Study of 256 fiber array biaxial LiDAR optical assembly measurements.

This paper presents a method for measuring the optical assembly results based on multi-beam biaxial LiDAR. This method analyzes the optical assembly parameters of a LiDAR system affecting the LiDAR operation, and an experimental measurement system is built using a collimator to simulate the infinity imaging field. An InGaAs infrared camera is used to take pictures of the laser spot from the LiDAR transmitter and receiver, and then fit the laser spot images with Gaussian equations to calculate the biaxial LiDAR optical assembly results. Finally, the possible effecting factors of LiDAR alignment results are analyzed. This method is experimentally proven to achieve the measurement of the optical assembly results of a large scale multi-beam LiDAR. The possibility of further optimizing the measurement method by shaping the transmit laser is also reported.

Theoretical investigation on the elusive structure-activity relationship of bioinspired high-valence nickel-halogen complexes in oxidative fluorination reactions.

Very recently, bioinspired high-valence metal-halogen complexes have been proven to be competent oxidants in the C-H bond activation and heteroatom dihalogenation reactions. However, the structure-activity relationship of such active species and the reaction mechanisms of oxidations mediated by these oxidants are still elusive. In this study, density functional theory (DFT) calculations were performed to systematically study the oxidizing ability of the high-valence NiIII-X (X = F and Cl) complexes Et4N[NiIII(Cl/F)(L)], (1Cl/F, Et = ethyl, L = N,N'-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamide), such as the reaction mechanism of fluorination of 1,4-cyclohexadiene (CHD) by 1F in the presence of AgF and the reaction mechanism of difluorination of triphenyl phosphine (PPh3) by 1F. All calculated results fit well with the experiments and present new mechanistic findings. The C-H bond activation by the high-valence nickel(III)-halogen complexes was found to proceed via a hydrogen-atom transfer (HAT) mechanism by analysis of the molecular orbitals of the transition states. C-H bond activation by 1F takes a Ni-F-H angle of ca. 180°, whereas that by 1Cl takes an angle of ca. 120° on the transition states. These results indicate that the exchange-enhanced reactivity is responsible for the dramatic oxidative difference between these two oxidants. The role of AgF in C-H fluorination of CHD by 1F is proposed to act as a Lewis acid adduct, AgF-binding Ni(III)-fluorine complex 1F-Ag-F, which acts both as an oxidant in C-H bond activation and as a fluorine donor in the fluorination step. A cooperative oxidation mechanism involving two 1F oxidants was proposed for the difluorination of PPh3 by 1F. These theoretical findings will enrich the knowledge of high-valence metal-halogen chemistry and play a positive role in the rational design of new catalysts.

The chameleon-like nature of elusive cobalt-oxygen intermediates in C-H bond activation reactions.

High-valence metal-oxo (M-O, M = Fe, Mn, etc.) species are well-known reaction intermediates that are responsible for a wide range of pivotal oxygenation reactions and water oxidation reactions in metalloenzymes. Although extensive efforts have been devoted to synthesizing and identifying such complexes in biomimetic studies, the structure-function relationship and related reaction mechanisms of these reaction intermediates remain elusive, especially for the cobalt-oxygen species. In the present manuscript, the calculated results demonstrate that the tetraamido macrocycle ligated cobalt complex, Co(O)(TAML) (1), behaves like a chameleon: the electronic structure varies from a cobalt(III)-oxyl species to a cobalt(IV)-oxo species when a Lewis acid Sc3+ salt coordinates or an acidic hydrocarbon attacks 1. The dichotomous correlation between the reaction rates of C-H bond activation by 1 and the bond dissociation energy (BDE) vs. the acidity (pKa) was rationalized for the first time by different reaction mechanisms: for normal C-H bond activation, the Co(III)-oxyl species directly activates the C-H bond via a hydrogen atom transfer (HAT) mechanism, whereas for acidic C-H bond activation, the Co(III)-oxyl species evolves to a Co(IV)-oxo species to increase the basicity of the oxygen to activate the acidic C-H bond, via a novel PCET(PT) mechanism (proton-coupled electron transfer with a PT(proton-transfer)-like transition state). These theoretical findings will enrich the knowledge of biomimetic metal-oxygen chemistry.

Theoretical Investigation on the Elusive Reaction Mechanism of Spirooxindole Formation Mediated by Cytochrome P450s: A Nascent Feasible Charge-Shift C-O Bond Makes a Difference.

Spirooxindoles are pivotal biofunctional groups widely distributed in natural products and clinic drugs. However, construction of such subtle chiral skeletons is a long-standing challenge to both organic and bioengineering scientists. The knowledge of enzymatic spirooxindole formation in nature may inspire rational design of new catalysts. To this end, we presented a theoretical investigation on the elusive mechanism of the spiro-ring formation at the 3-position of oxindole mediated by cytochrome P450 enzymes (P450). Our calculated results demonstrated that the electrophilic attack of CpdI, the active species of P450, to the substrate, shows regioselectivity, i.e., the attack at the C9 position forms a tetrahedral intermediate involving an unusual feasible charge-shift C9δ+-Oδ- bond, while the attack at the C1 position forms an epoxide intermediate. The predominant route is the first route with the charge-shift bonding intermediate due to holding a relatively lower barrier by >5 kcal mol-1 than the epoxide route, which fits the experimental observations. Such a delocalized charge-shift bond facilitates the formation of a spiro-ring mainly through elongation of the C1-C9 bond to eliminate the aromatization of the tricyclic beta-carboline. Our theoretical results shed profound mechanistic insights for the first time into the elusive spirooxindole formation mediated by P450s.

A modified membrane filtration-ultraviolet photocatalytic system for the removal of trace sulfadiazine in drinking water (No. CHEM77354R1).

In this paper, the membrane filtration-photocatalytic coupling process was used to explore the mechanism and removal effect of trace concentrations of sulfadiazine (SD) in drinking water. First, 8 kinds of ultrafiltration membranes were successfully prepared, and their performance was verified by scanning electron microscopy and measurement of the contact angle, membrane pure water flux, porosity and average pore size. The results showed that the best-performing membranes were the PVDF-PP-TiO2-DA (dopamine) (PPT1D)- and PVDF-PP-TiO2-FeCl3 (PPT2Fe)-modified ultrafiltration membranes, in which TiO2 was modified with DA and FeCl3, forming the cooperation of TiO2/DA and TiO2/Fe3+, with removal rates of 91.4% and 92.6% and quasi-first-order rates of 0.0216 min-1 and 0.0214 min-1. At the same time, the effects of the two types of membrane, UV light and water quality characteristics on the removal performance of the membrane filtration-photocatalytic system were discussed. Among them, the PPT1D membrane was more suitable than the other membranes for the degradation of weakly alkaline water containing SD (pH = 7.5), except when NO3- was present, and the water quality characteristics had a significant inhibitory effect on the removal effect. The PPT2Fe membrane was more suitable for the degradation of acidic water containing SD (pH = 3). Additionally, the water quality characteristics had an obvious inhibitory effect on the removal effect, and the accuracy of the water distribution experimental results was verified by using an actual body of water. In the end, the reaction mechanism of the filtration-photocatalytic system was proposed, and it was found that OH played an indispensable role in the removal of SD.

Removal of sulfadiazine in a modified ultrafiltration membrane (PVDF-PVP-TiO2-FeCl3) filtration-photocatalysis system: parameters optimizing and interferences of drinking water.

The addition of Fe3+ to TiO2 is one of the effective methods to inhibit the recombination of photogenerated electrons and holes and thus improve the photocatalytic activity of TiO2. The effect of PVDF-PVP-TiO2-FeCl3 (PPTFe) membrane filtration-photocatalytic system on the removal of trace concentration of sulfadiazine (SD) in water was evaluated. A two-factor four-level experiment was established to optimize 16 self-made modified membranes. The optimal membrane was then characterized in seven tests (SEM, EDS, membrane pure water flux, contact angle, porosity, mean pore size, ATR-FTIR), resulting in the optimal ratio (PPTFe membrane with 1.2 wt%TiO2 and 0.8 wt%FeCl3). Compared with the original membrane, the pore number, pore size, permeability, and hydrophilicity of the PPTFe membrane were all enhanced. The removal efficiency (92.63%) of SD by PPTFe membrane filtration-photocatalysis system was investigated. The reaction rate (0.0214 min-1) of the removal SD of the system was determined according to the pseudo-first-order kinetic model. The removal performance of membrane type, pH, and water quality parameters (Cl-, SO42-, NO3-, HA) on PPTFe membrane filtration-photocatalytic system were also made a deep inquiry. The results reflected that acidic conditions (pH = 3) were beneficial to SD removal, the presence of Cl-, SO42-, and HA could inhibit SD removal, while the existence of NO3- was unaffected. Furthermore, the removal rate of SD in the actual water body was displayed well in this system. Finally, the possible photocatalytic degradation mechanism was proposed.Graphical abstract.

Ultraviolet trifrequency Rayleigh DWL for stratosphere atmospheric wind measurements during the daytime based on an ultranarrow-bandwidth optical receiver.

An ultranarrow-bandwidth-optical-receiver-based ultraviolet trifrequency Rayleigh Doppler wind lidar (DWL) technology is proposed that is able to simultaneously detect stratospheric wind with high precision during the daytime. The lidar system is designed, and the principle of wind measurement is analyzed. An ultranarrow-bandwidth element used for suppressing strong background light is designed as an important part of the ultranarrow-bandwidth optical receiver. A three-channel Fabry-Perot interferometer (FPI) is capable of measuring wind speed. A non-polarized beam splitter cube optically contacted on the three-channel FPI can offer a stable splitting ratio. The parameters of the three-channel FPI are optimized. The structure and parameters of the ultranarrow-bandwidth element are designed, and the transmission curve is measured. The transmission curve and stability of the three-channel FPI are validated. The background photon number is collected with the ultranarrow-bandwidth element and with an interference filter (IF) alternately from 08:00 to 18:00. Based on the selected system parameters and measured background photon number, the detection performance of the proposed lidar is simulated. Simulation results show that with 200 m range resolution from 15 to 25 km, 500 m range resolution from 25 to 40 km, and 30 min total accumulation time for paired line-of-sight (LOS) measurement, within $\pm {100}\;{\rm m/s}$±100m/s LOS wind speed range, the daytime LOS wind speed error is below 4.77 m/s from 15 to 40 km altitude. Compared with the traditional IF-based dual-FPI Rayleigh Doppler lidar, the wind speed accuracies are improved by 1.29-16.29 times and the detection altitudes are improved from 23.55 to 40 km with the same wind-detecting precision.

Fine gust front structure observed by coherent Doppler lidar at Lanzhou Airport (103°49$

Coherent Doppler lidar (CDL) has long been used to automatically identify gust front-induced wind shear signatures from the velocity data, but rare attention has been given to the fine structure of wind gust fronts. In this work, a compact and robust CDL with high efficiency and accuracy is equipped at Lanzhou Airport (103°49$^{\prime}$'E, 36°03$^{\prime}$'N) to conduct interpretation of wind gust front structures by using high-resolution CDL data. Outflows of gust fronts could be detected reliably from radial velocities, spectral widths, as well as radial shears. For the case study presented here, photographs of the velocity and spectrum width capacitates gust front characteristics such as height, advance speed, and radial shear, as well as vertical structure to be displayed in minute detail. Besides, the quasi-continuous vertical wind reveals the potential turbulent mixing and vertical transport process during the gust front event, which makes CDL a very attractive and essential technique for future development of gust front automatic detection systems.

Elimination of trichloroanisoles by UV/H2O2: Kinetics, degradation mechanism, water matrix effects and toxicity assessment.

The elimination of 2,3,6-trichloroanisole (2,3,6-TCA), which produces a musty-earthy off-odor in water, by an ultraviolet (UV)/H2O2 process was assessed. The removal of 88.1% of 2,3,6-TCA in ultrapure water (UPW) was achieved using an initial 2,3,6-TCA concentration of 1 µg L-1 (4.73 nM), a H2O2 concentration of 20 mg L-1 (0.588 mM), a UV intensity of 1.44 mW cm-2 and a pH of 8.2. The reaction was found to be pseudo first order with a rate constant (kobs) of 0.0340 min-1. Both the removal efficiency and kobs increased significantly upon increasing the H2O2 concentration from 10 to 50 mg L-1. The second order rate constant (kHO·,2,3,6-TCA) in competition kinetic trials was determined to be 8.17 × 107 M-1s-1. Degradation products generated during both the UV photolysis and UV/H2O2 treatment of 2,3,6-TCA solutions were analyzed using ultrahigh resolution gas chromatography/mass spectrometry, and the degradation mechanism was proposed. The toxicities of water solutions during both processes were assessed via a luminescence method in conjunction with Vibrio fischeri. The pH and Cl-, HCO3- and natural organic matter concentrations of the aqueous medium were all found to significantly affect the removal of 2,3,6-TCA. The degradation rates of trichloroanisoles (TCAs) in real-world water samples demonstrated that UV/H2O2 has significant potential with regard to controlling TCAs as pollutants in water.

Novel Lidar algorithm for horizontal visibility measurement and sea fog monitoring.

Traditionally, Klett and Fernald inversion estimates an initial value using the slope method for horizontal visibility, which causes inversion uncertainty. We proposed an algorithm to retrieve the extinction coefficient and visibility distribution information from scanning Lidar to overcome instability due to initial atmospheric extinction coefficient choice and assuming the Lidar ratio. Numerical simulations showed that extinction coefficient maximum relative was much larger for inhomogeneous atmosphere using the Klett method, reaching 0.31. In contrast, it is only 0.049 using the proposed algorithm. Experimental showed that the proposed algorithm and scanning Lidar system provide very high stability and accuracy, can work in different weather conditions and monitor sea fog evolution over real time, and is suitable for various situations with different visibility.