Photostationary State Research Articles

Photochemical Deracemization of Chiral Alkenes via Triplet Energy Transfer.

A visible-light-mediated, enantioselective approach to axially chiral alkenes is described. Starting from a racemic mixture, a major alkene enantiomer is formed due to selective triplet energy transfer from a catalytically active chiral sensitizer. A catalyst loading of 2 mol % was sufficient to guarantee consistently high enantioselectivities and yields (16 examples, 51%-quant., 81-96% ee). NMR studies and DFT computations revealed that triplet energy transfer is more rapid within the substrate-catalyst complex of the minor alkene enantiomer. Since this enantiomer is continuously racemized, the major enantiomer is enriched in the photostationary state.

Synthesis and photochromism of catechol-containing symmetrical azobenzene compounds.

Symmetrical azobenzene derivatives with two catechol groups, 1d–4d, were synthesized as kinds of novel compounds, and the structures were confirmed using mass spectrometry and nuclear magnetic resonance spectroscopy. These compounds could attain photostationary state rapidly in solution upon UV irradiation, and their photochromism had good reversibility. Substituents and their positions on azobenzene chromophore had obvious influence on the maximum absorption and photochromic performances of these as-synthesized compounds. Electron-donating group on ortho positions could contribute to the redshift π–π* band. The sulfonamide group that is bonded to dopamine molecules and azobenzene rings caused a negligible n–π* transition of cis isomer, resulting in photobleaching upon UV irradiation. Among the four compounds, 4d had the strongest electron-donating ortho-methoxy substituents and lower planarity; thus its absorption could decrease more significantly upon UV irradiation of the same intensity, and its cis-to-trans conversion could be up to 63%. Furthermore, owing to the presence of catechol groups, 4d showed an effective affinity and adhesion to substrate, and on the surface of substrate, a weak colour change could be observed upon UV irradiation, but the reversibility was poorer than that in solution.

Generation of Local Diffusioosmotic Flow by Light Responsive Microgels.

Here we show that microgels trapped at a solid wall can issue liquid flow and transport over distances several times larger than the particle size. The microgel consists of cross-linked poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAM-AA) polymer chains loaded with cationic azobenzene-containing surfactant, which can assume either a trans- or a cis-state depending on the wavelength of the applied irradiation. The microgel, being a selective absorber of trans-isomers, responds by changing its volume under irradiation with light of appropriate wavelength at which the cis-isomers of the surfactant molecules diffuse out of the particle interior. Together with the change in particle size, the expelled cis-isomers form an excess of the concentration and subsequent gradient in osmotic pressure generating a halo of local light-driven diffusioosmotic (l-LDDO) flow. The direction and the strength of the l-LDDO depends on the intensity and irradiation wavelength, as well as on the amount of surfactant absorbed by the microgel. The flow pattern around a microgel is directed radially outward and can be maintained quasi-indefinitely under exposure to blue light when the trans-/cis-ratio is 2/1, establishing a photostationary state. Irradiation with UV light, on the other hand, generates a radially transient flow pattern, which inverts from inward to outward over time at low intensities. By measuring the displacement of tracer particles around neutral microgels during a temperature-induced collapse, we can exclude that a change in particle shape itself causes the flow, i.e., just by expulsion or uptake of water. Ultimately, it is its ability to selectively absorb two isomers of photosensitive surfactant under different irradiation conditions that leads to an effective pumping caused by a self-induced diffusioosmotic flow.

Light-Control over Casein Kinase 1δ Activity with Photopharmacology: A Clear Case for Arylazopyrazole-Based Inhibitors.

Protein kinases are responsible for healthy cellular processes and signalling pathways, and their dysfunction is the basis of many pathologies. There are numerous small molecule inhibitors of protein kinases that systemically regulate dysfunctional signalling processes. However, attaining selectivity in kinase inhibition within the complex human kinome is still a challenge that inspires unconventional approaches. One of those approaches is photopharmacology, which uses light-controlled bioactive molecules to selectively activate drugs only at the intended space and time, thereby avoiding side effects outside of the irradiated area. Still, in the context of kinase inhibition, photopharmacology has thus far been rather unsuccessful in providing light-controlled drugs. Here, we present the discovery and optimisation of a photoswitchable inhibitor of casein kinase 1δ (CK1δ), important for the control of cell differentiation, circadian rhythm, DNA repair, apoptosis, and numerous other signalling processes. Varying the position at which the light-responsive azobenzene moiety has been introduced into a known CK1δ inhibitor, LH846, revealed the preferred regioisomer for efficient photo-modulation of inhibitory activity, but the photoswitchable inhibitor suffered from sub-optimal (photo)chemical properties. Replacement of the bis-phenyl azobenzene group with the arylazopyrazole moiety yielded a superior photoswitch with very high photostationary state distributions, increased solubility and a 10-fold difference in activity between irradiated and thermally adapted samples. The reasons behind those findings are explored with molecular docking and molecular dynamics simulations. Results described here show how the evaluation of privileged molecular architecture, followed by the optimisation of the photoswitchable unit, is a valuable strategy for the challenging design of the photoswitchable kinase inhibitors.

The Power of Far-Red Light at Night: Photomorphogenic, Physiological, and Yield Response in Pepper During Dynamic 24 Hour Lighting.

Supplemental light is needed during the winter months in high latitude regions to achieve the desired daily light integral (DLI) (photoperiod × intensity) for greenhouse pepper (Capsicum annuum) production. Peppers tend to have short internodes causing fruit stacking and higher labor time for plant maintenance when grown under supplemental light. Far-red light can increase internode length, and our previous study on tomatoes (Solanum lycopersicum) also discovered monochromatic blue light at night during continuous lighting (CL, 24 h) increased stem elongation. Furthermore, the use of low-intensity, long photoperiod lighting can reduce light fixture costs and overall electricity costs due to lower power prices during the night. Therefore, we investigated the use of blue and/or far-red light during the night period of CL to increase stem elongation. Three pepper cultivars with different internode lengths/growing characteristics (‘Maureno,’ ‘Gina,’ and ‘Eurix’) were used to investigate the effects on plant morphology in a short experiment, and one cultivar ‘Maureno’ was used in a long experiment to assess the impact on fruit yield. The five lighting treatments that were used are as follows: 16 h of white light during the day followed by either 8 h of darkness (16W – control), white light (24W), blue light only (16W + 8B), blue + far-red light (16W + 8BFR), or far-red light only (16W + 8FR). Calculated nighttime phytochrome photostationary state (PSS) was 0.833, 0.566, 0.315, and 0.186 for 24W, 16W + 8B, 16W + 8BFR, and 16W + 8FR respectively. All five treatments had the same DLI in photosynthetically active radiation (PAR) and far-red light. The 16W + 8BFR and 16W + 8FR treatments significantly increased internode length compared to 16W and 24W but neither was more impactful than the other. The 16W + 8B treatment also increased internode length but to a lesser extent than 16W + 8BFR and 16W + 8FR. This indicates that a nighttime PSS of 0.315 is sufficient to maximize stem elongation. Both 16W + 8B and 16W + 8BFR drove photosynthesis during the nighttime supporting a similar yield compared to 16W. Therefore, 16W + 8BFR is the most potential lighting strategy as it can lead to a greater reduction in the light fixture and electrical costs while maintaining yield and enhancing internode length.

Analysis of Ozone Photochemistry over Southern Tropical Megacity, Bengaluru, India.

Rapid infrastructure development, increased population, shift in land use practices and higher vehicular emissions have all influenced Ozone (O3 ) production through its precursor gases in southern megacity, Bengaluru, India. We have investigated the photochemistry using hourly measurements of O3 and associated precursor gases conducted in Bengaluru during January to December 2019. The rate of formation of O3 is analyzed for Bengaluru for the first time using a photochemical model involving NOx cycle. On the diurnal scale, O3 showed a midday peak (1200-1500 IST), while its precursors showed a bimodal trend with peaks at 0900 IST and 2100 IST. The photolytic rate constants for and were derived from the tropospheric ultraviolet and visible (TUV) radiation model. Using the photolytic rate constants for and under the triad NO-NO2 -O3 , photostationary state (PSS), Leighton ratio (Ф) and its deviations from unity were estimated over Bengaluru. Positive anomalies (Φ > 1) were obtained, and the computed Φ was utilized to determine the total mixing ratios of the peroxy radical (PO2 ). The seasonal variation in revealed that in the presence of intense solar radiation and NOx, VOCs, CO and NMVOCs in the mixing layer, O3 forms photochemically over the surface.

Photostationary State in Dynamic Covalent Networks.

We explore a cross-linked polymer network based on a visible light photodynamic [2 + 2] cycloaddition driven by styrylpyrene chemistry. Based on a polymer backbone with pendent styrylpyrene units, the network can be formed by using λ = 450 nm irradiation. Upon irradiation with λ = 340 nm, a photostationary state is generated within the network with ∼17% of the styrylpyrene units open compared to close to 2% in the visible light cured state. The limited fraction of open [2 + 2] couples is caused by their proximity and is in sharp contrast to solution experiments on the photoreactive moiety. Thus, the polymer network retains its mechanical properties even at the photostationary point. We hypothesize that the application of an additional stimulus could serve as a second gate for inducing network disintegration by spacing the [2 + 2] units during ultraviolet irradiation.

The One-Electron Reduced Active-Site FeFe-Cofactor of Fe-Nitrogenase Contains a Hydride Bound to a Formally Oxidized Metal-Ion Core.

The nitrogenase active-site cofactor must accumulate 4e-/4H+ (E4(4H) state) before N2 can bind and be reduced. Earlier studies demonstrated that this E4(4H) state stores the reducing-equivalents as two hydrides, with the cofactor metal-ion core formally at its resting-state redox level. This led to the understanding that N2 binding is mechanistically coupled to reductive-elimination of the two hydrides that produce H2. The state having acquired 2e-/2H+ (E2(2H)) correspondingly contains one hydride with a resting-state core redox level. How the cofactor accommodates addition of the first e-/H+ (E1(H) state) is unknown. The Fe-nitrogenase FeFe-cofactor was used to address this question because it is EPR-active in the E1(H) state, unlike the FeMo-cofactor of Mo-nitrogenase, thus allowing characterization by EPR spectroscopy. The freeze-trapped E1(H) state of Fe-nitrogenase shows an S = 1/2 EPR spectrum with g = [1.965, 1.928, 1.779]. This state is photoactive, and under 12 K cryogenic intracavity, 450 nm photolysis converts to a new and likewise photoactive S = 1/2 state (denoted E1(H)*) with g = [2.009, 1.950, 1.860], which results in a photostationary state, with E1(H)* relaxing to E1(H) at temperatures above 145 K. An H/D kinetic isotope effect of 2.4 accompanies the 12 K E1(H)/E1(H)* photointerconversion. These observations indicate that the addition of the first e-/H+ to the FeFe-cofactor of Fe-nitrogenase produces an Fe-bound hydride, not a sulfur-bound proton. As a result, the cluster metal-ion core is formally one-electron oxidized relative to the resting state. It is proposed that this behavior applies to all three nitrogenase isozymes.

Effect of the alkyl linker length on the photoisomerization of hydrazone switches on metal surfaces

A series of bistable hydrazone switches containing alkyl thiolate linkers of various lengths (Cn HAT, n = 3, 8, 10, and 11) were synthesized. We explore the length effect of the carbon chain on the photoisomerization of hydrazone switches using UV–vis spectroscopy and tip-enhanced Raman spectroscopy (TERS). The conversion efficiency (photostationary state, PSS, after irradiation at 415 or 340 nm) of the isomerization of Cn HAT monolayers on Au rises with the increasing length of the alkyl chain, with an optimum result for n-octyl (C8) thiolate or longer linkers. The low PSS415 of C3 HAT is attributed to strong quenching by the metal surface, as confirmed by density functional theory (DFT) calculations based on a one-dimensional double-well model. The partial trap of photo-induced hot carriers in the excited states of C3 HAT in the potential well of Au reduces the lifetime of its excited states. Such calculation results provide insight into the detailed mechanism of the surface quenching effect. Furthermore, UV–vis results suggest that after irradiation at 415 nm, Cn HATs cannot isomerize when bound to Ag; higher photon energies are necessary in this case. These results validate the previously proposed substrate-mediated isomerization mechanism.

Visible-Light Switching of Metallosupramolecular Assemblies.

A photoswitchable ligand and palladium(II) ions form a dynamic mixture of self‐assembled metallosupramolecular structures. The photoswitching ligand is an ortho‐fluoroazobenzene with appended pyridyl groups. Combining the E‐isomer with palladium(II) salts affords a double‐walled triangle with composition [Pd3L6]6+ and a distorted tetrahedron [Pd4L8]8+ (1 : 2 ratio at 298 K). Irradiation with 410 nm light generates a photostationary state with approximately 80 % of the E‐isomer of the ligand and results in the selective disassembly of the tetrahedron, the more thermodynamically stable structure, and the formation of the triangle, the more kinetically inert product. The triangle is then slowly transformed back into the tetrahedron over 2 days at 333 K. The Z‐isomer of the ligand does not form any well‐defined structures and has a thermal half‐life of 25 days at 298 K. This approach shows how a thermodynamically preferred self‐assembled structure can be reversibly pumped to a kinetic trap by small perturbations of the isomer distribution using non‐destructive visible light.

Shifting photo-stationary light-induced excited spin state trapping equilibrium towards higher temperature by increasing light fluence

The Light-Induced Excited Spin-State Trapping (LIESST) process allows tuning the electronic state of spin-crossover materials from low (LS) to high spin (HS) states. The photoinduced HS state is long-lived, up to a characteristic temperature, T(LIESST), above which the system relaxes rapidly to the LS state. We study the effect of light irradiance on competing LS → HS up-conversion and HS → LS thermal relaxation on the [Fe(phen)2(NCS)2] system. Raman spectroscopy and magnetic measurements are used to investigate this phenomenon. An empiric model describes the competition between up conversion and thermal relaxation mechanisms and the stabilization of photo-stationary state towards higher temperature.

Photochromic properties in a head coupled ruthenium complex with dithienylethene-ethynylthiophene

In order to compare the photochromic properties between the shoulder coupled and the head coupled dithienylethene ruthenium complexes, a ruthenium complex (2o) with dithienylethene-ethynylthiophene was synthesized. Complex 2o displays multistates through light irradiation and a reversible redox process, but the photocyclization conversion yield (18%) is much lower than that of the reported shoulder coupled ruthenium complex 1o (>95%), and the time taken to reach the photostationary state (PSS) (160 min) is much longer compared to that of 1o (160 s), which is probably attributed to the lower electronic density in 2o than that of 1o, leading to more difficulty in photocyclization reaction. The photochemical processes are well demonstrated and explained by UV-vis, NMR, electrochemical, and time-dependent density functional theory (TD-DFT) computational studies.

Effects of Green Light on Elongation Do Not Interact with Far-Red, Unless the Phytochrome Photostationary State (PSS) Changes in Tomato.

Simple SummaryThis paper focuses on the role of phytochromes (phys) in the interaction between green light and far-red light effects on “shade avoidance syndrome”. We grew wild type and phy mutants of tomato under a set of light conditions with different combinations of green, blue, red, and far-red light. Partial (20%) replacement of red/blue by green light in the absence of far-red light hardly affected the tomato plant morphology. However, when the spectrum contained far-red light, partially replacing red/blue by green light resulted in more elongation, which was associated with a lower phytochrome photostationary state (PSS) value. There was no effect of partial substitution of red/blue with green light when the PSS was kept constant. Thus, this study has revealed an interaction between green and far-red light effects on elongation unless PSS was kept constant. Green light was often a bit neglected in photobiology, but now an increasing number of researchers are realizing that green light deserves more attention. This study advances the understanding of light quality and plant growth and finding the optimal spectrum when growing plants under LED lighting in controlled environment agriculture.Green light (G) could trigger a “shade avoidance syndrome” (SAS) similarly to far-red light. We aimed to test the hypothesis that G interacts with far-red light to induce SAS, with this interaction mediated by phytochromes (phys). The tomato (Solanum lycopersicum cv. Moneymaker) wild-type (WT) and phyA, phyB1B2, and phyAB1B2 mutants were grown in a climate room with or without 30 µmol m−2 s−1 G on red/blue and red/blue/far-red backgrounds, maintaining the same photosynthetically active radiation (400–700 nm) of 150 µmol m−2 s−1 and red/blue ratio of 3. G hardly affected the dry mass accumulation or leaf area of WT, phyA, and phyB1B2 with or without far-red light. A lower phytochrome photostationary state (PSS) by adding far-red light significantly increased the total dry mass by enhancing the leaf area in WT plants but not in phy mutants. When the background light did not contain far-red light, partially replacing red/blue with G did not significantly affect stem elongation. However, when the background light contained far-red light, partially replacing red/blue with G enhanced elongation only when associated with a decrease in PSS, indicating that G interacts with far-red light on elongation only when the PSS changes.

Self-Assembled Monolayers of Arylazopyrazoles on Glass and Silicon Oxide: Photoisomerization and Photoresponsive Wettability.

Surface coatings that respond to external influences and change their physical properties upon application of external stimuli are of great interest, with light being a particularly desirable choice. Photoswitches such as azobenzenes have been employed in a range of photoresponsive coatings. One striking change in physical property of many photoresponsive coatings is their responsive wettability upon illumination. In this work, we present photoswitchable self-assembled monolayers based on arylazopyrazoles (AAPs). In solution, AAPs offer significant improvements in terms of the photostationary state, thermal stability, and fatigue resistance. The AAP photoswitch is coupled to triethoxysilanes for an easy, one-step functionalization of glass and silicon oxide surfaces. We show the synthesis of AAP-based silanes and the successful surface functionalization, and we confirm the excellent photoswitchability of the AAPs in a self-assembled monolayer upon alternating irradiation with UV (365 nm) and green (520 nm) light. The self-assembled monolayers are investigated by UV/vis spectroscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and contact angle goniometry. We furthermore investigate the effect of substitution of the AAPs on the photoresponsive wetting behavior and compare this with density functional theory (DFT) calculations of the dipole moments of the AAPs.

Photo- and thermo-responsive microgels with supramolecular crosslinks for wavelength tunability of the volume phase transition temperature.

Functional microgels have powerful applications, especially due to their quick responsiveness to different external stimuli such as temperature, pH, ionic strength, solvent composition and light. Here, we describe the synthesis of novel dual-responsive poly(N-isopropylacrylamide) (PNIPAM) microgels and demonstrate that, in addition to temperature, light changes their properties. The crosslinks inside the microgels were achieved by the host-guest interactions between the trans azobenzene (transAzo) and β-cyclodextrin (βCD) units. transAzo can be photoisomerized to cisAzo which exhibits significant lower binding affinity to βCD. As a consequence, the crosslink density, and thus several microgel properties, can be controlled by light irradiation. Surprisingly, this irradiation with light can significantly change the volume phase transition temperature (VPTT) by several degrees centigrade, presumably due to the fact that the polar βCD shields the transAzo bound to it, whereas the unbound cisAzo is rather apolar. As a result, continuous irradiation with specific wavelengths until reaching the respective photostationary state allows for a full control over the VPTT within the physiologically relevant range between 32 °C and 38 °C.

Optical Membrane Control with Red Light Enabled by Red-Shifted Photolipids.

Photoswitchable phospholipids, or "photolipids", that harbor an azobenzene group in their lipid tails are versatile tools to manipulate and control lipid bilayer properties with light. So far, the limited ultraviolet-A/blue spectral range in which the photoisomerization of regular azobenzene operates has been a major obstacle for biophysical or photopharmaceutical applications. Here, we report on the synthesis of nano- and micrometer-sized liposomes from tetra-ortho-chloro azobenzene-substituted phosphatidylcholine (termed red-azo-PC) that undergoes photoisomerization on irradiation with tissue-penetrating red light (≥630 nm). Photoswitching strongly affects the fluidity and mechanical properties of lipid membranes, although small-angle X-ray scattering and dynamic light scattering measurements reveal only a minor influence on the overall bilayer thickness and area expansion. By controlling the photostationary state and the photoswitching efficiency of red-azo-PC for specific wavelengths, we demonstrate that shape transitions such as budding or pearling and the division of cell-sized vesicles can be achieved. These results emphasize the applicability of red-azo-PC as a nanophotonic tool in synthetic biology and for biomedical applications.

Photochemical Deracemization at sp3-Hybridized Carbon Centers via a Reversible Hydrogen Atom Transfer.

A photochemical deracemization of 5-substituted 3-phenylimidazolidine-2,4-diones (hydantoins) is reported (27 examples, 69%-quant., 80-99% ee). The reaction is catalyzed by a chiral diarylketone which displays a two-point hydrogen bonding site. Mechanistic evidence (DFT calculations, radical clock experiments, H/D labeling) suggests the reaction to occur by selective hydrogen atom transfer (HAT). Upon hydrogen binding, one substrate enantiomer displays the hydrogen atom at the stereogenic center to the photoexcited catalyst allowing for a HAT from the substrate and eventually for its conversion into the product enantiomer. The product enantiomer is not processed by the catalyst and is thus enriched in the photostationary state.

Inside Back Cover: Irradiation‐Wavelength Directing Circularly Polarized Luminescence in Self‐Organized Helical Superstructures Enabled by Hydrogen‐Bonded Chiral Fluorescent Molecular Switches (Angew. Chem. Int. Ed. 52/2021)

Irradiation-wavelength directing circularly polarized luminescence in emissive self-organized helical superstructures is demonstrated by Jinbao Guo, Quan Li, and co-workers in their Research Article on page 27158. Phototuning of the turning-off and the polarization inversion of circularly polarized luminescence signals was achieved in the corresponding photostationary state of the same helical superstructure constructed from the light-driven hydrogen-bonded chiral fluorescent molecular switch.

Transition kinetics of mixed lipid:photosurfactant assemblies studied by time-resolved small angle X-ray scattering

HypothesisPhotoswitchable surfactants are used in the design of many light-responsive colloids and/or self-assemblies. Photo-isomerization enables to control molecular equilibrium, and triggers transient reorganizations with possibly out-of-equilibrium intermediate states that have been overlooked. Here, we address this question by an in depth structural investigation of intermediate lipid-surfactant assemblies that occur during fast isothermal photo-triggered transition in lipid:surfactant mixtures. ExperimentsThe structural parameters of mixed assemblies of azobenzene-containing cationic surfactant (AzoTMA) and dioleoylphosphatidylcholine (DOPC) lipids were studied by light scattering and time-resolved small angle X-ray scattering. Structural and compositional information about the assemblies and unimers in bulk were determined at the photostationary states, as well as at intermediate kinetic states formed during UV or blue light illumination. FindingsDOPC:AzoTMA systems form mixed assemblies representative of phospholipid:cationic surfactant mixtures, that evolve from spheroid, to rod-like micelles, and vesicles with increasing DOPC fraction. Transient assemblies detected during the photo-triggered kinetics are similar to the ones found in stationary states. But changes of AzoTMA unimers in bulk can be considerably faster than mass reorganizations of the mixed assemblies, suggesting that out-of-equilibrium conditions are transiently reached. Mass reorganization of the surfactant-enriched assemblies is much faster than in the lipid enriched ones, providing insight into the role of lipids in a slow reorganization of the assemblies.

Ambient ozone over mid-Brahmaputra Valley, India: effects of local emissions and atmospheric transport on the photostationary state.

This study presents the characteristics of ground level atmospheric ozone (O3) over the rural mid-Brahmaputra Valley region of the northeastern India. Ozone and oxides of nitrogen (NOx = NO + NO2) concentration data were obtained from continuous measurement of O3 and NOx housed at the MAPAN-AQM station at Tezpur University. The meteorological parameters were obtained from the same station. The diel, monthly, and seasonal variations of O3 were studied. The O3-NOx photostationary state (PS) was carefully examined and it was found that the net O3 concertation deviated substantially from the PS during the winter season. The deviation could be attributed to local biomass burning, biogenic VOC emission from forest and agriculture, and long-range transport of peroxyacyl nitrate (PAN). The long-range transport has been ascertained by examining the ventilation coefficients (VC), which correlated with the steep growth of net O3 concentrations in the morning hours. The HYSPLIT air mass back trajectories were used in concentration-weighted trajectory (CWT) analyses of O3 to assess the long-range regional transport of O3 precursors, which positively influenced local O3 concentrations.Supplementary informationThe online version contains supplementary material available at 10.1007/s10661-021-09572-3.