High-Pressure Limit and Pressure-Dependent Rate Rules for ß-Scission Reaction Class of Hydroperoxyl Alkyl Hydroperoxyl Radicals (•P(OOH)2) in Normal-Alkyl Cyclohexanes Combustion.

Chemical kinetic studies of the ß-scission reaction class of hydroperoxyl alkyl hydroperoxyl radicals (•P(OOH)2) from normal-alkyl cyclohexanes are carried out systematically through high-level ab initio calculations. Geometry optimizations and frequency calculations for all species involved in the reactions are performed at the B3LYP/CBSB7 level of theory. Electronic single-point energy calculations are calculated at the CBS-QB3 level of theory. Rate constants for the reactions of ß-scission, in the temperature range of 500-1500 K and the pressure range of 0.01-100 atm, are calculated using transition state theory (TST) and Rice-Ramsberger-Kassel-Marcus/Master-Equation (RRKM/ME) theory taking asymmetric Eckart tunneling corrections and the one-dimensional hindered rotor approximation into consideration. The rate rules are obtained by averaging the rate constants of the representative reactions of this class. These rate rules can greatly assist in constructing more accurate low-temperature combustion mechanisms for normal-alkyl cyclohexanes.

A Theoretical Kinetic Study on Concerted Elimination Reaction Class of Peroxyl-hydroperoxyl-alkyl Radicals (•OOQOOH) in Normal-alkyl Cyclohexanes.

The concerted elimination reaction class of peroxyl-hydroperoxyl alkyl radicals (•OOQOOH) plays a crucial role in the low-temperature combustion of normal-alkyl cyclohexanes. The generation of the relatively unreactive HO2 radicals in this reaction is one of the factors leading to the negative temperature coefficient (NTC) behavior, which hinders the low-temperature oxidation of normal-alkyl cyclohexanes. In this study, 44 reactions are selected and divided into 4 different subclasses according to the nature of the carbon atom where the H atom is eliminated and the reaction center position. Utilizing the CBS-QB3 method, we compute the energy barriers for the concerted elimination reactions of peroxyl-hydroperoxyl alkyl radicals. Following this, we assess both the high-pressure limit and pressure-dependent rate constants for all reactions by applying TST and RRKM/ME theory. These calculations allow for the development of rate rules, which come to fruition through an averaging process involving the rate constants of representative reactions within each subclass. Our work provides accurate rate constants and rate rules for this reaction class, which can aid in constructing more accurate combustion mechanisms for normal-alkyl cyclohexanes.

High-Pressure-Limit and Pressure-Dependent Rate Rules for Unimolecular Reactions Related to Hydroperoxy Alkyl Radicals in Normal Alkyl Cyclohexane Combustion. 1. Concerted HO2 Elimination Reaction Class and ß-Scission Reaction Class.

The reactions of the concerted HO2 elimination from alkyl peroxy radicals and the ß-scission of the C-OOH bond from hydroperoxy alkyl radicals, which lead to the formation of olefins and HO2 radicals, are two important reaction classes that compete with the second O2 addition step of hydroperoxy alkyl radicals, which are responsible for the chain branching in the low-temperature oxidation of normal alkyl cycloalkanes. These two reaction classes are also believed to be responsible for the negative temperature coefficient behavior due to the formation of the relatively unreactive HO2 radical, which has the potential to inhibit ignition of normal alkyl cycloalkanes. In this work, the kinetics of the above two reaction classes in normal alkyl cycloalkanes are studied, where reactions in the concerted elimination class are divided into subclasses depending upon the types of carbons from which the H atom is eliminated and the positions of the reaction center (on the alkyl side chain or on the cycle), and the reactions in the ß-scission reaction class are divided into subclasses depending upon the types of the carbons on which the radical is located and the positions of the reaction center. Energy barriers by using quantum chemical methods at the CBS-QB3 level, high-pressure-limit rate constants by using canonical transition state theory, and pressure-dependent rate constants at pressures from 0.01 to 100 atm by using Rice-Ramsberger-Kassel-Marcus/Master Equation theory are calculated for a representative set of reactions from methyl cyclohexane to n-butyl cyclohexane in each subclass, from which high-pressure-limit rate rules and pressure-dependent rate rules for each subclass are derived from the average rate constants of reactions within each subclass. A comparison of the rate constants for the reactions in the two reaction classes calculated in this work is made with the rate constants of the same reactions from available mechanisms published in the literature, where most of the rate constants are approximately estimated from analogous reactions in alkanes or small alkyl cyclohexanes, and it is found that a large difference may exist between them, indicating that the present work, which provides more accurate kinetic parameters and reasonable rate rules for these reaction classes, can be helpful to construct higher-accuracy mechanism models for normal alkyl cyclohexane combustion.

High-Pressure-Limit and Pressure-Dependent Rate Rules for Unimolecular Reactions Related to Hydroperoxy Alkyl Radicals in Normal-Alkyl Cyclohexane Combustion. 2. Cyclization Reaction Class.

The hydroperoxy alkyl radicals are important intermediates in the low-temperature combustion for normal-alkyl cycloalkanes, and the cyclization reactions of hydroperoxy alkyl radicals to form cyclic ethers are responsible for a major fraction of the OH formation, which has the potential to promote ignition. In most of the previous modeling studies for normal-alkyl cycloalkane combustion, the kinetic data of the cyclization reactions in the detailed combustion mechanism were mainly taken from the analogous reactions in cyclohexane, methyl cyclohexane, and alkanes in published literature studies. In this work, the kinetics of the cyclization reaction class of hydroperoxy alkyl radicals in normal-alkyl cycloalkanes is studied, where the reaction class is divided into subclasses depending upon the ring size of the transition states, the types of the carbons on which the -OOH site is located and the types of the carbons on which the radical site is located, and the positions of the cyclization (on the alkyl side chain, on the cycle, or between the alkyl side chain and the cycle). Energy barriers and high-pressure-limit site rate constants and pressure-dependent rates for reactions in all subclasses are calculated, and rate rules for all subclasses are developed. The high-pressure-limit rate constants are determined from CBS-QB3 electronic structure calculations combined with canonical transition-state theory calculations, and pressure-dependent rate constants are calculated by using the Rice-Ramsberger-Kassel-Marcus/Master Equation theory at pressures varying from 0.01 to 100 atm. Comparisons of the rate constants for cyclization reactions of hydroperoxy alkyl cyclohexylperoxy radicals calculated in this work with the values of the corresponding reactions in some of the popular combustion mechanisms show that it is unreasonable to use the kinetic data of analogous reactions in alkanes, cyclohexanes, or smaller normal-alkyl cyclohexanes. Therefore, the accurate kinetic calculations and the construction of rate rules for normal-alkyl cycloalkanes are necessary and significant for the reliable modeling of the low-temperature combustion of normal-alkyl cyclohexanes.

[Knowledge and attitude of clinical interns on pain management].

OBJECTIVE: To investigate clinical interns' knowledge and attitude on pain management, influential factors and requirement.
 METHODS: A total of 212 clinical interns were investigated by the self-designed general condition questionnaire and the Chinese version of the knowledge and attitude survey regarding pain (KASRP).
 RESULTS: The correct answer rate for the knowledge and attitude questionnaire was (51.70±14.18)%. The education background, the condition of pain education in clinical practice and the use of pain assessment tools were the key factors that impact the scores of knowledge and attitude on pain management.
 CONCLUSION: Clinical interns' perception on pain management is insufficient. It cannot meet the clinical actual needs. The medical colleges are lack of pain management education courses and standardization training. Schools and hospitals are encouraged to offer and strengthen pain education for clinical interns to create a good environment for pain treatment and to improve the management level for patients' quality of life.

Unraveling the atmospheric oxidation mechanism and kinetics of naphthalene: Insights from theoretical exploration.

Naphthalene, the most abundant polycyclic aromatic hydrocarbon in the atmosphere, significantly influences OH consumption and secondary organic aerosol (SOA) formation. Naphthoquinone (NQ) is a significant contributor to ring-retaining SOA from naphthalene degradation, impacting the redox properties and toxicity of ambient particles. However, inconsistencies persist regarding concentrations of its isomers, 1,2-NQ and 1,4-NQ. In present work, our theoretical investigation into naphthalene's reaction with OH and subsequent oxygenation unveils their role in SOA formation. The reaction kinetics of initial OH and subsequent O2 oxidation was extensively studied using high-level quantum chemical methods (DLPNO-CCSD(T)/aug-ccpVQZ//M052x-D3/6-311++G(d,p)) combined with RRKM/master equation simulations. The reactions mainly proceed through electrophilic addition and abstraction from the aromatic ring. The total rate coefficient of naphthalene + OH at 300 K and 1 atm from our calculation (7.2 × 10-12 cm3 molecule-1 s-1) agrees well with previous measurements (∼1 × 10-11 cm3 molecule-1 s-1). The computed branching ratios facilitate accurate product yield determination. The largest yield of 1-hydroxynaphthalen-1-yl radical (add1) producing the major precursor of RO2 is computed to be 93.8 % in the ambient environment. Our calculated total rate coefficient (5.2 × 10-16 cm3 molecule-1 s-1) for add1 + O2 closely matches that of limited experimental data (8.0 × 10-16 cm3 molecule-1 s-1). Peroxy radicals (RO2) generated from add1 + O2 include 4-cis/trans-(1-hydroxynaphthalen-1-yl)-peroxy radical (add1-4OOadd-cis/trans, 66.0 %/17.5 %), 2-cis/trans-(1-hydroxynaphthalen-1-yl)-peroxy radical (add1-2OOadd-cis/trans, 10.3 %/6.3 %). Regarding the debated predominance of 1,4-NQ (corresponding to the parent RO2, i.e., add1-4OOadd-cis/trans) and 1,2-NQ (corresponding to the parent RO2, i.e., add1-2OOadd-cis/trans) in the atmosphere, our findings substantiate the dominance of 1,4-NQ. This study also indicates potential weakening of 1,4-NQ's dominance due to competition from decomposition reactions of add1-4OOadd-cis/trans and add1-2OOadd-cis/trans. Precise reaction kinetics data are essential for characterizing SOA transformation derived from naphthalene and assessing their climatic impacts within modeling frameworks.

The integrated impact of GDP growth, industrialization, energy use, and urbanization on CO2 emissions in developing countries: Evidence from the panel ARDL approach.

Developing economies are an important engine of world economic growth. However, ensuring the quality of environmental assets is maintained amid rapid economic change remains a major challenge for most developing countries. Using the Panel Autoregressive Distributed Lag (ARDL) approach and the heterogeneous causality test, this study analyzes the combined effects of energy usage, industrialization, gross domestic product (GDP) growth, and urbanization on CO2 emissions for 23 developing countries across the 1995 to 2018 period. From our analysis, the long-run results reveal that a 1% increase in energy use, economic growth, industrialization, and urbanization increases CO2 emissions by 0.23%, 0.17%, 0.54%, and 2.32%, respectively. Moreover, our model's short- to long-term equilibriums are adjusted at a yearly rate of 0.19%. Finally, to verify the panel ARDL long-run results, robustness tests were carried out using the Fully Modified Ordinary Least Squares (FMOLS) and Dynamic Ordinary Least Squares (DOLS) approaches. Our results confirm that in the case of developing countries, CO2 emissions are primarily influenced by GDP growth, energy use, industrialization, and urbanization. Furthermore, the panel causality analysis identified a bidirectional causal relationship between energy use, GDP growth, urbanization, industrialization, and CO2 emissions. While these results can play an instrumental role in formulating CO2 emission policies among our selected countries, our research can also assist policy makers and stakeholders in other developing economies implement important policy initiatives. These include, tax incentives and infrastructural developments that nurture environmentally friendly industrialization, deploy low-carbon technologies, promote sustainable forms of urbanization and urban planning, while also facilitating increases in both the investment in and adoption of renewable energy platforms. The establishment of such a comprehensive policy agenda can help emerging economies achieve strong and environmentally sustainable GDP growth over the long-term.

A Velvet Transcription Factor Specifically Activates Mating through a Novel Mating-Responsive Protein in the Human Fungal Pathogen Cryptococcus deneoformans.

Sexual reproduction facilitates infection by the production of both a lineage advantage and infectious sexual spores in the ubiquitous human fungal pathogen Cryptococcus deneoformans. However, the regulatory determinants specific for initiating mating remain poorly understood. Here, we identified a velvet family regulator, Cva1, that strongly promotes sexual reproduction in C. deneoformans. This regulation was determined to be specific, based on a comprehensive phenotypic analysis of cva1Δ under 26 distinct in vitro and in vivo growth conditions. We further revealed that Cva1 plays a critical role in the initiation of early mating events, including sexual cell-cell fusion, but is not important for the late sexual development stages or meiosis. Thus, Cva1 specifically contributes to mating activation. Importantly, a novel mating-responsive protein, Cfs1, serves as the key target of Cva1 during mating, since its absence nearly blocks cell-cell fusion in C. deneoformans and its sister species C. neoformans. Together, our findings provide insight into how C. deneoformans ensures the regulatory specificity of mating. IMPORTANCE The human fungal pathogen C. deneoformans is a model organism for studying fungal sexual reproduction, which is considered to be important to infection. However, the specific regulatory determinants for activation of sexual reproduction remain poorly understood. In this study, by combining transcriptomic and comprehensive phenotypic analysis, we identified a velvet family regulator Cva1 that specifically and critically elicits early mating events, including sexual cell-cell fusion. Significantly, Cva1 induces mating through the novel mating-responsive protein Cfs1, which is essential for cell-cell fusion in C. deneoformans and its sister species C. neoformans. Considering that Cva1 and Cfs1 are highly conserved in species belonging to Cryptococcaeceae, they may play conserved and specific roles in the initiation of sexual reproduction in this important fungal clade, which includes multiple human fungal pathogens.

Regulatory basis for reproductive flexibility in a meningitis-causing fungal pathogen.

Pathogenic fungi of the genus Cryptococcus can undergo two sexual cycles, involving either bisexual diploidization (after fusion of haploid cells of different mating type) or unisexual diploidization (by autodiploidization of a single cell). Here, we construct a gene-deletion library for 111 transcription factor genes in Cryptococcus deneoformans, and explore the roles of these regulatory networks in the two reproductive modes. We show that transcription factors crucial for bisexual syngamy induce the expression of known mating determinants as well as other conserved genes of unknown function. Deletion of one of these genes, which we term FMP1, leads to defects in bisexual reproduction in C. deneoformans, its sister species Cryptococcus neoformans, and the ascomycete Neurospora crassa. Furthermore, we show that a recently evolved regulatory cascade mediates pre-meiotic unisexual autodiploidization, supporting that this reproductive process is a recent evolutionary innovation. Our findings indicate that genetic circuits with different evolutionary ages govern hallmark events distinguishing unisexual and bisexual reproduction in Cryptococcus.

Predicting prognosis in patients with stroke treated with intravenous alteplase through the 24-h trajectory of blood pressure changes.

Blood pressure (BP) monitored within 24 h from the beginning of intravenous thrombolysis (IVT) with alteplase, is one of the important factors affecting the prognosis of patients with acute ischemic stroke (AIS). This study aimed to explore longitudinal BP trajectory patterns and determine their association with stroke prognosis after thrombolysis. From November 2018 to September 2019, a total of 391 patients were enrolled consecutively during the study period, and 353 patients were ultimately analyzed. Five systolic (SBP) and four diastolic blood pressure (DBP) trajectory subgroups were identified. The regression analysis showed that when compared with the rapidly moderate stable group, the continuous fluctuation-very high level SBP group (odds ratio [OR]: 2.743, 95% confidence interval [CI]: 1.008-7.467) was associated with early neurological deterioration (END). Both the rapid drop-high level SBP (OR: 0.448, 95% CI: 0.219-0.919) and DBP groups (OR: 0.399, 95% CI: 0.219-0.727) were associated with early neurological improvement (ENI). Moreover, there was a U-shaped correlation between the OR value of SBP trajectory group and favorable outcome (the modified Rankin Scale [mRS] score 0-2) at 3 months: the slow drop-low level SBP group represent a well-established unfavorable outcome risk factor (OR:5.239, 95% CI: 1.271-21.595), and extremely high SBP-the continuous fluctuation-very high level SBP group, are equally associated with elevated unfavorable outcome risk (OR:3.797, 95% CI: 1.486-9.697). The continuous fluctuation-very high level DBP group was statistically significant in mRS (OR: 3.387, CI: 1.185-9.683). The BP trajectory groups show varying clinical features and risk of neurological dysfunction. The findings may help identify potential candidates for clinical BP monitoring, control, and specialized care.

Dihydromyricetin Attenuates TNF-α-Induced Endothelial Dysfunction through miR-21-Mediated DDAH1/ADMA/NO Signal Pathway.

Accumulating studies demonstrate that dihydromyricetin (DMY), a compound extracted from Chinese traditional herb, Ampelopsis grossedentata, attenuates atherosclerotic process by improvement of endothelial dysfunction. However, the underlying mechanism remains poorly understood. Thus, the aim of this study is to investigate the potential mechanism behind the attenuating effects of DMY on tumor necrosis factor alpha- (TNF-α-) induced endothelial dysfunction. In response to TNF-α, microRNA-21 (miR-21) expression was significantly increased in human umbilical vein endothelial cells (HUVECs), in line with impaired endothelial dysfunction as evidenced by decreased tube formation and migration, endothelial nitric oxide synthase (eNOS) (ser1177) phosphorylation, dimethylarginine dimethylaminohydrolases 1 (DDAH1) expression and metabolic activity, and nitric oxide (NO) concentration as well as increased asymmetric dimethylarginine (ADMA) levels. In contrast, DMY or blockade of miR-21 expression ameliorated endothelial dysfunction in HUVECs treated with TNF-α through downregulation of miR-21 expression, whereas these effects were abolished by overexpression of miR-21. In addition, using a nonspecific NOS inhibitor, L-NAME, also abrogated the attenuating effects of DMY on endothelial dysfunction. Taken together, these data demonstrated that miR-21-mediated DDAH1/ADMA/NO signal pathway plays an important role in TNF-α-induced endothelial dysfunction, and DMY attenuated endothelial dysfunction induced by TNF-α in a miR-21-dependent manner.