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Photodegradation of Fluoxetine Applying Different Photolytic Reactors: Evaluation of the Process Efficiency and Mechanism
摘要： Photolytic degradation of fluoxetine (FLX), a medicine commonly known as Prozac?, was evaluated by using different photochemical processes. The ultraviolet/microwave (UV/MW) process showed higher efficiency in all the aspects evaluated in this study. The energy consumption was equivalent to 1.94 × 10-4 kW h mg-1 L (UV/MW), while in the UV process the value was 1.20 × 10-2 kW h mg-1 L. The degradation kinetics were applied to the FLX, with rate constant (k) = 0.15 ± 0.01 min-1 and linear correlation coefficient (R2) = 0.980 for UV, and k = 6.15 ± 0.08 min-1 and R2 = 0.998 for UV/MW. The FLX degradation of 99.16% (UV/MW 5 min) and 98.90% (UV 120 min) were observed, evidencing higher efficiency for the first process. The monitoring of transformation products (TPs) through chromatographic analysis enabled the identification of 9 TPs, proving that for the UV/MW process, the hydroxylated structures are verified in high quantity.
关键词： photolysis,fluoxetine,transformation products,photochemical reactor,kinetics
更新于2025-11-19 16:56:35
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Photolysis of PCl <sub/>3</sub> /POCl <sub/>3</sub> with Oxygen Dopant Using 193?nm ArF Excimer at Low Temperatures: Oxygen Insertion through ‘Phosphadioxirane’ Pathway
摘要： Photolysis was performed on PCl3 and POCl3 in the presence of oxygen dopant in Ar matrix at low temperatures using 193 nm ArF excimer laser. The photo irradiation initially facilitated the formation of ozone in situ in the low temperature matrix. For PCl3 + O2 photolysis with 193 nm ArF excimer, initially POCl3 was produced and subsequent oxygen atom insertion on POCl3 generated PO2Cl3. Furthermore, secondary reaction channel opens up in PCl3 + O2 photolysis to form a variety of photoproducts such as POCl, PIIIO2Cl, PVO2Cl and PO3Cl. The insertion of oxygen atom on POCl through phosphadioxirane intermediate generated PIIIO2Cl and the direct oxygen atom addition resulted in PVO2Cl. A successive oxygen insertion on PVO2Cl triggered the PO3Cl generation. The identification of all the photoproducts was confirmed through 18O2 isotopic experiments and quantum chemical computations performed using density functional theory (DFT). Computations carried out at B3LYP level of theory with 6–311 + + G(d,p) basis set were used to correlate the structure of photo products obtained experimentally. Interestingly, photo irradiation of POCl3 with oxygen dopant in Ar matrix @193 nm ArF excimer resulted in the generation of PO2Cl3, PO3Cl3 and PO4Cl3 photo products by a sequential insertion of oxygen atoms through phosphadioxirane intermediate. A compelling evidence for the passage of the reaction through phosphadioxirane intermediate is established through 18O2 isotopic substitution experiments.
关键词： DFT computations,matrix isolation,infrared spectroscopy,photolysis,phosphadioxirane intermediate
更新于2025-09-23 15:23:52
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A radiative transfer module for calculating photolysis rates and solar heating in climate models: Solar-J v7.5
摘要： Solar-J is a comprehensive radiative transfer model for the solar spectrum that addresses the needs of both solar heating and photochemistry in Earth system models. Solar-J is a spectral extension of Cloud-J, a standard in many chemical models that calculates photolysis rates in the 0.18–0.8 μm region. The Cloud-J core consists of an eight-stream scattering, plane-parallel radiative transfer solver with corrections for sphericity. Cloud-J uses cloud quadrature to accurately average over correlated cloud layers. It uses the scattering phase function of aerosols and clouds expanded to eighth order and thus avoids isotropic-equivalent approximations prevalent in most solar heating codes. The spectral extension from 0.8 to 12 μm enables calculation of both scattered and absorbed sunlight and thus aerosol direct radiative effects and heating rates throughout the Earth’s atmosphere. The Solar-J extension adopts the correlated-k gas absorption bins, primarily water vapor, from the shortwave Rapid Radiative Transfer Model for general circulation model (GCM) applications (RRTMG-SW). Solar-J successfully matches RRTMG-SW’s tropospheric heating profile in a clear-sky, aerosol-free, tropical atmosphere. We compare both codes in cloudy atmospheres with a liquid-water stratus cloud and an ice-crystal cirrus cloud. For the stratus cloud, both models use the same physical properties, and we find a systematic low bias of about 3 % in planetary albedo across all solar zenith angles caused by RRTMG-SW’s two-stream scattering. Discrepancies with the cirrus cloud using any of RRTMG-SW’s three different parameterizations are as large as about 20–40 % depending on the solar zenith angles and occur throughout the atmosphere. Effectively, Solar-J has combined the best components of RRTMG-SW and Cloud-J to build a high-fidelity module for the scattering and absorption of sunlight in the Earth’s atmosphere, for which the three major components – wavelength integration, scattering, and averaging over cloud fields – all have comparably small errors. More accurate solutions with Solar-J come with increased computational costs, about 5 times that of RRTMG-SW for a single atmosphere. There are options for reduced costs or computational acceleration that would bring costs down while maintaining improved fidelity and balanced errors.
关键词： solar heating,clouds,Cloud-J,climate models,radiative transfer,photolysis rates,scattering,aerosols,RRTMG-SW,Solar-J
更新于2025-09-23 15:22:29
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Solar photodegradation of oxytetracycline in brackish aquaculture water: New insights about effects of Ca2+ and Mg2+
摘要： Oxytetracycline (OTC) is an antibiotic used in aquaculture able to complex with the major cations Ca2+ and Mg2+, existing in brackish water. The effects of these cations on the solar photodegradation of OTC have been investigated. Calcium promotes a faster OTC photo-degradation in aqueous solution, while the same does not occur with Mg2+. For some authors the accelerating effect of Ca2+ is attributed to the occurrence of self-sensitized photodegradation of the complexes with Ca2+, which is not possible in the complexes with Mg2+, due to different binding patterns of these cations. In this work, the controversy concerning the binding sites of these cations in OTC is discussed. Based on spectroscopic evidence, similar binding patterns of OTC with Ca2+ and Mg2+ and a lower quantum yield of the direct photolysis of the complexes with Mg2+ are proposed. In addition, it was demonstrated that Mg2+ inhibits the formation of some OTC photoproducts observed in the presence of Ca2+, while at least two new OTC photoproducts are formed in the presence of Mg2+.
关键词： Photoproducts,Complexes,Quantum yields,Antibiotic,Photolysis,Spectroscopy
更新于2025-09-23 15:22:29
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Highly efficient removal of phosphonates from water by a combined Fe(III)/UV/co-precipitation process
摘要： Considerable amount of phosphorous is present as organic phosphonates (usually in the form of metal complexes, e.g., Ca(II)-phosphonate) in domestic and industrial effluents, which cannot be effectively removed by traditional processes for phosphate. Herein, we employed a proprietary process, i.e., Fe(III) displacement/UV irradiation/co-precipitation (denoted Fe(III)/UV/NaOH), to enable an efficient removal of Ca(II)-phosphonate complexes from water. The combined process includes three basic steps, i.e., Fe(III) replacement with the complexed Ca(II) to form Fe(III)-phosphonate of high photo-reactivity, UV-mediated degradation of Fe(III)-phosphonate to form phosphate and other intermediates, and the final phosphorous removal via co-precipitation at pH=6. The operational conditions for the combined process to remove a typical phosphonate Ca(II)-NTMP (nitrilotrismethylenephosphonate) are optimized, where ~60% NTMP is transformed to phosphate with the total phosphorous reduction from 1.81 mg/L to 0.17 mg/L. Under UV irradiation, the cleavage of NTMP is identified at the C-N and C-P bonds to form the intermediate products and phosphate in sequence. Also, the combined process is employed for treatment of two authentic effluents before and after activated sludge treatment, resulting in the phosphorous drop from 4.3 mg/L to 0.23 mg/L and from 0.90 mg/L to 0.14 mg/L respectively, which is much superior to other processes including Fenton/co-precipitation. In general, the combined process exhibits great potential for efficient removal of phosphonates from contaminated waters.
关键词： Photolysis,Fe(III) replacement,Advanced treatment,Phosphonates
更新于2025-09-23 15:22:29
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Ketone derivatives as photoinitiators for both radical and cationic photopolymerizations under visible LED and application in 3D printing
摘要： Six ketones (abbreviated as ketones 1-6) varying by the substitution pattern of the central cyclohexanones and the choice of the peripheral groups (thiophene or furane) were synthesized and proposed as unprecedented visible light sensitive photoinitiators, in combination with an amine and an iodonium salt, for the free radical polymerization of acrylates upon LED irradiation at 405 nm. For the photopolymerization of acrylates carried out as thin samples in laminate, all these ketones showed high photoinitiating abilities. Conversely, when tested as photoinitiators for thick samples, compared to the other 4 ketones, ketone 3 and ketone 5 both based onpiperidin-4-one as the central core and comprising furanes as peripheral groups proved to be the most efficient photoinitiators. Notably, the highest final polymerization conversion of Ebecryl 40, a tetrafunctional polyether acrylate, could be obtained using these two photoinitiators. The high photoreactivity of ketone 3 was highlighted by the steady state photolysis experiments. Meanwhile, ketone 3 could also promote the cationic polymerization of epoxides upon LED irradiation at 405 nm, in the presence of an iodonium salt. Interestingly, some 3D patterns could also be fabricated by free radical polymerization of Ebecryl 40 while using the ketone 3-based photoinitiating system.
关键词： free radical polymerization,ketones,cyclohexanone,photolysis,3D printing,cationic polymerization,LED,photoinitiating system
更新于2025-09-23 15:21:01
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Rapid Generation of Hierarchically Porous Metal-Organic Frameworks through Laser Photolysis
摘要： Hierarchically porous metal–organic frameworks (HP-MOFs) facilitate mass transfer due to mesoporosity while preserving the advantage of microporosity. This unique feature endows HP-MOFs with remarkable application potential in multiple fields. Recently, new methods such as the construction of HP-MOFs have emerged. To further enrich the synthetic toolkit of MOFs, we report a controlled photolytic removal of linkers to create mesopores within microporous MOFs at tens of milliseconds. Ultraviolet (UV) laser has been applied to eliminate “photolabile” linkers without affecting the overall crystallinity and integrity of the original framework. Presumably, the creation of mesopores can be attributed to the missing-cluster defects, which can be tuned through varying the time of laser exposure and ratio of photolabile/robust linkers. Upon laser exposure, MOF crystals shrank while metal oxide nanoparticles formed giving rise to the HP-MOFs. In addition, photolysis can also be utilized for the fabrication of complicated patterns with high precision, paving the way towards MOF lithography, which has enormous potential in sensing and catalysis.
关键词： linker photolysis,metal-organic frameworks,hierarchical pores
更新于2025-09-23 15:21:01
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Rapid Generation of Hierarchically Porous Metal-Organic Frameworks through Laser Photolysis
摘要： Hierarchically porous metal–organic frameworks (HP-MOFs) facilitate mass transfer due to mesoporosity while preserving the advantage of microporosity. This unique feature endows HP-MOFs with remarkable application potential in multiple fields. Recently, new methods such as the construction of HP-MOFs have emerged. To further enrich the synthetic toolkit of MOFs, we report a controlled photolytic removal of linkers to create mesopores within microporous MOFs at tens of milliseconds. Ultraviolet (UV) laser has been applied to eliminate “photolabile” linkers without affecting the overall crystallinity and integrity of the original framework. Presumably, the creation of mesopores can be attributed to the missing-cluster defects, which can be tuned through varying the time of laser exposure and ratio of photolabile/robust linkers. Upon laser exposure, MOF crystals shrank while metal oxide nanoparticles formed giving rise to the HP-MOFs. In addition, photolysis can also be utilized for the fabrication of complicated patterns with high precision, paving the way towards MOF lithography, which has enormous potential in sensing and catalysis.
关键词： linker photolysis,metal-organic frameworks,hierarchical pores
更新于2025-09-23 15:21:01
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Mechanism of the Laser Flash Photolysis of Rydimeric e-Tautomers of 4-N,N-Diethylaminoazobenzene in a 2-Propanol Medium
摘要： Difference transit absorption spectra (TASes) obtained via flash photolysis of isopropanol solutions of 4-N,N-diethylaminoazobenzene (DEAB) using 15 ns laser pulses at wavelengths of λex = 265 and 353 nm are analyzed. The inconsistency of constructing the mechanism of trans (t) → cis (c) photisomerization of DEAB based on the concept of this dye having a monomeric structure is shown. Based on the rydimeric concept of aminoazobenzene dyes, which include Rydberg dimers DEAB2, an adequate explanation is given of the nature of TAS signals with structures that change dramatically when in wavelength λex is altered. TAS signals of DEAB2 are compared to ultrahigh-speed (subpico- and pico-second) TAS signals of rydimers of a reference aminoazobenzene (AAB2) dye. It is established that the main difference between the structures of DEAB2 TAS signals generated by pulses with indicated wavelengths λex is due to the excitation of various rydimeric e-tautomers. In addition, a rydimeric e-tautomer that is unstable in the ground state acquires increased stability in propanol and, by absorbing radiation with λex = 353 nm, alters the structure of one of its monomers to quinoid while remaining a rydimer. It is shown that when excited with radiation pulses at λex = 265 nm, a rydimeric e-tautomer (which is more stable in the ground state) dissociates into individual monomers, one of which isomerizes to form cis-DEAB molecules.
关键词： diethylaminoazobenzene rydimers,rydimer photonics,laser flash photolysis,trans–cis isomerization,visible laser spectroscopy
更新于2025-09-23 15:21:01
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From micro to macro-contaminants: The impact of low-energy titanium dioxide photocatalysis followed by filtration on the mitigation of drinking water organics
摘要： This study evaluated strategies targeting macro- and micro-organic contaminant mitigation using low-energy titanium dioxide photocatalysis. Energy inputs of 1, 2, and 5 kWh m-3 resulted in incomplete oxidation of macro-organic natural organic matter, signified by greater reductions of UV254 and specific ultraviolet UV absorbance (SUVA) in comparison to dissolved organic carbon (DOC). The rate of UV254 removal was 3 orders of magnitude greater than the rate of DOC degradation. Incomplete oxidation improved operation of downstream filtration processes. Photocatalysis at 2 kWh m-3 increased the bed life of downstream granular activated carbon (GAC) filter by 340% relative to direct filtration pretreatment. Likewise, photocatalysis operated ahead of microfiltration decreased fouling, resulting in longer filter run times. Using 2 kWh m-3 photocatalysis increased filter run time by 36 times in comparison to direct filtration. Furthermore, levels of DOC and UV254 in the membrane permeate improved (with no change in removal across the membrane) using low-energy photocatalysis pretreatments. While high-energy UV inputs provided high levels of removal of the estrogenic micro-organics estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethynlestradiol (EE2), low-energy photocatalysis did not enhance removal of estrogens beyond levels achieved by photolysis alone. In the cases of E1 and E3, the addition of TiO2 as a photocatalyst reduced degradation rates of estrogens compared to UV photolysis. Overall, process electrical energy per order magnitude reductions (EEOs) greatly improved using photocatalysis, versus photolysis, for the macro-organics DOC, UV254, and SUVA; however, energy required for removal of estrogens was similar between photolysis and photocatalysis.
关键词： granular activated carbon (GAC),estrogens,UV photolysis,dissolved organic carbon (DOC),advanced oxidation process (AOP),natural organic matter (NOM)
更新于2025-09-23 15:21:01