Radical Chlorination of Non-Resonant Heterobenzylic C-H Bonds and High-Throughput Diversification of Heterocycles.

Site-selective functionalization of the heterobenzylic C(sp3)-H bonds of pyridines and related heteroaromatic compounds presents challenges associated with the basic nitrogen atom and the variable reactivity among different positions on the heteroaromatic ring. Methods for functionalization of 2- and 4-alkylpyridines are increasingly available through polar pathways that leverage resonance stabilization of charge build-up at these positions. In contrast, functionalization of 3-alkylpyridines is largely inaccessible. Here, we report a photochemically promoted method for chlorination of non-resonant heterobenzylic C(sp3)-H sites in 3-alkylpyridines and related alkylheteroaromatics. Density functional theory calculations show that the optimal reactivity reflects a balance between the energetics of the two radical-chain propagation steps, with the preferred reagent consisting of an N-chlorosulfonamide. The operationally simple chlorination protocol enables access to heterobenzylic chlorides which serve as versatile intermediates in C-H cross-coupling reactions between heteroaromatic building blocks and diverse oxidatively sensitive nucleophiles using high-throughput experimentation.

A Photoenzymatic Pathway for Gram-Scale Synthesis of 25-Hydroxyvitamin D3.

Vitamin D and its analogues play a crucial role in promoting the well-being of both humans and animals. However, the current synthesis of this vital class of nutrients heavily relies on chemical transformations, which suffer from low step- and atom-efficiency due to lengthy synthetic pathways. To enhance sustainability in the chemical industry, it is necessary to develop alternative synthetic processes. Herein, we present a photoenzymatic approach for synthesizing 25-hydroxyvitamin D3 from 7-dehydrocholesterol. In this sequential synthesis, 7-dehydrocholesterol is initially hydroxylated at the C25 C-H bond, resulting in an 85% conversion to 25-hydroxyl-7-dehydrocholesterol. Subsequently, by employing photo-irradiation using a monochromatic LED ultraviolet light source in a batch reactor and thermal isomerization, 25-hydroxyvitamin D3 is obtained in satisfactory yield. This photoenzymatic process significantly reduces the need for purification steps and allows for gram-scale synthesis of the target product. Our work offers a selective, efficient, and environmentally friendly method for synthesizing 25-OH-vitamin D3, addressing the limitations of current synthetic approaches.

Overriding Cage Effect in Electron Donor-Acceptor Photoactivation of Diaryliodonium Reagents: Synthesis of Chalcogenides.

In recent times, diaryliodonium reagents (DAIRs) have witnessed a resurgence as arylating reagents, especially under photoinduced conditions. However, reactions proceeding through electron donor-acceptor (EDA) complex formation with DAIRs are restricted to electron-rich reacting partners serving as donors due to the well-known cage effect. We discovered a practical and high-yielding visible-light-induced EDA platform to generate aryl radicals from the corresponding DAIRs and use them to synthesize key chalcogenides. In this process, an array of DAIRs and dichalcogenides react in the presence of 1,4 diazabicyclo[2.2.2]octane (DABCO) as a cheap and readily available donor, furnishing a variety of di(hetero)aryl and aryl/alkyl chalcogenides in good yields. The method is scalable, features a broad scope with good yields, and operates under open-to-air conditions. The photoinduced chalcogenation technology is suitable for late-stage functionalizations and disulfide bioconjugations and facilitates access to biologically relevant thioesters, dithiocarbamates, sulfoximines, and sulfones. Moreover, the method applies to synthesizing diverse pharmaceuticals, such as vortioxetine, promazine, mequitazine, and dapsone, under amenable conditions.

Synthetic Protein Nanoparticles via Photoreactive Electrohydrodynamic Jetting.

Protein nanoparticles are an attractive class of materials for nanomedicine applications due to the intrinsic biocompatibility, biodegradability, and intrinsic functionality of their constituent proteins. Despite the clinical success of select protein nanoparticles, this class of nanocarriers remains understudied and underdeveloped compared to lipid and polymer nanoparticles due to challenges related to formulation optimization, large design space, and their structural complexity. In this work, a modular strategy for protein nanoparticle preparation based on the concept of photoreactive jetting is introduced. The process relies on continuous ultraviolet irradiation during electrohydrodynamic (EHD) jetting of protein solutions that contain a homobifunctional photocrosslinker. Protein nanoparticles exhibit nanogel-like architectures comprised of proteins that are linked via synthetic moieties. Compared to conventional protein nanoparticles, this method reduces nanoparticle processing times to minutes, rather than hours to days. The inclusion of an emissive structural motif as the molecular scaffold of the photocrosslinker is used to study the supramolecular architecture of the stable nanoparticles via time-resolved fluorescence spectroscopy.

Chlorophyll fluorescence, physiology, and yield of winter wheat under different irrigation and shade durations during the grain-filling stage.

The uneven spatial and temporal distribution of light resources and water scarcity during the grain-filling stage pose significant challenges for sustainable crop production, particularly in the arid areas of the Loess Plateau in Northwest China. This study aims to investigate the combined effects of drought and shading stress on winter wheat growth and its physio-biochemical and antioxidative responses. Wheat plants were subjected to different drought levels- full irrigation (I100), 75% of full irrigation (I75), 50% of full irrigation (I50), and 25% of full irrigation (I25), and shading treatments - 12, 9, 6, 3 and 0 days (SD12, SD9, SD6, SD3, and CK, respectively) during the grain-filling stage. The effects of drought and shading treatments reduced yield in descending order, with the most significant reductions observed in the SD12 and I25 treatments. These treatments decreased grain yield, spikes per plant, 1000-grain weight, and spikelets per spike by 160.67%, 248.13%, 28.22%, and 179.55%, respectively, compared to the CK. Furthermore, MDA content and antioxidant enzyme activities exhibited an ascending trend with reduced irrigation and longer shading durations. The highest values were recorded in the I75 and SD12 treatments, which increased MDA, SOD, POD, and CAT activities by 65.22, 66.79, 65.07 and 58.38%, respectively, compared to the CK. The Pn, E, Gs, and iCO2 exhibited a decreasing trend (318.14, 521.09, 908.77, and 90.85%) with increasing shading duration and decreasing irrigation amount. Drought and shading treatments damage leaf chlorophyll fluorescence, decreasing yield and related physiological and biochemical attributes.

Dual, Photo-Responsive and Redox-Active Supramolecular Foldamers.

We report on dual, light-responsive and redox-active foldamers that demonstrate reversible and robust stimuli-induced behaviour. Herein, UV/Vis, 1H NMR and circular dichroism (CD) spectroscopy and cyclic voltammetry have been used to establish the reversibility and highly robust nature of the light- and redox-driven behaviour of these new foldamers with minimal levels of fatigue observed even upon multiple cyclic treatments with irradiative/non-irradiative and oxidative/reductive conditions. This proof-of-concept work paves the way towards the creation of novel stimuli-responsive foldamers of increasing sophistication capable of demonstrating reversible and robust responses to multiple distinct stimuli.

Unraveling C-Selective Ring-Opening of Phosphiranes with Carboxylic Acids and Other Nucleophiles: A Mechanistically-Driven Approach.

Phosphiranes are weak Lewis bases reacting with only a limited number of electrophiles to produce the corresponding phosphiranium ions. These salts are recognized for their propensity to undergo reactions with oxygen pronucleophiles at the phosphorus site, leading to the formation of phosphine oxide adducts. Building on a thorough mechanistic understanding, we have developed an unprecedented approach that enables the selective reaction of carboxylic acids, and other nucleophiles, at the carbon site of phosphiranes. This method involves the photochemical generation of highly reactive carbenes, which react with 1-mesitylphosphirane to yield ylides. The latter undergoes a stepwise reaction with carboxylic acids, resulting in the production of the desired phosphines. In addition to DFT calculations, we have successfully isolated and fully characterized the key intermediates involved in the reaction.

Recent Advances in Photoinduced Oxidative Cleavage of Alkenes.

Oxidative cleavage of alkenes leading to valuable carbonyl derivatives is a fundamental transformation in synthetic chemistry. In particular, ozonolysis is the mainstream method for the oxidative cleavage of alkenes that has been widely implemented in the synthesis of natural products and pharmaceutically relevant compounds. However, due to the toxicity and explosive nature of ozone, alternative approaches employing transition metals and enzymes in the presence of oxygen and/or strong oxidants have been developed. These protocols are often conducted under harsh reaction conditions that limit the substrate scope. Photochemical approaches can provide milder and more practical alternatives for this synthetically useful transformation. In this review, we outline recent visible-light-promoted oxidative cleavage reactions that involve photocatalytic activation of oxygen via electron transfer and energy transfer. Also, an emerging field featuring visible-light-promoted oxidative cleavage under anaerobic conditions is discussed. The methods highlighted in this review represent a transformative step toward more sustainable and efficient strategies for the oxidative cleavage of alkenes.

Forecasting Photo-Dissolution for Future Oil Spills at Sea: Effects of Oil Properties and Composition.

Photo-dissolution, the photochemical production of water-soluble species from oil, can transfer oil-derived dissolved organic carbon (DOC) from floating surface slicks to the underlying seawater. Photo-dissolution was likely a quantitatively relevant fate process for the Macondo crude oil spilled during the 2010 Deepwater Horizon spill, but the importance of photo-dissolution for other oils is poorly constrained. This study evaluated the photo-dissolution reactivities (apparent quantum yields) and modeled rates for oils with diverse physical properties and chemical compositions, including an ultra low sulfur fuel oil (ULSFO). Photo-dissolution from UV (310 nm) light was strongly positively correlated with the fraction of small, gas-oil range compounds (

Simultaneous Color- and Dose-Controlled Thiol-Ene Resins for Multimodulus 3D Printing with Programmable Interfacial Gradients.

Drawing inspiration from nature's own intricate designs, synthetic multimaterial structures have the potential to offer properties and functionality that exceed those of the individual components. However, several contemporary hurdles, from a lack of efficient chemistries to processing constraints, preclude the rapid and precise manufacturing of such materials. Herein, the development of a photocurable resin comprising color-selective initiators is reported, triggering disparate polymerization mechanisms between acrylate and thiol functionality. Exposure of the resin to UV light (365 nm) leads to the formation of a rigid, highly crosslinked network via a radical chain-growth mechanism, while violet light (405 nm) forms a soft, lightly crosslinked network via an anionic step-growth mechanism. The efficient photocurable resin is employed in multicolor digital light processing 3D printing to provide structures with moduli spanning over two orders of magnitude. Furthermore, local intensity (i.e., grayscale) control enables the formation of programmable stiffness gradients with ≈150× change in modulus occurring across sharp (≈200 µm) and shallow (≈9 mm) interfaces, mimetic of the human knee entheses and squid beaks, respectively. This study provides composition-processing-property relationships to inform advanced manufacturing of next-generation multimaterial objects having a myriad of applications from healthcare to education.

Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion Pairs.

The singlet fission characteristics of aqueous nanoparticles, self-assembled from ion pairs of tetracene dicarboxylic acid and various amines with or without chirality, are thoroughly investigated. The structure of the ammonium molecule, the counterion, is found to play a decisive role in determining the molecular orientation of the ion pairs and its regularity, spectroscopic properties, the strength of the intermolecular coupling between the tetracene chromophores, and the consequent singlet fission process. Using chiral amines has led to the formation of crystalline nanosheets and efficient singlet fission with a triplet quantum yield as high as 133% ±20% and a rate constant of 6.99 × 109 s-1. The chiral ion pairs also provide a separation channel to free triplets with yields as high as 33% ±10%. In contrast, nanoparticles with achiral counterions do not show singlet fission, which gave low or high fluorescence quantum yields depending on the size of the counterions. The racemic ion pair produces a correlated triplet pair intermediate by singlet fission, but no decorrelation into two free triplets is observed, as triplet-triplet annihilation dominates. The introduction of chirality enables higher control over orientation and singlet fission in self-assembled chromophores. It provides new design guidelines for singlet fission materials.

The role of solar photolysis in the atmospheric removal of methacrolein oxide and the methacrolein oxide-water van-der Waals complex in pristine environments.

Biogenic hydrocarbons are emitted into the Earth's atmosphere by terrestrial vegetation as by-products of photosynthesis. Isoprene is one such hydrocarbon and is the second most abundant volatile organic compound emitted into the atmosphere (after methane). Reaction with ozone represents an important atmospheric sink for isoprene removal, forming carbonyl oxides (Criegee intermediates) with extended conjugation. In this manuscript, we argue that the extended conjugation of these Criegee intermediates enables electronic excitation of these compounds, on timescales that are competitive with their slow unimolecular decay and bimolecular chemistry. We show that the complexation of methacrolein oxide with water enhances the absorption cross section of the otherwise dark S1 state, potentially revealing a new avenue for forming lower volatility compounds via tropospherically relevant photochemistry.

Photochemical Generation and Characterization of C-Aminophenyl-Nitrilimines: Insights on Their Bond-Shift Isomers by Matrix-Isolation IR Spectroscopy and Density Functional Theory Calculations.

The intriguing ability of C-phenyl-nitrilimine to co-exist as allenic and propargylic bond-shift isomers motivated us to investigate how substituents in the phenyl ring influence this behavior. Building on our previous work on the meta- and para-OH substitution, here we extended this investigation to explore the effect of the NH2 substitution. For this purpose, C-(4-aminophenyl)- and C-(3-aminophenyl)-nitrilimines were photogenerated in an argon matrix at 15 K by narrowband UV-light irradiation (λ = 230 nm) of 5-(4-aminophenyl)- and 5-(3-aminophenyl)-tetrazole, respectively. The produced nitrilimines were further photoisomerized to carbodiimides via 1H-diazirines by irradiations at longer wavelengths (λ = 380 or 330 nm). Combining IR spectroscopic measurements and DFT calculations, it was found that the para-NH2-substituted nitrilimine exists as a single isomeric structure with a predominant allenic character. In contrast, the meta-NH2-substituted nitrilimine co-exists as two bond-shift isomers characterized by propargylic and allenic structures. To gain further understanding of the effects of phenyl substitution on the bond-shift isomerism of the nitrilimine fragment, we compared geometric and charge distribution data derived from theoretical calculations performed for C-phenyl-nitrilimine with those performed for the derivatives resulting from NH2 (electron-donating group) and NO2 (electron-withdrawing group) phenyl substitutions.

Regulating Atomically-Precise Pt Sites for Boosting Light-Driven Dry Reforming of Methane.

Light-driven dry reforming of methane is a promising and mild route to convert two greenhouse gas into valuable syngas. However, developing facile strategy to atomically-precise regulate the active sites and realize balanced and stable syngas production is still challenging. Herein, we developed a spatial confinement approach to precisely control over platinum species on TiO2 surfaces, from single atoms to nanoclusters. The configuration comprising single atoms and sub-nanoclusters engenders pronounced electronic metal-support interactions, with resultant interfacial states prompting surface charge rearrangement. The unique geometric and electronic properties of these atom-cluster assemblies facilitate effective activation of CH4 and CO2, accelerating intermediate coupling and minimizing side reactions. Our catalyst exhibits an outstanding syngas generation rate of 34.41 mol gPt-1 h-1 with superior durability, displaying high apparent quantum yield of 9.1% at 365 nm and turnover frequency of 1289 h-1. This work provides insightful understanding for exploring more multi-molecule systems at an atomic scale.

Cooperative NHC and Photoredox Catalyzed Radical Aminoacylation of Alkenes to Tetrahydropyridazines.

Tetrahydropyridazines constitute an important structural motif found in numerous natural products and pharmaceutical compounds. Herein, we report an aminoacylation reaction of alkenes that enables the synthesis of 1,4,5,6-tetrahydropyridazines through cooperative N-heterocyclic carbene (NHC) and photoredox catalysis. This approach involves the 6-endo-trig cyclization of N-centered hydrazonyl radicals, generated via single-electron oxidation of hydrazones, followed by a radical-radical coupling step. The mild process tolerates a wide range of common functional groups and affords a variety of tetrahydropyridazines in moderate to high yields. Preliminary investigations using chiral NHC catalysts demonstrate the potential of this protocol for asymmetric radical reactions.

Geographic Drivers of Mercury Entry into Aquatic Food Webs Revealed by Mercury Stable Isotopes in Dragonfly Larvae.

Atmospheric mercury (Hg) emissions and subsequent transport and deposition are major concerns within protected lands, including national parks, where Hg can bioaccumulate to levels detrimental to human and wildlife health. Despite this risk to biological resources, there is limited understanding of the relative importance of different Hg sources and delivery pathways within the protected regions. Here, we used Hg stable isotope measurements within a single aquatic bioindicator, dragonfly larvae, to determine if these tracers can resolve spatial patterns in Hg sources, delivery mechanisms, and aquatic cycling at a national scale. Mercury isotope values in dragonfly tissues varied among habitat types (e.g., lentic, lotic, and wetland) and geographic location. Photochemical-derived isotope fractionation was habitat-dependent and influenced by factors that impact light penetration directly or indirectly, including dissolved organic matter, canopy cover, and total phosphorus. Strong patterns for Δ200Hg emerged in the western United States, highlighting the relative importance of wet deposition sources in arid regions in contrast to dry deposition delivery in forested regions. This work demonstrates the efficacy of dragonfly larvae as biosentinels for Hg isotope studies due to their ubiquity across freshwater ecosystems and ability to track variation in Hg sources and processing attributed to small-scale habitat and large-scale regional patterns.

Light-Induced Electron Transfer in a [NiFe] Hydrogenase Opens a Photochemical Shortcut for Catalytic Dihydrogen Cleavage.

[NiFe] hydrogenases catalyze the reversible cleavage of molecular hydrogen into protons and electrons. Here, we have studied the impact of temperature and illumination on an oxygen-tolerant and thermostable [NiFe] hydrogenase by IR and EPR spectroscopy. Equilibrium mixtures of two catalytic [NiFe] states, Nia-C and Nia-SR'', were found to drastically change with temperature, indicating a thermal exchange of electrons between the [NiFe] active site and iron-sulfur clusters of the enzyme. In addition, IR and EPR experiments performed under illumination revealed an unusual photochemical response of the enzyme. Nia-SR'', a fully reduced hydride intermediate of the catalytic cycle, was found to be reversibly photoconverted into another catalytic state, Nia-L. In contrast to the well-known photolysis of the more oxidized hydride intermediate Nia-C, photoconversion of Nia-SR'' into Nia-L is an active-site redox reaction that involves light-driven electron transfer towards the enzyme's iron-sulfur clusters. Omitting the ground-state intermediate Nia-C, this direct interconversion of these two states represents a potential photochemical shortcut of the catalytic cycle that integrates multiple redox sites of the enzyme. In total, our findings reveal the non-local redistribution of electrons via thermal and photochemical reaction channels and the potential of accelerating or controlling [NiFe] hydrogenases by light.

Boron-Nitrogen-Containing Benzene Valence Isomers.

Benzene is one of the most ubiquitous structural motifs in chemistry. The valence isomers of benzene have also attracted synthetic chemists' attention due to their unique structures, bonding, and reactivity. We have been investigating boron-nitrogen-containing benzene valence isomers via photoisomerization of 1,2-azaborines. In this contribution, we summarize recent developments of these highly strained BN-heterocyclic compounds including their synthesis, characterization, proposed mechanism of formation, and their potential applications.

Comprehensive measurement of carbonyls in Lhasa, Tibetan Plateau: Implications for strong atmospheric oxidation capacity.

Carbonyls are ubiquitous in the troposphere and play a crucial role in atmospheric oxidation capacity (AOC), particularly in photochemistry-active regions such as the Tibetan Plateau (TP). However, the composition and evolution of carbonyls over the TP is still poorly understood due to a lack of comprehensive observations and modelling. Here, we conducted an intensive field measurement of 37 carbonyls and their precursors at a suburban site in Lhasa during summer 2022. Markedly higher levels of carbonyls (7.24 ± 3.83 ppbv) were found during ozone pollution episodes, with 36 % higher than those during non-episodes. Formaldehyde was the most abundant carbonyl (38 %), which primarily originating from photochemical secondary formations. Simulations using the Rapid adaptive Optimization Model for Atmospheric Chemistry (ROMAC) indicated strong AOC in Lhasa, with the daytime maximum of ·OH and ·HO2 of 9.8 × 106 and 4.2 × 108 molecules cm-3, respectively, which were even higher than that in most of the megacities in China. Notably, AOC significantly enhanced with the increasing carbonyls during the episodes, with the concentrations of ·OH and ·HO2 were boosted 21 % and 67 % than those during non-episodes, respectively. Budget analysis revealed that the ·HO2 + NO (88 %) and ·OH + VOC (74 %) pathways dominated the generation and loss of ·OH, respectively. And for ·HO2, they were ·RO2 + NO (67 %) and ·HO2 + NO (83 %). This study provides valuable insights into the strong AOC in the ecologically-fragile and climate-sensitive TP region, and highlighted the crucial role of anthropogenic-biogenic interactions in the active photochemistry of TP.