Fe-Catalyzed Three-Component Coupling Reaction of α,ß,γ,δ-Unsaturated Carbonyl Compounds and Conjugate Dienes with Alkylsilyl Peroxides and Nucleophiles.

An Fe(OTf)2-catalyzed three-component coupling reaction of α,ß,γ,δ-unsaturated carbonyl compounds with alkylsilyl peroxides in the presence of certain heteronucleophiles (ROH and indole) is realized under mild reaction conditions. A variety of α,ß,γ,δ-diene carbonyl substrates with different substituents were successfully employable via combination with several different alkylsilyl peroxides. This new approach is also applicable to the double functionalization of diene substrates.

TDDFT study on aluminum and fluoride dual-sensing mechanism of a Schiff-Base sensor.

The aluminum and fluoride dual-sensing mechanism of a previously reported sensor with a Schiff-base moiety (Spectrochim. Acta A, 2017, 183, 267-274) has been investigated by density functional theory (DFT) and time-dependent DFT (TDDFT) methods. The present calculations reproduce the photoproperties of the sensor as well as its aluminum and fluoride complexes, which illustrates that DFT and TDDFT constitute a reliable tool for uncovering detailed fluorescence-based sensing mechanisms in diverse electronic states. Theoretical results indicate that there are two OH⋯N hydrogen bonds in the sensor and two OH⋯F hydrogen bonds in its F¯ complex. Different degrees of coplanarity caused by these hydrogen bonds are responsible for their distinct absorption wavelengths. However, excited-state geometry optimization and a scan of the potential-energy surface show that there is twisted intramolecular charge transfer about the CN bond in the sensor molecule and an excited-state proton-transfer process from the fluoride anion to the neighboring N atom in the fluoride-sensor complex, whereby the fluorescence is quenched. A chelation-enhanced fluorescence effect associated with the aluminum-sensor complex shows a different excited-state process. The local excitation and emission occur exclusively within the planar fluorophore, and negligible structural change upon excitation of the aluminum-sensor complex leads to its strong fluorescence. Therefore, it is theoretically explained why the sensor may be successfully used to analyze the fluoride anion by absorption spectroscopy and the aluminum cation by emission spectroscopy.

Study of one-step photosynthesis of Ag nanoparticles.

During photosynthesis of metal nanoparticles (NPs) in aromatic ketone systems, the aromatic ketone triplets are explored as hydrogen atom/electron abstractors which yield highly reactive radicals. However, their electron donation ability is sparsely recognized. Here we report the investigations of benzophenone (BP)-initiated one-step photosynthesis of Ag NPs in H donor free system using spectroscopic and theoretical methods. Experimentally, the direct observations of BP cation radical (BP+·) and Ag NPs via transit and steady-state absorption spectroscopy demonstrate the electron donation ability of BP triplets which directly reduce Ag+ to Ag0. In the following reactions, both theoretical calculation and experimental results reveal that the generated BP+· recovers itself to BP by grabbing an electron from NO3- and the generated nitrate radicals (NO3·) then decay to nitrogen oxides. Notably, BP plays a role as photocatalyst in our system. This study details the mechanism of one-step photosynthesis of Ag NPs which provides a new insight of aromatic ketones in photochemistry and may offer a facile approach to photosynthesis of metal NPs.

[Further study on possibility of diffusion of Oncomelania hupensis with water in river channels of the east route of South-to-North Water Diversion Project].

OBJECTIVE: To study the drifting law of floats and potential risks of Oncomelania hupensis diffusion in the water diversion rivers of the east route of South-to-North Water Diversion Project. METHODS: The O. hupensis snails in the river channels were monitored by the salvage method and snail luring method with rice straw curtains, and the diffusion possibility of snails along with water was assessed through the drift test of floats with GPS. RESULTS: In the flood seasons from 2006 to 2013, totally 8 338.0 kg of floats were salvaged, and 2 100 rice straw curtains were put into water in the Li Canal and Jinbao shipping channel, but no Oncomelania snails were found. The drift test of floats with GPS before water diversion showed that the flow velocity on water surface (northbound) was 0.45 m/s, the average drift velocity of the floats was 0.56 - 0.60 m/s, and the average drift distances each time were 999.70 - 1 995.50 m in the Gaoshui River section, while there were no obvious drift in Jinbao shipping channel section. During the water diversion period, the flow velocity on water surface (northbound) was 0.45 m/s, the average drift velocity of the floats was 0.35 - 0.41m/s, and the average drift distances each time were 1 248.06 -1 289.44 m in the Gaoshui River, while in Jinbao shipping channel section, the flow velocity on water surface was 0.28 m/s, the average drift velocity of the floats was 0.25 - 0.27 m/s, and the average drift distances each time were 477.76 - 496.38 m. The drift test showed that the floats gradually closed to the river bank as affected by water flow, wind direction and ship waves, when blocked by the reeds, water plants or other obstacles, and they would stopped and could not continue to drift without outside help. CONCLUSIONS: There are no Oncomelania snails found in the river channels of the east route of South-to-North Water Diversion Project. The drifting distance of the floating debris along with the water is restricted by the flow rate and shore environment.

Formation of hydroxyl radical from the photolysis of salicylic acid.

Photodissociation dynamics of salicylic acid (SA) in the gas phase at different photolysis wavelengths (266, 315-317 nm) is investigated by probing the nascent OH photoproduct employing the single-photon laser-induced fluorescence (LIF) technique. At all the photolysis wavelengths it is found that the nascent OH radicals are produced mostly in a vibrationally ground state (υ'' = 0) and have similar rotational state distributions. The two spin-orbit and Λ-doublet states of the OH fragment formed in the dissociation are measured to have a nonstatistical distribution at each photolysis wavelength. The LIF signal of the OH could be observed upon photolysis at 317 nm but not at 317.5 nm. The threshold of OH formation from SA photodissociation is estimated to be 98.2 ± 0.9 kcal/mol. The effect of the phenolic OH group on the dissociation of SA is discussed.

OH produced from o-nitrophenol photolysis: a combined experimental and theoretical investigation.

Photodissociation dynamics of o-nitrophenol in the gas phase at different photolysis wavelengths (361-390 nm) is investigated, and the nascent OH radical is observed by the single-photon laser-induced fluorescence technique. At all the photolysis wavelengths, the OH radicals are formed in vibrationally cold state (upsilon(")=0) and have similar rotational state distributions. The average rotational temperature for all the photolysis wavelengths is approximately 970+/-120 K, corresponding to a rotational energy of 1.9+/-0.2 kcal mol(-1). The spin orbit and Lambda-doublet states of the OH fragments formed in the dissociation are measured to have nonstatistical distributions. To get an insight into the dissociative mechanism leading to OH formation in the photolysis of o-nitrophenol, the potential energy surfaces of the OH-forming channels are mapped by ab initio theoretical calculations. According to both experimental and theoretical results, a possible mechanism for OH formation is proposed.

Photolysis of o-nitrobenzaldehyde in the gas phase: a new OH* formation channel.

Photolysis of gaseous o-nitrobenzaldehyde (o-NBA) with selected different excitation wavelengths (355-400 nm) is investigated, and the nascent OH radical is detected by the single-photon laser-induced fluorescence (LIF) technique. The relative quantum yield and rotational excitation of OH formation are found to be dependent on the excitation energy. The distributions of rotational, spin-orbit, and Lambda-doublet states are obtained at 355-400 nm by analyzing the experimental data. The OH radicals are found to be vibrationally cold at all photolysis wavelengths. The spin-orbit and Lambda-doublet states have nonstatistical distributions. To understand the dissociative process involved in the OH-generating channel, DFT calculations are performed. Based on both experimental and theoretical results, possible photolysis channels of o-NBA leading to the OH fragment are proposed and discussed.

Dynamics of OH formation in the photodissociation of o-nitrobenzoic acid at 295 and 355 nm.

Photodissociation dynamics of o-nitrobenzoic acid at 295 and 355 nm is studied by probing the nascent OH photoproduct employing the single-photon laser-induced fluorescence technique. At both of the photolysis wavelengths, the OH fragments are found to be vibrationally cold but have different rotational state distributions. Upon photolysis at 295 nm, the relative population of OH in different rotational states does not follow the Boltzmann equilibrium distribution, whereas upon photolysis at 355 nm, a Boltzmann distribution is observed with a rotational temperature of 1010 +/- 100 K. Between the two spin-orbit states, (2)Pi(3/2) and (2)Pi(1/2), the former is found to be preferentially populated, and the distribution of the Pi(A') state for the Lambda-doublet is dominant at both of the wavelengths studied. Several possible dissociation pathways of o-nitrobenzoic acid leading to formation of the OH fragment are investigated computationally. On the basis of the theoretical and experimental studies, a possible mechanism of OH formation from the photodissociation of o-nitrobenzoic acid at 295 and 355 nm is proposed.

OH fragment from benzoic acid monomer photolysis: threshold and product state distribution.

Photodissociation dynamics of benzoic acid monomer (BAM) at different ultraviolet excitation wavelengths (280-295 nm) has been investigated. The nascent OH product state distributions were measured using the laser-induced fluorescence (LIF) technique. The rotational state distributions, the Lambda-doublet-state ratio, and spin-orbit state distributions of the OH fragment were also measured at 280-294 nm. The OH fragments are vibrationally cold, and their rotational state distributions are peaked at J'' = 3.5 at each photolysis wavelength. No LIF signal of OH fragments was observed at 295 nm. The photodissociation threshold is determined to be 102.5-103.9 kcal/mol for OH channel. The dissociative state and mechanism have been discussed for OH produced from the photodissociation of BAM.