Pulsed Photolysis Research Articles

Plasmonic Au-MoS2 Nanohybrids Using Pulsed Laser-Induced Photolysis Synthesis for Enhanced Visible-Light Photocatalytic Dye Degradation.

The Au-MoS2 nanocomposites (NCPs) exhibit excellent visible-light photocatalytic activity and potential applications in the photocatalytic degradation of organic dyes. In this study, an Au-MoS2 heterojunction structure with Au nanoparticles (NPs) deposited on MoS2 nanosheets was synthesized via the pulsed laser-induced photolysis method. The influence of Au content on the photocatalytic performance was systematically investigated, and the working mechanism under visible light excitation was elucidated. The optimal Au-MoS2 NCPs exhibited efficient degradation of methylene blue (MB) dye, mainly attributed to the plasmon resonance effect of Au NPs which facilitated the visible light harvesting and hot electron injection. The Au/MoS2 interface promoted the separation and transfer of photogenerated charge carriers. The electrostatic adsorption between positively charged MB molecules and the negatively charged MoS2 surface favored the affinity toward active sites. Furthermore, the photogenerated electrons and holes participated in generating reactive oxygen species such as superoxide and hydroxyl radicals, which initiated the oxidative degradation of MB. The PLIP-introduced Au NPs not only endowed the material with excellent visible light responsivity but also possibly modulated the electronic structure and photocatalytic active sites of MoS2 through an intrinsic effect, providing new insights for further enhancing the photocatalytic performance of Au-MoS2 NCPs.

Degradation of imidazolium-based ionic liquids by UV photolysis and pulsed corona discharge: The effect of persulfates addition

Ionic liquids (ILs) are salts with exceptional properties important for future development, although potentially hazardous for humans and aquatic life due to their high aqueous solubility and toxicity. Biodegradation of ILs depends on the anion nature and cation structure: many ILs are not readily degraded during conventional wastewater treatment, thus requiring alternative cost-effective and energy-efficient solutions. In this research, the degradation of aqueous imidazolium-based ILs by pulsed corona discharge (PCD) and UV photolysis combined with persulfates was studied, using peroxymonosulfate (PMS) and peroxydisulfate (PDS) as extrinsic oxidants. 1-Ethyl-3-methylimidazolium chloride ([Emim][Cl]), 1-methyl-3-octylimidazolium chloride ([Omim][Cl]), and 1-ethyl-3-methylimidazolium bromide ([Emim][Br]) were chosen as imidazolium-based ILs with different alkyl chain lengths and anions in oxidation experiments under variable operation factors - pH, concentrations of persulfates, pulse repetition frequency in PCD. Pulsed corona discharge has previously shown high energy efficiency in the degradation of micropollutants but has not yet been applied to ionic liquids. The experimental results showed the ability of PCD, PCD/oxidant and UV/oxidant combinations to completely degrade the ILs with the degradation rates in descending order [Emim][Cl] > [Omim][Cl] > [Emim][Br], indicating an impact of both the alkyl chain length and the type of anion on the oxidation rate. The strong activation of persulfates was observed in UV/oxidant combinations, whereas PCD demonstrated the effect of persulfates addition between slight acceleration and moderate deceleration of oxidation dependent on the concentration of extrinsic oxidants. The addition of the sulfate radicals’ scavenger, however, showed the presence of those in all combinations indicating a certain replacement of PCD-generated reactive oxygen species with secondary reactants formed from persulfates. The unassisted PCD and UV/PDS combination demonstrated similar energy efficiencies of about 54 and 26 mmol kWh−1 for [Emim][Cl] and [Emim][Br] degradation, respectively, while for [Omim][Cl] the UV/PDS combination showed energy efficiency 1.42 times higher than unassisted PCD.

Atmospheric Hydroxyl Radical Reaction Rate Coefficient and Total Environmental Lifetime of α-Endosulfan.

Endosulfan is a persistent organochlorine pesticide that was globally distributed before it was banned and continues to cycle in the Earth system. The chemical kinetics of the gas-phase reaction of α-endosulfan with the hydroxyl radical (OH) was studied by means of pulsed vacuum UV flash photolysis and time-resolved resonance fluorescence (FP-RF) as a function of temperature in the range of 348-395 K and led to a second-order rate coefficient kOH = 5.8 × 10-11 exp(-1960K/T) cm3 s-1 with an uncertainty range of 7 × 10-12 exp(-1210K/T) to 4 × 10-10 exp(-2710K/T) cm3 s-1. This corresponds to an estimated photochemical atmospheric half-life in the range of 3-12 months, which is much longer than previously assumed (days to weeks). Comparing the atmospheric concentrations observed after the global ban of endosulfan with environmental multimedia model predictions, we find that photochemical degradation in the atmosphere is slower than the model-estimated biodegradation in soil or water and that the latter limits the total environmental lifetime of endosulfan. We conclude that the lifetimes typically assumed for soil and aquatic systems are likely underestimated and should be revisited, in particular, for temperate and warm climates.

Porous silicon decorated with Au/TiO2 nanocomposites for efficient photoinduced enhanced Raman spectroscopy.

In this study, we investigated the potential of porous silicon (PSi) modified with Au/TiO2 nanocomposites (NCPs) as a substrate for photoinduced enhanced Raman spectroscopy (PIERS). One-step pulsed laser-induced photolysis (PLIP) was used to embed Au/TiO2 NCPs in the surface of PSi. Scanning electron microscopy revealed that adding TiO2 nanoparticles (NPs) during PLIP led to the formation of predominantly spherical Au NPs with a diameter of approximately 20 nm. Furthermore, modifying the PSi substrate with Au/TiO2 NCPs considerably enhanced the Raman signal of rhodamine 6G (R6G) after 4 h of ultraviolet (UV) irradiation. Real-time monitoring of the Raman signals of R6G at different concentrations under UV irradiation revealed that the amplitude of the signals increased with the irradiation time for R6G concentrations ranging from 10-3 M to 10-5 M. PSi substrates decorated with Au/TiO2 NCPs may be used to develop materials for PIERS applications.

Generation of Sub-nanosecond H Atom Pulses for Scattering from Single-Crystal Epitaxial Graphene.

Pulsed molecular beams allow high-density gas samples to be cooled to low internal temperatures and to produce narrow speed distributions. They are particularly useful in combination with pulsed-laser-based detection schemes and have also been used as pump pulses in pump-probe experiments with neutral matter. The mechanical response of pulsed valves and chopper wheels limits the duration of these pulses typically to about 10-100 μs. Bunch compression photolysis has been proposed as a means to produce atomic pulses shorter than 1 ns─an experimental capability that would allow new measurements to be made on chemical systems. This technique employs a spatially chirped femtosecond duration photolysis pulse that produced an ensemble of H atom photoproducts that rebunches into a short pulse downstream. To date, this technique could not produce strong enough beams to allow new experiments to be carried out. In this paper, we report production of pulsed H atom beams consistent with a 700 ps pulse duration and with sufficient intensity to carry out differentially resolved inelastic H scattering experiments from a graphene surface. We observe surprisingly narrow angular distributions for H atoms incident normal to the surface. At low incidence energies quasi-elastic scattering dominates, and at high incidence energy we observe a strongly inelastic scattering channel. These results provide the basis for future experiments where the H atoms synchronously collide with a pulsed-laser-excited surface.

Visible Light-Induced Photocatalyst with Au/TiO2 Nanocomposites Fabricated through Pulsed Laser-Induced Photolysis

Gold–titanium oxide nanocomposites (Au–TiO2 NCPs) were fabricated through pulsed laser-induced photolysis (PIPS) and verified to be usable for the visible light catalytic degradation of methylene blue (MB). The PIPS method can produce a sufficient amount of NCPs quickly and has potential to be commercialized. In contrast to other studies, we clarified the optical spectrum of the light sources, including peak power, bandwidth, and total intensity used for photodegradation reactions and discovered that the photodegradation efficiency of the produced Au–TiO2 NCPs in the wavelength range of 405 nm could reach 37% in 30 min due to the charge transfer between Au and TiO2. The control experiment shows that the addition of individual Au and TiO2 nanoparticles (NPs) to an MB solution has no enhancement of degradation ability under visible light illumination. The photodegradation of Au–TiO2 NCPs can be further improved by increasing the concentrations of auric acid and TiO2 NPs in a precursor under PIPS fabrication.

An Experimental and Theoretical Investigation of the Gas-Phase C(3P) + N2O Reaction. Low Temperature Rate Constants and Astrochemical Implications.

The reaction between atomic carbon in its ground electronic state, C(3P), and nitrous oxide, N2O, has been studied below room temperature due to its potential importance for astrochemistry, with both species considered to be present at high abundance levels in a range of interstellar environments. On the experimental side, we measured rate constants for this reaction over the 50-296 K range using a continuous supersonic flow reactor. C(3P) atoms were generated by the pulsed photolysis of carbon tetrabromide at 266 nm and were detected by pulsed laser-induced fluorescence at 115.8 nm. Additional measurements allowing the major product channels to be elucidated were also performed. On the theoretical side, statistical rate theory was used to calculate low temperature rate constants. These calculations employed the results of new electronic structure calculations of the 3A″ potential energy surface of CNNO and provided a basis to extrapolate the measured rate constants to lower temperatures and pressures. The rate constant was found to increase monotonically as the temperature falls (kC(3P)+N2O (296 K) = (3.4 ± 0.3) × 10-11 cm3 s-1), reaching a value of kC(3P)+N2O (50 K) = (7.9 ± 0.8) × 10-11 cm3 s-1 at 50 K. As current astrochemical models do not include the C + N2O reaction, we tested the influence of this process on interstellar N2O and other related species using a gas-grain model of dense interstellar clouds. These simulations predict that N2O abundances decrease significantly at intermediate times (103 - 105 years) when gas-phase C(3P) abundances are high.

Rate Constants and Branching Ratios for the Self-Reaction of Acetyl Peroxy (CH3C(O)O2•) and Its Reaction with CH3O2

The self-reaction of acetylperoxy radicals (CH3C(O)O2•) (R1) as well as their reaction with methyl peroxy radicals (CH3O2•) (R2) have been studied using laser photolysis coupled to a selective time resolved detection of three different radicals by cw-CRDS in the near-infrared range: CH3C(O)O2• was detected in the Ã-X˜ electronic transition at 6497.94 cm−1, HO2• was detected in the 2ν1 vibrational overtone at 6638.2 cm−1, and CH3O2• radicals were detected in the Ã-X˜ electronic transition at 7489.16 cm−1. Pulsed photolysis of different precursors at different wavelengths, always in the presence of O2, was used to generate CH3C(O)O2• and CH3O2• radicals: acetaldehyde (CH3CHO/Cl2 mixture or biacetyle (CH3C(O)C(O)CH3) at 351 nm, and acetone (CH3C(O)CH3) or CH3C(O)C(O)CH3 at 248 nm. From photolysis experiments using CH3C(O)C(O)CH3 or CH3C(O)CH3 as precursor, the rate constant for the self-reaction was found with k1 = (1.3 ± 0.3) × 10−11 cm3s−1, in good agreement with current recommendations, while the rate constant for the cross reaction with CH3O2• was found to be k2 = (2.0 ± 0.4) × 10−11 cm3s−1, which is nearly two times faster than current recommendations. The branching ratio of (R2) towards the radical products was found at 0.67, compared with 0.9 for the currently recommended value. Using the reaction of Cl•-atoms with CH3CHO as precursor resulted in radical profiles that were not reproducible by the model: secondary chemistry possibly involving Cl• or Cl2 might occur, but could not be identified.

Gas-Phase Reaction Kinetics of the Ortho and Ipso Adducts 1,2,4,5-Tetramethylbenzene–OH with O2

The reversible reaction of OH radicals with 1,2,4,5-tetramethylbenzene (1245-TeMB, durene) leads to adducts at the substituted (ipso) and unsubstituted (ortho) positions of the ring. By the use of flash photolysis for production and resonance fluorescence for detection of OH, the gas-phase reactions of O2 with these adducts were investigated over the temperature range of 300–340 K in He at 200 mbar. The decay of OH, generated by pulsed vacuum-UV photolysis of H2O, was monitored under slow-flow conditions in the presence of 1245-TeMB and O2 at concentrations of up to 19 × 1012 cm–3 and 2 × 1016 cm–3, respectively. Triexponential OH decays resulted from the unimolecular decomposition of the two adducts, representing OH reservoirs with different stabilities. In the presence of O2, additional adduct loss pathways exist, leading to faster OH consumption. Triexponential functions fitted to these decays were analyzed to obtain rate constants for the reactions of O2 with both adducts. Rate constants in the range of (4–13) × 10–15 and (0.3–3) × 10–15 cm3 s–1 were obtained for the ortho and the ipso adducts, respectively, depending on temperature and assumptions regarding details of the underlying mechanism of adduct isomer formation and isomerization. At O2 concentrations exceeding about 1 × 1016 cm–3, deviations from a linear dependence of the adduct loss rates on the O2 concentration indicate an even more complex mechanism. The validity of the rate constants is therefore confined to O2 concentrations below 1 × 1016 cm–3. The adduct + O2 rate constants for 1245-TeMB are greater than the corresponding previously obtained rate constants for benzene, toluene, and p- and m-xylene but smaller than those for hexamethylbenzene. The results are discussed in terms of the current knowledge about the mechanism of OH-induced degradation of aromatic compounds in the presence of O2.

Enhanced Photoinduced Electron Transfer Through a Tyrosine Relay in a De Novo Designed Protein Scaffold Bearing a Photoredox Unit and a FeIIS4 Site

AbstractElectron transfer (ET) processes in biology over long distances often proceed via a series of hops, which reduces the distance dependence of the rate of ET. The protein matrix itself can be involved in mediating ET directly through the participation of redox‐active amino acids. We have designed an electron transfer chain incorporated into a de novo protein scaffold, which is capable of photoinduced intramolecular electron transfer between a photoredox unit and a FeIIS4 site through a tyrosine amino acid relay. The kinetics were characterized by nanosecond laser pulse photolysis and revealed that electron transfer from [RuIIIbpymal]3+ proceeds most efficiently via a tyrosine located ∼16 Å from Rubpymal (bpymal=1‐((1‐([2,2′‐bipyridin]‐4‐yl)‐1H‐1,2,3‐triazol‐4‐yl)methyl)‐1H‐pyrrole‐2,5‐dione). Removal of the tyrosine as the electron relay station results in a 20‐fold decrease in the apparent rate constant for the electron transfer.

Experimental and Theoretical Investigations of the Radical-Radical Reaction: N2H3 + NO2.

The N2H3 + NO2 reaction plays a key role during the early stages of hypergolic ignition between N2H4 and N2O4. Here for the first time, the reaction kinetics of N2H3 in excess NO2 was studied in 2.0 Torr of N2 and in the narrow temperature range 298-348 K in a pulsed photolysis flow-tube reactor coupled to a mass spectrometer. The temporal profile of the product, HONO, was determined by direct detection of the m/z +47 amu ion signal. For each chosen [NO2], the observed [HONO] trace was fitted to a biexponential kinetics expression, which yielded a value for the pseudo-first-order rate coefficient, k', for the reaction of N2H3 with NO2. The slope of the plot of k' versus [NO2] yielded a value for the observed bimolecular rate coefficient, kobs, which could be fitted to an Arrhenius expression of (2.36 ± 0.47) × 10-12 exp((520 ± 350)/T) cm3 molecule-1 s-1. The errors are 1σ and include estimated uncertainties in the NO2 concentration. The potential energy surface of N2H3 + NO2 was investigated by advanced ab initio quantum chemistry theories. It was found that the reaction occurs via a complex reaction mechanism, and all of the reaction channels have transition state energies below that of the entrance asymptote. The radical-radical addition forms the N2H3NO2 adducts, while roaming-mediated isomerization reactions yield the N2H3ONO isomers, which undergo rapid dissociation reactions to several sets of distinct products. The RRKM multiwell master equation simulations revealed that the major product channel involves the formation of trans-HONO and trans-N2H2 below 500 K and the formation of NO + NH2NHO above 500 K, which is nearly pressure independent. The pressure-dependent rate coefficients of the product channels were computed over a wide pressure-temperature range, which encompassed the experimental data.

Dynamics of solvated electrons during femtosecond laser-induced plasma generation in water.

We studied the dynamics of solvated electrons in the early stage of plasma generation in water induced with an intense femtosecond laser pulse. According to the decay kinetics of solvated electrons, a fast recombination process of solvated electrons (geminate recombination) occurred with a more prolonged lifetime (500 ps to 1 ns) than that observed in previous pulse photolysis studies (10-100 ps). This unusually longer lifetime is attributed to additional production of solvated electrons due to abundant free electrons generated with the laser-induced plasma, implying significant influence of free electrons on the dynamics of solvated electrons.

Fragmentation of Protonated Dimethylaminoazobenzene during Laser Pulsed Photolysis in a Cryogenic Atmosphere of Rarefied Helium

An analysis is performed for data on the composition of cationic fragments formed during the pulsed photolysis of protonated form of dimethylaminoazobenzene dye in a rarefied helium atmosphere at T ≈ 40 K. It is shown that the interpretation of the mechanism of photolysis, which is based on the traditional representation of this dye as a monomeric azonium cation, is incorrect. An adequate mechanism of the process is obtained using a new concept, according to which the ground state of protonated dimethylaminoazobenzene and its substituted derivatives are rydimers with two protonated amino groups. It was established that the photoexcitation of these rydimers in an atmosphere of rarefied helium results their deprotonation, accompanied by the formation of electrically neutral monomers and monomers with positive charges on sp2 orbitals. Both types of monomers react in a helium atmosphere with released protons, splitting into different cationic fragments. Formulas for the structure of fragments and schemes of monomer fragmentation are presented.

Excitation-Contraction Coupling in the Goldfish (Carassius auratus) Intact Heart.

Cardiac physiology of fish models is an emerging field given the ease of genome editing and the development of transgenic models. Several studies have described the cardiac properties of zebrafish (Denio rerio). The goldfish (Carassius auratus) belongs to the same family as the zebrafish and has emerged as an alternative model with which to study cardiac function. Here, we propose to acutely study electrophysiological and systolic Ca2+ signaling in intact goldfish hearts. We assessed the Ca2+ dynamics and the electrophysiological cardiac function of goldfish, zebrafish, and mice models, using pulsed local field fluorescence microscopy, intracellular microelectrodes, and flash photolysis in perfused hearts. We observed goldfish ventricular action potentials (APs) and Ca2+ transients to be significantly longer when compared to the zebrafish. The action potential half duration at 50% (APD50) of goldfish was 370.38 ± 8.8 ms long, and in the zebrafish they were observed to be only 83.9 ± 9.4 ms. Additionally, the half duration of the Ca2+ transients was also longer for goldfish (402.1 ± 4.4 ms) compared to the zebrafish (99.1 ± 2.7 ms). Also, blocking of the L-type Ca2+ channels with nifedipine revealed this current has a major role in defining the amplitude and the duration of goldfish Ca2+ transients. Interestingly, nifedipine flash photolysis experiments in the intact heart identified whether or not the decrease in the amplitude of Ca2+ transients was due to shorter APs. Moreover, an increase in temperature and heart rate had a strong shortening effect on the AP and Ca2+ transients of goldfish hearts. Furthermore, ryanodine (Ry) and thapsigargin (Tg) significantly reduced the amplitude of the Ca2+ transients, induced a prolongation in the APs, and altogether exhibited the degree to which the Ca2+ release from the sarcoplasmic reticulum contributed to the Ca2+ transients. We conclude that the electrophysiological properties and Ca2+ signaling in intact goldfish hearts strongly resembles the endocardial layer of larger mammals.

The absorption spectrum and absolute absorption cross sections of acetylperoxy radicals, CH3C(O)O2 in the near IR

The Ã-X˜ electronic transition of acetylperoxy radicals (CH3C(O)O2) in the near-infrared was measured at 67hPa synthetic air in the spectral ranges from 6094 cm−1 to 6180 cm−1 and 6420 cm−1 to 6600 cm−1. CH3C(O)O2 radicals were generated by the pulsed photolysis of a acetaldehyde/Cl2/O2 mixture at 351 nm and subsequently measured by time-resolved continuous-wave cavity ring-down spectroscopy (cw-CRDS). The absorption cross sections of eight discrete absorption lines were determined relative to the absorption cross section of HO2, which has previously been reported. The strongest absorption cross section was found at 6510.73 cm−1 and was determined to be (4.9 ± 2.5) × 10−20 cm2.

CH2OO Criegee intermediate UV absorption cross-sections and kinetics of CH2OO + CH2OO and CH2OO + I as a function of pressure.

The UV absorption cross-sections of the Criegee intermediate CH2OO, and kinetics of the CH2OO self-reaction and the reaction of CH2OO with I are reported as a function of pressure at 298 K. Measurements were made using pulsed laser flash photolysis of CH2I2/O2/N2 gas mixtures coupled with time-resolved broadband UV absorption spectroscopy at pressures between 6 and 300 Torr. Results give a peak absorption cross-section of (1.37 ± 0.29) × 10-17 cm2 at ∼340 nm and a rate coefficient for the CH2OO self-reaction of (8.0 ± 1.1) × 10-11 cm3 s-1, with no significant pressure dependence of the absorption cross-sections or the self-reaction kinetics over the range investigated. The rate coefficient for the reaction between CH2OO and I demonstrates pressure dependence over the range investigated, with a Lindemann fit giving k0 = (4.4 ± 1.0) × 10-29 cm6 s-1 and k∞ = (6.7 ± 0.6) × 10-11 cm3 s-1. The origins of IO in the system have been investigated, the implications of which are discussed.

Furodihydroquinolines as Novel Photosensitizers for Photochemotherapy

New derivatives of furodihydroquinoline (FDHQ) with substituents at the 5 position of the benzene ring have been synthesized, and their photophysical and photochemical properties have been studied. The triplet nature of short-lived states generated on photoexcitation of FDHQ has been shown with the use of pulse photolysis and triplet–triplet energy transfer to biscarbocyanine dye. Spectral and kinetic parameters of the triplet states for the synthesized FDHQ have been established. It has been shown that the FDHQ triplet state participates in the formation of the reactive oxygen species (ROS). Processes involving the FDHQ triplet state are important for PUVA-therapy and other processes of photochemotherapy.

Photochemical Processes in Molecular Polymethine Dye Probes in the Presence of Bile Salts

Primary photochemical processes in polymethine dye probes 3,3′-di(γ-sulfopropyl)-4,5,4′,5′-dibenzo-9-ethylthiacarbocyanine betaine (DEC) and 3,3′,9-trimethylthiacarbocyanine iodide (Cyan 2) in micellar systems of bile-acid salts (BASs) sodium cholate, deoxycholate, and taurocholate and sodium dodecyl sulfate (SDS) as a reference are studied by flash photolysis. Signals due to photoisomerization of dye trans-isomers and dark reverse isomerization of the resulting cis-photoisomers are observed during pulse photolysis of air-saturated aqueous dye solutions in the presence of BAS and SDS micelles. The lifetimes of the photoisomers are 60–190 μs. Pulse photolysis of Cyan 2 and DEC solutions without oxygen and with BAS and SDS micelles induced photoisomerization and transition of the dyes into an excited triplet state followed by the reverse transition (intersystem crossing) into the initial singlet state. Triplet–triplet absorption spectra of these dyes isomers in polar (EtOH, i-PrOH) and nonpolar (dioxane) solvents were obtained for comparison using triplet–triplet energy transfer from anthracene. The conclusion was drawn that the photochemical behavior of the dyes in BAS and SDS micellar systems were similar.

Dye-Photosensitized Decomposition of 2-Mercaptobenzothiazole

It has been shown that dyes (eosin, erythrosine, Rose Bengal, fluorescein, Rhodamine C, Rhodamine 6G, 2,7-dichlorofluorescein, Methylene Blue, and Acridine Orange) sensitize the decomposition of 2-mercaptobenzothiazole in aqueous solutions. The quantum yields of photosensitized decomposition of 2-mercaptobenzothiazole depend linearly on the quantum yields of dye triplets. As shown by pulse photolysis, the triplet state of the dyes (eosin, erythrosine, and Rose Bengal) is quenched by 2-mercaptobenzothiazole. A mechanism has been suggested for the photosensitization of 2-mercaptobenzothiazole decomposition by irradiation of the dyes.

Laser‐Mediated Photo‐High‐p,T Intensification of Vitamin D3 Synthesis in Continuous Flow

AbstractA new reactor design for photosynthesis in microflow is presented based on spatial overlap of a laser beam through a capillary tube. A conical Archimedean spiral facilitates exposure of the entire volume of the reaction solution to the irradiation beam. In this fashion, photo‐high‐p,T intensification of the photolysis of 7‐dehydrocholesterol is achieved using either a pulsed ultraviolet (UV) laser excitation (in the order of femtoseconds) alone or in tandem with a conventional UV lamp. The goal is to control the kinetics of the side photoreactions under pulsed photolysis, as well as to reduce the reaction time and enhance the vitamin D3 yield. Three kinds of effects are targeted: a) Utilizing a very large and spatially homogeneous photon flux inside the flowing solution; b) the novel process window of combining photo‐ with thermal intensification to promote the final, irreversible thermal step to vitamin D3; and c) the use of sub‐ps laser pulses to supply excitation energy on a timescale shorter than the formation of side photoproducts. Finally, photo‐processing with the laser alone is compared to the tandem irradiation by the laser‐UV lamp.