ABSTRACT
In this study, the reactivity of organochalcogen compounds toward a representative alkyl-lead bond compound under light was investigated in detail. Under light irradiation, the Cy-Pb bond of Cy6Pb2 (Cy = cyclohexyl) undergoes homolytic cleavage to generate a cyclohexyl radical (Cyâ¢). This radical can be successfully captured by diphenyl diselenide, which exhibits excellent carbon-radical-capturing ability. In the case of (PhS)2 and (PhTe)2, the yields of the corresponding cyclohexyl sulfides and tellurides were lower than that of (PhSe)2. This probably occurred due to the low carbon-radical-capturing ability of (PhS)2 and the high photosensitivity of the cyclohexyl-tellurium bond.
ABSTRACT
This study describes the syntheses of 2,3-bis(selanyl)quinoxalines via the photoinduced cyclizations of o-diisocyanoarenes with diaryl or dialkyl diselenides, in addition to providing a detailed discussion of the corresponding mechanism and revealing that the developed procedure can also be applied to prepare 2-thiolated quinoxaline derivatives from o-diisocyanoarenes and thiols. The developed technique does not need the use of additives or metal catalysts and features the advantages of a high conversion, a broad substrate scope, and mild reaction conditions, thereby rendering it a valuable addition to the quinoxaline synthesis toolbox.
ABSTRACT
The photoinduced reactions of tetraphenyldiphosphine disulfide with a range of organic dichalcogenides successfully afforded a series of phosphorus(V)-chalcogen interelement compounds via a radical process. The relative reactivities of the organic dichalcogenides (i.e., (PhS)2, (PhSe)2, and (PhTe)2) toward the PIII or PV groups in the diphosphine analogues under light were investigated in detail, and a convenient method was developed to form P-S or P-Se interelement compounds from tetraphenyldiphosphine disulfide and (PhS)2 or (PhSe)2 upon photoirradiation. Furthermore, the relative photochemical properties and reactivities of tetraphenyldiphophine (P-P interelement compound) and its analogues toward photoinduced radical addition reactions were also discussed. The formed P-E (E = S, Se) interelement compounds could be utilized for ionic reactions, and they could be transformed into various phosphine reagents via one-pot processes.
ABSTRACT
Using tetraaryllead compounds (PbAr4) as arylating reagents, isocyanides undergo selective diarylation in the presence of palladium catalysts such as Pd(OAc)2 or Pd(PPh3)4 to afford imines and/or α-diimines based on the isocyanide employed. With aliphatic isocyanides, imines are obtained preferentially, whereas α-diimines are formed in the case of electron-rich aromatic isocyanides. The differences in imine/α-diimine selectivity can be attributed to the stability of imidoylpalladium intermediates formed in this catalytic reaction. Compared with other arylating reagents, tetraaryllead compounds are excellent candidates for use in the selective transformations to imines and/or α-diimines, especially in terms of inhibiting the oligomerization of isocyanides, which results in a lower product selectivity in many transition-metal-catalyzed reactions of isocyanides.
ABSTRACT
Human error is an important factor leading to nuclear power plant (NPP) accidents. Human reliability analysis (HRA) is considered an effective method to reduce human error. Therefore, this article proposes a method to quantify human reliability based on the standardized plant analysis risk-human reliability analysis (SPAR-H) method. Firstly, the method used the performance shaping factors of SPAR-H to build a human reliability model. Secondly, the triangular fuzzy number was used to quantify the qualitative information of root nodes, and the fuzzy IF-THEN rule was used to determine the prior probability distribution of intermediate nodes. Finally, Bayesian reasoning was used to quantify human reliability based on the human reliability model. The result of the developed method is consistent with the result of cognitive reliability and error analysis methods (CREAM). The developed method can be used as a tool to quantify human reliability in the NPP system.
Subject(s)
Nuclear Power Plants , Humans , Bayes Theorem , Reproducibility of Results , ProbabilityABSTRACT
The transition-metal-catalyzed diarylation of isocyanides with triarylbismuthines was investigated in detail, and rhodium catalysts such as [RhCl(nbd)]2 were found to selectively afford N-alkyl diaryl ketimines. On the other hand, palladium-catalyzed diarylation proceeded with the incorporation of two molecules of isocyanide, preferentially yielding N,N'-dialkyl or N,N'-diaryl α-diimines. In addition, a cascade synthesis of 2,3-diarylquinoxalines starting from the palladium-catalyzed diarylation of isocyanides with triarylbismuthines was successfully achieved.
ABSTRACT
Developing an early warning model to predict the driver's mental workload (MWL) is critical and helpful, especially for new or less experienced drivers. The present study aims to investigate the correlation between new drivers' MWL and their work performance, regarding the number of errors. Additionally, the group method of data handling is used to establish the driver's MWL predictive model based on subjective rating (NASA task load index [NASA-TLX]) and six physiological indices. The results indicate that the NASA-TLX and the number of errors are positively correlated, and the predictive model shows the validity of the proposed model with an R2 value of 0.745. The proposed model is expected to provide a reference value for the new drivers of their MWL by providing the physiological indices, and the driving lesson plans can be proposed to sustain an appropriate MWL as well as improve the driver's work performance.
Subject(s)
Automobile Driving/psychology , Task Performance and Analysis , Workload/psychology , Adolescent , Attention , Blinking/physiology , Fixation, Ocular , Heart Rate , Humans , Male , Mental Processes/physiology , Pupil/physiology , Simulation Training , Students/psychology , Young AdultABSTRACT
We examined the effect of a single 120 s of exposure to +3Gz (head-to-foot inertial forces) centrifugation as orthostatic stress on cerebral oxygenation (oxy-Hb) and cerebral blood volume (CBV) changes in response to stand test, in order to relate the occurrence of altered cerebral oxygenation control to any increase in sympathetic activity. Frontal near-infrared spectroscopy and mean arterial blood pressure at brain level (MAPbrain) were recorded in 14 subjects in supine and then in standing (10 min) position, before and after +3Gz centrifugation. The decrease in oxy-Hb (-7 +/- 5 a.u. versus -27 +/- 4 a.u., P<0.001) and in CBV (-6 +/- 10 a.u. versus -15 +/- 8 a.u., P<0.05) upon standing was more important after +3Gz centrifugation, with unchanged MAPbrain (-8 +/- 8 mmHg versus -3 +/- 11 mmHg). Upon standing, the high-frequency component of heart rate was lower (1090 +/- 460 ms2 versus 827 +/- 412 ms2, P<0.05) after +3Gz centrifugation. These findings suggest a downward shift in the static cerebral autoregulatory curve. We conclude that cerebral vasoconstriction might have occurred without centrally mediated increase in the entire peripheral sympathetic activity of the body.
Subject(s)
Brain/blood supply , Cerebrovascular Circulation/physiology , Gravitation , Hypotension, Orthostatic/physiopathology , Stress, Physiological/physiopathology , Adult , Blood Flow Velocity , Blood Pressure/physiology , Electrocardiography , Electroencephalography , Electromyography , Functional Laterality/physiology , Heart Rate/physiology , Hemoglobins/metabolism , Humans , Male , Middle Aged , Spectroscopy, Near-Infrared/methodsABSTRACT
The aim of the present experiment was to study the influence of +Gz acceleration (head-to-foot inertial forces) onset on cerebral oxygenation changes (cerebral oxy- and deoxy-hemoglobin) and cerebral blood volume (CBV) in order to evaluate the role of cerebral hypoxemia and ischemia in the appearance of +Gz-induced loss of consciousness (G-LOC). We used five rhesus monkeys which were equipped with near infrared spectroscopy optodes fixed onto the parietooccipital cranial bone. G-LOC (isoelectric electrocorticogram) was detected with silver balls electrodes in contact with the dura matter. The animals were centrifuged up to +12 Gz with two onset rates (0.1 and 3 G/s). Cerebral deoxy-hemoglobin increased significantly (max: +30 +/- 6% of control, P < 0.01) only during the 0.1 G/s run. At G-LOC, CBV changes were not related to G-onset rate (P = 0.30; mean change: -32 +/- 6% of control). We conclude that cerebral ischemia is the main mechanism in the occurrence of G-LOC.