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1.
Iron is one of the most microbiologically and chemically important metals in natural waters. The biogeochemical cycling of iron is significantly influenced by the redox cycling of Fe(II) and Fe(III). Because of the unique chemistry of iron, it is often needed to analyze iron at nano-molar concentrations. This article describes a reverse flow injection analysis (rFIA) based method with ferrozine spectrophotometric detection to quantify total iron concentration in stream water at nanomolar concentrations. The rFIA system has a 0.65 nM detection limit and a linear dynamic range up to 1.40 μM for the total iron analysis. The detection limit was achieved using a 1.0 m long liquid waveguide capillary flow cell, 1.50 m long knotted reaction coil, 87.50 μL injection loop and a miniature fiber optics spectrophotometer. The optimized colorimetric reagent has 1.0 mM ferrozine, 0.1 M ascorbic acid, 1.0 mM citric acid and 0.10 M acetate buffer adjusted to pH 4.0. The best sample flow rate is 2.1 mL min?1 providing a sample throughput of more than 15 samples h?1. The linear dynamic range of the method can be adjusted by changing the volume of the injection loop. The rFIA manifold was assembled exclusively from commercially available components.  相似文献   
2.
采用密度泛函理论B3LYP方法研究了咔咯锰(Ⅴ)氧配合物(MnO corrole)与苯乙烯氧原子转移(oxygen atom transfer,OAT)反应途径和吸电子取代基的影响。计算结果发现氧原子进攻苯乙烯中双键的β碳原子形成过渡态,结合内禀反应坐标法(intrinsic reaction coordinate method,IRC)和最小能量交叉点(minimum-energy crossing point,MECP)计算,给出该反应发生直接氧转移的机理。咔咯大环中位连的吸电子五氟苯基可通过改变锰原子的亲电性,加大取代基与氧原子的静电排斥作用,增加MnO corrole的氧化性。反应能垒随五氟苯基数目的增加而降低,且三重态的反应能垒明显低于单重态。体系可从单重态反应物开始,在MECP处易发生自旋翻转并形成三重态,然后以能量更低的三重态过渡态反应路径进行氧转移反应直至生成产物。  相似文献   
3.
张业文  杨青青  周策峰  李平  陈润锋 《化学进展》2022,34(10):2146-2158
热激活延迟荧光(Thermally activated delayed fluorescence, TADF)材料由于三线态激子可通过反系间窜越(Reverse intersystem crossing, RISC)转换为单线态激子,在有机发光二极管(Organic light-emitting diodes, OLEDs)中理论上可达到100%的激子利用率而被广泛关注。但实验上开发设计高性能TADF材料较为复杂且研究周期较长,理论研究可以从本质上建立材料结构-性能的关系,预测材料的性质并提供一定的分子设计策略。本文围绕高性能TADF材料的开发,从发光原理出发,系统阐述了分子的设计策略及光物理参数如材料单-三线态能级差(Single-triplet energy gap, ΔEST)、系间/反系间窜越速率、吸收/发射光谱、辐射/非辐射速率等的计算原理、计算方法和研究进展。最后我们探讨了TADF材料理论研究面临的机遇和挑战,通过对TADF材料的理论研究综述和研究前景的展望,期待吸引更多的研究工作者,推动该领域的发展和突破。  相似文献   
4.
This paper concentrates on considering the down/up crossing property of weighted Markov collision processes. The joint probability generating function of down crossing and up crossing numbers of weighted Markov collision processes until its extinction are obtained by constructing and studying a related multi-dimensional Markov chain. Hence, the joint probability distribution of down crossing and up crossing numbers and the mean numbers are obtained.  相似文献   
5.
The mechanisms including spin-inversion have been systematically studied for the M+ + OCS → MS+ + CO/MO+ + CS (M denotes a transition metal from Sc to Cu) ion-molecule reactions using the automated reaction path search method. We used the lowest mixed-spin potential energy surface obtained from the diagonalization of the spin-coupled Hamiltonian matrix, whose diagonal elements are taken to be the lowest two spin states. This scheme can effectively locate approximate minimum energy crossing points between the two potential energy surfaces with different spin multiplicities. The spin-orbit couplings at spin-inversion points have been calculated to understand the efficiencies of nonadiabatic transitions. The obtained reaction pathways and the calculated spin-orbit couplings are employed to interpret previous experimental studies.  相似文献   
6.
Ab initio and density functional CCSD(T)-F12/cc-pVQZ-f12//B2PLYPD3/6-311G** calculations have been performed to unravel the reaction mechanism of triplet and singlet methylene CH2 with ketene CH2CO. The computed potential energy diagrams and molecular properties have been then utilized in Rice–Ramsperger–Kassel–Marcus-Master Equation (RRKM-ME) calculations of the reaction rate constants and product branching ratios combined with the use of nonadiabatic transition state theory for spin-forbidden triplet-singlet isomerization. The results indicate that the most important channels of the reaction of ketene with triplet methylene lead to the formation of the HCCO + CH3 and C2H4 + CO products, where the former channel is preferable at higher temperatures from 1000 K and above. In the C2H4 + CO product pair, the ethylene molecule can be formed either adiabatically in the triplet electronic state or via triplet-singlet intersystem crossing in the singlet electronic state occurring in the vicinity of the CH2COCH2 intermediate or along the pathway of CO elimination from the initial CH2CH2CO complex. The predominant products of the reaction of ketene with singlet methylene have been shown to be C2H4 + CO. The formation of these products mostly proceeds via a well-skipping mechanism but at high pressures may to some extent involve collisional stabilization of the CH3CHCO and cyclic CH2COCH2 intermediates followed by their thermal unimolecular decomposition. The calculated rate constants at different pressures from 0.01 to 100 atm have been fitted by the modified Arrhenius expressions in the temperature range of 300–3000 K, which are proposed for kinetic modeling of ketene reactions in combustion. © 2018 Wiley Periodicals, Inc.  相似文献   
7.
The 4f-4f emissions from lanthanide trication (Ln3+) complexes are widely used in bioimaging probes. The emission intensity from Ln3+ depends on the surroundings, and thus, the design of appropriate photo-antenna ligands is indispensable. In this study, we focus on two probes for detecting hydrogen peroxide, for which emission intensities from Tb3+ are enhanced chemo-selectively by the H2O2-mediated oxidation of ligands. To understand the mechanism, the Gibbs free energy profiles of the ground and excited states related to emission and quenching are computed by combining our approximation—called the energy shift method—and density functional theory. The different emission intensities are mainly attributed to different activation barriers for excitation energy transfer from the ligand-centered triplet (T1) to the Tb3+-centered excited state. Additionally, quenching from T1 to the ground state via intersystem crossing was inhibited by intramolecular hydrogen bonds only in the highly emissive Tb3+ complexes. © 2018 Wiley Periodicals, Inc.  相似文献   
8.
9.
Spin–orbit charge-transfer intersystem crossing (SOCT-ISC) is useful for the preparation of heavy atom-free triplet photosensitisers (PSs). Herein, a series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC is prepared. The photophysical properties of the dyads were studied with steady-state and time-resolved spectroscopies. Efficient triplet state formation (quantum yield ΦT=60 %) was observed, with a triplet state lifetime (τT=436 μs) much longer than that accessed with the conventional heavy atom effect (τT=62 μs). The SOCT-ISC mechanism was unambiguously confirmed by direct excitation of the charge transfer (CT) absorption band by using nanosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The factors affecting the SOCT-ISC efficiency include the geometry, the potential energy surface of the torsion, the spin density for the atoms of the linker, solvent polarity, and the energy matching of the 1CT/3LE states. Remarkably, these heavy atom-free triplet PSs were demonstrated as a new type of efficient photodynamic therapy (PDT) reagents (phototoxicity, EC50=75 nm ), with a negligible dark toxicity (EC50=78.1 μm ) compared with the conventional heavy atom PSs (dark toxicity, EC50=6.0 μm, light toxicity, EC50=4.0 nm ). This study provides in-depth understanding of the SOCT-ISC, unveils the design principles of triplet PSs based on SOCT-ISC, and underlines their application as a new generation of potent PDT reagents.  相似文献   
10.
Zinc(II) bis(dipyrrin) complexes, which feature intense visible absorption and efficient symmetry breaking charge transfer (SBCT) are outstanding candidates for photovoltaics but their short lived triplet states limit applications in several areas. Herein we demonstrate that triplet excited state dynamics of bis(dipyrrin) complexes can be efficiently tuned by attaching electron donating aryl moieties at the 5,5′-position of the complexes. For the first time, a long lived triplet excited state (τT=296 μs) along with efficient ISC ability (ΦΔ=71 %) was observed for zinc(II) bis(dipyrrin) complexes, formed via SBCT. The results revealed that molecular geometry and energy gap between the charge transfer (CT) state and triplet energy levels strongly control the triplet excited state properties of the complexes. An efficient triplet–triplet annihilation upconversion system was devised for the first time using a SBCT architecture as triplet photosensitizer, reaching a high upconversion quantum yield of 6.2 %. Our findings provide a blueprint for the development of triplet photosensitizers based on earth abundant metal complexes with long lived triplet state for revolutionary photochemical applications.  相似文献   
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