Photoinitiated Reaction Research Articles

Facile Synthesis of Prussian Blue Derivate‐Modified Mesoporous Material via Photoinitiated Thiol–Ene Click Reaction for Cesium Adsorption

A novel strategy to synthesize a functional mesoporous material for efficient removal of cesium is reported. Specifically, Prussian blue derivate-modified SBA-15 (SBA-15@FC) was prepared by photoinitiated thiol-ene reaction between thiol-modified SBA-15 and pentacyano(4-vinyl pyridine)ferrate complex. The effects of weight percentage of the Prussian blue derivate, pH, adsorbent dose, co-existing ions, and initial concentration were evaluated on the adsorption of cesium ions. The adsorption kinetically follows a pseudo-second-order model and reaches equilibrium within 2 h with a high adsorption capacity of about 13.90 mg Cs g(-1) , which indicates that SBA-15@FC is a promising adsorbent to effectively remove cesium from aqueous solutions.

Fast preparation of a highly efficient organic monolith via photo-initiated thiol-ene click polymerization for capillary liquid chromatography

A novel organic monolith was firstly prepared in a UV-transparent fused-silica capillary by a single-step approach via photo-initiated thiol-ene click polymerization reaction of 1,2,4-trivinylcyclohexane (TVCH) and pentaerythriol tetra(3-mercaptopropionate) (4SH) within 10min. The effects of both composition of prepolymerization solution and polymerization time on the morphology and permeability of monolithic column were investigated in detail. Then, the optimal condition was acquired to fabricate a homogeneous and permeable organic monolith. The chemical groups of the monolithic column were confirmed by Fourier transform infrared spectroscopy (FT-IR). The SEM graphs showed the organic monolith possessed a uniform porous structure, which promotes the highest column efficiency of ∼133,000 plates per meter for alkylbenzenes at the linear velocity of 0.65mm/s in reversed-phase liquid chromatography. Finally, the organic monolithic column was further applied for separation of basic compounds, pesticides and EPA610, indicating satisfactory separation ability.

Feasibility of Valence-to-Core X-ray Emission Spectroscopy for Tracking Transient Species.

X-ray spectroscopies, when combined in laser-pump, X-ray-probe measurement schemes, can be powerful tools for tracking the electronic and geometric structural changes that occur during the course of a photoinitiated chemical reaction. X-ray absorption spectroscopy (XAS) is considered an established technique for such measurements, and X-ray emission spectroscopy (XES) of the strongest core-to-core emission lines (Kα and Kβ) is now being utilized. Flux demanding valence-to-core XES promises to be an important addition to the time-resolved spectroscopic toolkit. In this paper we present measurements and density functional theory calculations on laser-excited, solution-phase ferrocyanide that demonstrate the feasibility of valence-to-core XES for time-resolved experiments. We discuss technical improvements that will make valence-to-core XES a practical pump–probe technique.

Rational design of an efficient, genetically encodable, protein-encased singlet oxygen photosensitizer.

Singlet oxygen, O(2)(a(1)Δ(g)), plays a key role in many processes of cell signaling. Limitations in mechanistic studies of such processes are generally associated with the difficulty of controlling the amount and location of O(2)(a(1)Δ(g)) production in or on a cell. As such, there is great need for a system that (a) selectively produces O(2)(a(1)Δ(g)) in appreciable and accurately quantifiable yields and (b) can be localized in a specific place at the suborganelle level. A genetically encodable, protein-encased photosensitizer is one way to achieve this goal. Through a systematic and rational approach involving mutations to a LOV2 protein that binds the chromophore flavin mononucleotide (FMN), we have developed a promising photosensitizer that overcomes many of the problems that affect related systems currently in use. Specifically, by decreasing the extent of hydrogen bonding between FMN and a specific amino acid residue in the local protein environment, we decrease the susceptibility of FMN to undesired photoinitiated electron-transfer reactions that kinetically compete with O(2)(a(1)Δ(g)) production. As a consequence, our protein-encased FMN system produces O(2)(a(1)Δ(g)) with the uniquely large quantum efficiency of 0.25 ± 0.03. We have also quantified other key photophysical parameters that characterize this sensitizer system, including unprecedented H(2)O/D(2)O solvent isotope effects on the O(2)(a(1)Δ(g)) formation kinetics and yields. As such, our results facilitate future systematic developments in this field.

광개시 반응을 통한 폴리에틸렌 분말에의 폴리메타크릴산 그라프팅과 PE-g-PMA의 특성 분석

광개시 반응을 통한 폴리에틸렌 분말에의 폴리메타크릴산 그라프팅과 PE-g-PMA의 특성 분석

Self‐Repairable Polyurethane Networks by Atmospheric Carbon Dioxide and Water

Sugar moieties were incorporated into cross-linked polyurethane (PUR) networks in an effort to achieve self-repairing in the presence of atmospheric carbon dioxide (CO2) and water (H2O). When methyl-α-D-glucopyranoside (MGP) molecules are reacted with hexamethylene diisocyanate trimer (HDI) and polyethylene glycol (PEG) to form cross-linked MGP-polyurethane (PUR) networks, these materials are capable of self-repairing in air. This process requires atmospheric amounts of CO2 and H2O, thus resembling plant behavior of carbon fixation during the photosynthesis cycle. Molecular processes responsible for this unique self-repair process involve physical diffusion of cleaved network segments as well as the formation of carbonate and urethane linkages. Unlike plants, MGP-PUR networks require no photo-initiated reactions, and they are thus capable of repair in darkness under atmospheric conditions.

Synthesis of non-linear protein dimers through a genetically encoded Thiol-ene reaction.

Site-specific incorporation of bioorthogonal unnatural amino acids into proteins provides a useful tool for the installation of specific functionalities that will allow for the labeling of proteins with virtually any probe. We demonstrate the genetic encoding of a set of alkene lysines using the orthogonal PylRS/PylTCUA pair in Escherichia coli. The installed double bond functionality was then applied in a photoinitiated thiol-ene reaction of the protein with a fluorescent thiol-bearing probe, as well as a cysteine residue of a second protein, showing the applicability of this approach in the formation of heterogeneous non-linear fused proteins.

Photoactivated bioconjugation between ortho-azidophenols and anilines: a facile approach to biomolecular photopatterning.

Methods for the surface patterning of small molecules and biomolecules can yield useful platforms for drug screening, synthetic biology applications, diagnostics, and the immobilization of live cells. However, new techniques are needed to achieve the ease, feature sizes, reliability, and patterning speed necessary for widespread adoption. Herein, we report an easily accessible and operationally simple photoinitiated reaction that can achieve patterned bioconjugation in a highly chemoselective manner. The reaction involves the photolysis of 2-azidophenols to generate iminoquinone intermediates that couple rapidly to aniline groups. We demonstrate the broad functional group compatibility of this reaction for the modification of proteins, polymers, oligonucleotides, peptides, and small molecules. As a specific application, the reaction was adapted for the photolithographic patterning of azidophenol DNA on aniline glass substrates. The presence of the DNA was confirmed by the ability of the surface to capture living cells bearing the sequence complement on their cell walls or cytoplasmic membranes. Compared to other light-based DNA patterning methods, this reaction offers higher speed and does not require the use of a photoresist or other blocking material.

Trigger-Responsive Poly(β-amino ester) Hydrogels.

Water-soluble, acrylate-terminated poly(β-amino esters) with built-in trigger-responsive domains were synthesized through Michael addition of trigger-responsive diacrylates and primary amines. They were used as macromolecular precursors for photoinitiated cross-linking reactions to prepare trigger-responsive hydrogels for protein encapsulation. The encapsulated proteins could be rapidly released upon external triggering.

The Photoinitiated Reaction Pathway of Full-length Cyanobacteriochrome Tlr0924 Monitored Over 12 Orders of Magnitude

The coupling of photochemistry to protein chemical and structural change is crucial to biological light-activated signaling mechanisms. This is typified by cyanobacteriochromes (CBCRs), members of the phytochrome superfamily of photoreceptors that exhibit a high degree of spectral diversity, collectively spanning the entire visible spectrum. CBCRs utilize a basic E/Z isomerization of the bilin chromophore as the primary step in their photocycle, which consists of reversible photoconversion between two photostates. Despite intense interest in these photoreceptors as signal transduction modules a complete description of light-activated chemical and structural changes has not been reported. The CBCR Tlr0924 contains both phycocyanobilin and phycoviolobilin chromophores, and these two species photoisomerize in parallel via spectrally and kinetically equivalent intermediates before the second step of the photoreaction where the reaction pathways diverge, the loss of a thioether linkage to a conserved cysteine residue occurs, and the phycocyanobilin reaction terminates in a red-absorbing state, whereas the phycoviolobilin reaction proceeds more rapidly to a final green-absorbing state. Here time-resolved visible transient absorption spectroscopy (femtosecond to second) has been used, in conjunction with time-resolved IR spectroscopy (femtosecond to nanosecond) and cryotrapping techniques, to follow the entire photoconversion of the blue-absorbing states to the green- and red-absorbing states of the full-length form of Tlr0924 CBCR. Our analysis shows that Tlr0924 undergoes an unprecedented long photoreaction that spans from picoseconds to seconds. We show that the thermally driven, long timescale changes are less complex than those reported for the red/far-red photocycles of the related phytochrome photoreceptors.

A Photoinduced, Benzyne Click Reaction

The [3 + 2] cycloaddition of azides and alkynes has proven invaluable across numerous scientific disciplines for imaging, cross-linking, and site-specific labeling among many other applications. We have developed a photoinitiated, benzyne-based [3 + 2] cycloaddition that is tolerant of a variety of functional groups as well as polar, protic solvents. The reaction is complete on the minute time scale using a single equivalent of partner azide, and the benzyne photoprecursor is stable for months under ambient light at room tempurature. Herein we report the optimization and scope of the photoinitiated reaction as well as characterization of the cycloaddition products.

Clickable poly(ionic liquid)s for modification of glass and silicon surfaces

Covalent attachment of poly(ionic liquid)s (PILs) by click chemistry on glass or silicon (Si) surfaces was performed. Poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (polyVBBI+Tf2N−), and copolymers of polyVBBI+Tf2N− with fluorescein O-methacrylate were synthesized by conducting an atom transfer radical polymerization (ATRP) from initiators containing azide or thioacetate groups. The azide- and thiol-terminated PILs were then successfully grafted onto alkyne and alkene modified glass/Si wafers by thermal azide–alkyne cycloaddition and photoinitiated thiol-ene click reactions, respectively. The modified surfaces were characterized by contact angle measurements and ellipsometry. The fluorescent PIL functionalized surfaces showed strong fluorescence under UV irradiation. This procedure of tethering PILs to substrates also provides an easy way to change the surface hydrophilicity by replacing the anions in the grafted PILs. The present approach could be readily applied for surface modifications with other types of PILs or their copolymers to achieve different functionalities on various surfaces.

π-conjugated sulfonium-based photoacid generators: an integrated molecular approach for efficient one and two-photon polymerization

D–π–A type π-conjugated photoacid generators through the para-to-meta substitution strategy show high efficiency in photoinitiated cationic polymerization reactions at 405 nm and 800 nm excitation.

Real time monitoring of click chemistry self-healing in polymer composites

A photo-healable rubber composite based on effective and fast thiol–alkyne click chemistry as a self-healing agent prestored in glass capillaries is reported. The click reaction and its effect on the mechanical properties of the composite are monitored in real time by dynamic mechanical analysis, showing that the successful bleeding of healing agents to the crack areas and the effective photoinitiated click reaction result in a 30% storage modulus increase after only 5 min of UV light exposure. X-ray tomography confirms capillary-driven bleeding of reactants to the damaged areas. The effect of storing the click chemistry reactants in separate capillaries is also studied, and results show the importance of stoichiometry in achieving a significant level of repair of the composite. No reactant degradation or premature chemical reaction is observed over time in samples stored in the absence of UV radiation; they are able to undergo the self-healing reaction even one month after preparation.

Extracellular-controlled breast cancer cell formation and growth using non-UV patterned hydrogels via optically-induced electrokinetics

The culturing of cancer cells on micropatterned substrates can provide insight into the factors of the extracellular environment that enable the control of cell growth. We report here a novel non-UV-based technique to quickly micropattern a poly-(ethylene) glycol diacrylate (PEGDA)-based hydrogel on top of modified glass substrates, which were then used to control the growth patterns of breast cancer cells. Previously, the fabrication of micropatterned substrates required relatively complicated steps, which made it impractical for researchers to rapidly and systematically investigate the effects of different cell growth patterns. The technique presented herein operates on the principle of optically-induced electrokinetics (OEKs) and uses computer-generated projection light patterns to dynamically pattern the hydrogel on a hydrogenated amorphous silicon (a-Si:H) thin-film, atop an indium tin oxide (ITO) glass substrate. This technique allows us to pattern lines, circles, pentagons, and more complex shapes in the hydrogel with line widths below 3 μm and thicknesses of up to 6 μm within 8 s by simply controlling the projected illumination pattern and applying an appropriate AC voltage between the two ITO glass substrates. After separating the glass substrates to expose the patterned hydrogel, we experimentally demonstrate that MCF-7 breast cancer cells will adhere to the bare a-Si:H surface, but not to the hydrogel patterned in various geometric shapes and sizes. Theoretical analysis and finite-element model simulations reveal that the dominant OEK forces in our technique are the dielectrophoresis (DEP) force and the electro-osmosis force, which enhance the photo-initiated cross-linking reaction in the hydrogel. Our preliminary cultures of breast cancer cells demonstrate that this reported technique could be applied to effectively confine the growth of cancer cells on a-Si:H surfaces and affect individual cell geometry during their growth.

Fabrication of Cysteine‐Responsive Biomimetic Single Nanochannels by a Thiol‐yne Reaction Strategy and Their Application for Sensing in Urine Samples

A photoinitiated thiol-yne click reaction strategy is used to fabricate a novel responsive biomimetic nanochannel platform. It displays a selective response for Cys by way of covalent bond formation on the channel surface. This system can be applied for Cys sensing with high specificity and non-interference performance in complex matrices and human urine samples.

Synthesis of a novel sulfur-bearing secondary antioxidant with a high molecular weight and its comparative study on antioxidant behavior in polypropylene with two commercial sulfur-bearing secondary antioxidants having relatively low molecular weight

A novel sulfur-bearing secondary antioxidant with a high molecular weight of 2252 (OS-POSS), successfully synthesized via photoinitiated thiol-ene click reaction, was compared with two commercial sulfur-bearing secondary antioxidants on the stabilization of polypropylene (PP). The results of their oxidation induction time (OIT) via differential scanning calorimeter measurement (DSC) showed that the higher the molecular weight of secondary antioxidant is, the longer the OIT value, whether such sulfur-bearing antioxidant is used singly or in combination with primary antioxidant. The study of their long-term accelerated thermal aging in the air oven at 150 °C displayed that the molecular structure of sulfur-bearing secondary antioxidant, besides molecular weight, is another highly important factor determining the antioxidant efficiency, i.e., physical loss of antioxidants with the relatively low molecular weight may determine antioxidant efficiency, whereas thioether groups having neighboring ester carbonyl moieties may decompose more hydroperoxides with quicker rate.

Oxygen‐Dependent Photochemistry and Photophysics of “MiniSOG,” a Protein‐Encased Flavin

Selected photochemical and photophysical parameters of flavin mononucleotide (FMN) have been examined under conditions in which FMN is (1) solvated in a buffered aqueous solution, and (2) encased in a protein likewise solvated in a buffered aqueous solution. The latter was achieved using the so-called "mini Singlet Oxygen Generator" (miniSOG), an FMN-containing flavoprotein engineered from Arabidopsis thaliana phototropin 2. Although FMN is a reasonably good singlet oxygen photosensitizer in bulk water (ϕΔ = 0.65 ± 0.04), enclosing FMN in this protein facilitates photoinitiated electron-transfer reactions (Type-I chemistry) at the expense of photosensitized singlet oxygen production (Type-II chemistry) and results in a comparatively poor yield of singlet oxygen (ϕΔ = 0.030 ± 0.002). This observation on the effect of the local environment surrounding FMN is supported by a host of spectroscopic and chemical trapping experiments. The results of this study not only elucidate the behavior of miniSOG but also provide useful information for the further development of well-characterized chromophores suitable for use as intracellular sensitizers in mechanistic studies of reactive oxygen species.

Mathematical modeling of photoinitiated coating degradation: Effects of coating glass transition temperature and light stabilizers

A mathematical model, describing coating degradation mechanisms of thermoset coatings exposed to ultraviolet radiation and humidity at constant temperature, was extended to simulate the behavior of a coating with a low glass transition temperature. The effects of adding light stabilizers (a UV absorber and a radical scavenger) to the coating were also explored. The extended model includes photoinitiated oxidation reactions, intrafilm oxygen permeability, water absorption and diffusion, reduction of crosslink density, absorption of ultraviolet radiation, a radical scavenger reaction, and simulates the transient development of an oxidation zone. Simulations are in good agreement with experimental data for a fast degrading epoxy-amine coating with a glass transition temperature of −50°C. It was found that the degradation rate of the non-stabilized coating was influenced significantly by the diffusion rate of oxygen in the oxidation zone, whereas light absorption by the photoproducts formed was only a secondary effect. On the other hand, the degradation rate of the stabilized coating was mainly influenced by the light absorption capability of the coating and in this case there was no oxygen diffusion resistance. Finally, simulations showed that the rate constants of the photoinitiating and oxidation reactions, taking place within the epoxy-amine family of coatings, are strong functions of the specific crosslinker used and must be estimated, in each case, by calibration of the model against adequate experimental data series.

A Photoinduced Nanoparticle Separation in Microchannels via pH-Sensitive Surface Traps

A microfluidic surface trap was developed for capturing pH-sensitive nanoparticles via a photoinitiated proton-releasing reaction of o-nitrobenzaldehyde (o-NBA) that reduces the solution pH in microchannels. The surface trap and nanoparticles were both modified with a pH-responsive polymer-poly(N-isorpopylacylamide-co-propylacrylic acid), P(NIPAAm-co-PAA). The o-NBA-coated microchannel walls demonstrated rapid proton release upon UV light irradiation, allowing the buffered solution pH in the microchannel to decrease from 7.4 to 4.5 in 60 s. The low solution pH switched the polymer-modified surfaces to be more hydrophobic, which enabled the capture of the pH-sensitive nanobeads onto the trap. When a photomask was utilized to limit the UV irradiation to a specific channel region, we were able to restrict the particle separation to only the exposed region. Via control of the UV irradiation, this technique enables not only prompt pH changes within the channel but also the capture of target molecules at specific channel locations.