was scaled up to multigram quantities in a batch autoclave. These reactions were monitored using an automated liquid-phase sampling system. Ultimately, in less than a week of total experimental time, multigram quantities of the target enantiopure alcohol product were provided by this automation-assisted approach.

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Homogeneously catalyzed reactions often make use of additives and promotors that affect reactivity patterns and improve catalytic performance. While the role of reaction promotors is often discussed in view of their chemical reactivity, we demonstrate that they can be involved in catalysis indirectly. In particular, we demonstrate that promotors can adjust the thermodynamics of key transformations in homogeneous hydrogenation catalysis and enable reactions that would be unfavorable otherwise. We identified this phenomenon in a set of well-established and new Mn pincer catalysts that suffer from persistent product inhibition in ester hydrogenation. Although alkoxide base additives do not directly participate in inhibitory transformations, they can affect the equilibrium constants of these processes. Experimentally, we confirm that by varying the base promotor concentration one can control catalyst speciation and inflict substantial changes to the standard free energies of the key steps in the catalytic cycle. Despite the fact that the latter are universally assumed to be constant, we demonstrate that reaction thermodynamics and catalyst state are subject to external control. These results suggest that reaction promotors can be viewed as an integral component of the reaction medium, on its own capable of improving the catalytic performance and reshaping the seemingly rigid thermodynamic landscape of the catalytic transformation.

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Activation of homogeneous catalysts is an important step in ensuring efficient operation of any catalytic system as a whole. For the majority of pincer catalysts, the activation step leans heavily on the metal ligand cooperative chemistry that allows these complexes to react with small molecule substrates and engage in catalytic transformations. While the majority of such catalysts require a single activation event to become cooperative, herein we report an exception to this trend. Specifically, we demonstrate that a Ru-PN³P aminopyridine pincer catalyst, which lacks conventional reactivity with hydrogen upon typical one-fold activation, can exhibit this reactivity when a sequential two-step activation is performed. The resulting anionic complexes readily activate molecular hydrogen and react further with CO₂ showing the previously unknown reactivity that is critical for CO₂ hydrogenation catalysts. While active in CO₂ hydrogenation, Ru-PN³Ps are significantly more efficient in hydrogenation of bicarbonates - a likely consequence of the chemistry of these pincers requiring formation of anionic complexes for hydrogen activation.

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While Mn-catalyzed (de)hydrogenation of carbonyl derivatives has been well established, the reactivity of Mn hydrides with olefins remains very rare. Herein, we report a Mn(I) pincer complex that effectively promotes site-controlled transposition of olefins. This reactivity is shown to emerge once the N–H functionality within the Mn/NH bifunctional complex is suppressed by alkylation. While detrimental for carbonyl (de)hydrogenation, such masking of the cooperative N–H functionality allows for the highly efficient conversion of a wide range of allylarenes to higher-value 1-propenybenzenes in near-quantitative yield with excellent stereoselectivities. The reactivity toward a single positional isomerization was also retained for long-chain alkenes, resulting in the highly regioselective formation of 2-alkenes, which are less thermodynamically stable compared to other possible isomerization products. The detailed mechanistic analysis of the reaction between the activated Mn catalyst and olefins points to catalysis operating via a metal–alkyl mechanism─one of the three conventional transposition mechanisms previously unknown in Mn complexes@en

The specific identity of electrolyte cations has many implications in various electrochemical reactions. However, the exact mechanism by which cations affect electrochemical reactions is not agreed upon in the literature. In this report, we investigate the role of cations during the electrochemical reduction of CO2 by chelating the cations with cryptands, to change the interaction of the cations with the components of the electric double layer. As previously reported we do see the apparent suppression of CO2 reduction in the absence of cations. However, using in situ-SEIRAS we see that CO2 reduction does indeed take place albeit at very reduced scales. We also observe that cations play a role in tuning the absorption strengths of not only CO2 as has been speculated, but also that of reaction products such as CO.

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Polymer glasses have an irregular structure. Among the causes for such complexity are the chemically distinct chain end groups that are the most abundant irregularities in any linear polymer. In this work, we demonstrate that chain end induced defects allow polymer glasses to create confined environments capable of hosting small emissive molecules. Using environmentally sensitive luminescent complexes, we show that the size of these confinements depends on molecular weight and can dramatically affect the photoluminescence of free or covalently bound emissive complexes. We confirm the impact of chain end confinement on the bulk glass transition in poly(methyl acrylate) (pMA) and show that commonly observed Tg changes induced by the chain ends should have a structural origin. Finally, we demonstrate that the size and placement of luminescent molecular probes in pMA can dramatically affect the probe luminescence and its temperature dependence, suggesting that polymer glass is a highly irregular and complex environment, marking its difference with conventional small molecule solvents. Considering the ubiquity of luminescent glassy materials, our work lays down a blueprint for designing them with structural considerations in mind, ones where packing density and chain end size are key factors.@en

Any catalyst should be efficient and stable to be implemented in practice. This requirement is particularly valid for manganese hydrogenation catalysts. While representing a more sustainable alternative to conventional noble metal-based systems, manganese hydrogenation catalysts are prone to degrade under catalytic conditions once operation temperatures are high. Herein, we report a highly efficient Mn(I)-CNP pre-catalyst which gives rise to the excellent productivity (TOF° up to 41 000 h⁻¹) and stability (TON up to 200 000) in hydrogenation catalysis. This system enables near-quantitative hydrogenation of ketones, imines, aldehydes and formate esters at the catalyst loadings as low as 5–200 p.p.m. Our analysis points to the crucial role of the catalyst activation step for the catalytic performance and stability of the system. While conventional activation employing alkoxide bases can ultimately provide catalytically competent species under hydrogen atmosphere, activation of Mn(I) pre-catalyst with hydride donor promoters, e.g. KHBEt₃, dramatically improves catalytic performance of the system and eliminates induction times associated with slow catalyst activation.

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Formic acid and formate salts are key intermediates along the pathways for CO₂utilization and hydrogen storage. Herein we report a highly efficient multiphase catalytic system utilizing a ruthenium PNP pincer catalyst for converting supersaturated bicarbonate solutions and slurries to aqueous formate solutions up to 12 M in molarity. The biphasic catalytic system delivers turnover frequencies up to 73 000 h⁻¹and remains stable for up to 474 000 turnovers once reaction conditions are optimized.

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Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, OtBu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.

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Catalytic reductions of carbonyl-containing compounds are highly important for the safe, sustainable, and economical production of alcohols. Herein, we report on the efficient transfer hydrogenation of ketones catalyzed by a highly potent Mn(I)−NHC complex. Mn−NHC 1 is practical at metal concentrations as low as 75 ppm, thus approaching loadings more conventionally reserved for noble metal based systems. With these low Mn concentrations, catalyst deactivation is found to be highly temperature dependent and becomes especially prominent at increased reaction temperature. Ultimately, understanding of deactivation pathways could help close the activity/stability-gap with Ru and Ir catalysts towards the practical implementation of sustainable earth-abundant Mn-complexes.

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The original Fig. 6 presented incorrect thermodynamic data for the conversion 4c + KOtBu → 2 + KOMe. A revised Fig. 6 is now provided. These changes do not affect the article text and its conclusions.

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Aromatization of furan and substituted furans over zeolite catalysts is a promising reaction to convert cellulose-derived compounds into valuable aromatic hydrocarbons and light olefins. A lack of understanding of the reaction mechanism however hinders further development of this process. Here, we propose the reaction mechanism, underlying the chemistry of furan and methanol co-aromatization over HZSM-5 zeolite catalyst. Applying ¹³C isotope labeling in a combination with NMR spectroscopy and high temporal resolution gas chromatography-mass spectrometry analysis, we demonstrate that aromatization of furan and methanol are not mechanistically separated and can be described within the dual-cycle hydrocarbon pool mechanism. Cofeeding furan with methanol leads to a significant enhancement of light aromatics selectivity and increased catalyst lifetime.

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Photoluminescent compounds can undergo various structural changes upon interaction with light. When these changes manifest themselves in the excited state, the resulting emitters can obtain a sensory function. In this work, we designed coordination compounds that can vary their emission color in response to thermal and mechanical stimuli. When embedded in a polymer matrix, Cu-NHC sensors act as mechanophores, and their color-based response can readily describe mechanical stress and phase transition phenomena. A strong practical advantage of new mechanophores over previous generations of organometallic stress sensors stems from their reliance on emission color variations that are easy to detect. In a broad context, our work implies that emission color variations that we often view as thermally governed can also be triggered mechanically and used to generate sensory information.

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The catalytic asymmetric transfer hydrogenation (ATH) of ketones is a powerful methodology for the practical and efficient installation of chiral centers. Herein, we describe the synthesis, characterization, and catalytic application of a series of manganese complexes bearing simple chiral diamine ligands. We performed an extensive experimental and computational mechanistic study and present the first detailed experimental kinetic study of Mn-catalyzed ATH. We demonstrate that conventional mechanistic approaches toward catalyst optimization fail and how apparently different precatalysts lead to identical intermediates and thus catalytic performance. Ultimately, the Mn-N,N complexes under study enable quantitative ATH of acetophenones to the corresponding chiral alcohols with 75-87% ee.

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A recently discovered photodecarboxylase from Chlorella variabilis NC64A ( CvFAP) bears the promise for the efficient and selective synthesis of hydrocarbons from carboxylic acids. CvFAP, however, exhibits a clear preference for long-chain fatty acids thereby limiting its broad applicability. In this contribution, we demonstrate that the decoy molecule approach enables conversion of a broad range of carboxylic acids by filling up the vacant substrate access channel of the photodecarboxylase. These results not only demonstrate a practical application of a unique, photoactivated enzyme but also pave the way to selective production of short-chain alkanes from waste carboxylic acids under mild reaction conditions.

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