Thermochemical Properties (Δ_f<i>H</i>°(298 K), <i>S</i>°(298 K), <i>C_p</i>(<i>T</i>)) and Bond Dissociation Energies for C1–C4 Normal Hydroperoxides and Peroxy Radicals

Structure and thermochemical properties of the normal hydroperoxides, C_<i>n</i>H_2<i>n</i>+1OOH (1 ≤ <i>n</i> ≤ 4), and corresponding peroxy radicals, C_<i>n</i>H_2<i>n</i>+1OO·(1 ≤ <i>n</i> ≤ 4), are determined by density functional M06-2X, multilevel G4, composite CBS-QB3, and CBS-APNO level calculations. Unique to this study is that the Δ_f<i>H</i>°₂₉₈ values are determined using several isodesmic reactions which utilize experimental standard enthalpy data for CH₃OOCH₃ and CH₃CH₂OOCH₂CH₃ as reference species, where previous studies used atomization or work reactions with alcohols or other nonperoxide species. The <i>S</i>°₂₉₈ and <i>C_p</i>(<i>T</i>) (300 ≤ <i>T</i>/K ≤ 1500) from vibration, translation, and external rotation contributions are calculated based on the vibration frequencies and structures obtained from the density functional study. Potential barriers for the internal rotations are calculated at B3LYP/6-31+G­(d,p) level, the hindered internal rotation contributions to <i>S</i>°₂₉₈ and <i>C_p</i>(<i>T</i>) are calculated using direct integration over energy levels of the internal rotational potentials. The results show the following Δ_f<i>H</i>°₂₉₈ values (units in kcal mol^–1): CH₃OOH (−31.0), CH₃CH₂OOH (−39.0), CH₃CH₂CH₂OOH (−44.0), CH₃CH₂CH₂CH₂OOH (−48.9),CH₃OO· (2.4), CH₃CH₂OO· (−6.2), CH₃CH₂CH₂OO· (−11.4), and CH₃CH₂CH₂CH₂OO· (−16.6). Bond dissociation energies for the R–OOH, RO–OH, ROO–H, R–OOj, and RO–Oj bonds are reported. The enthalpy values from the use of experimental data as a reference show very good agreement and support the data obtained from calculation methods. They should be used for reference values. Entropy and heat capacity values show good agreement with the calculation literature. The standard entropies for butyl hydroperoxide, propyl peroxy, and butyl peroxy are corrected

Thermochemical Properties and Bond Dissociation Energies for Fluorinated Methanol, CH_3–<i>x</i>F_<i>x</i>OH, and Fluorinated Methyl Hydroperoxides, CH_3–<i>x</i>F_<i>x</i>OOH: Group Additivity

Oxygenated fluorocarbons are routinely found in sampling of environmental soils and waters as a result of the widespread use of fluoro and chlorofluoro carbons as heat transfer fluids, inert materials, polymers, fire retardants and solvents; the influence of these chemicals on the environment is a growing concern. The thermochemical properties of these species are needed for understanding their stability and reactions in the environment and in thermal process. Structures and thermochemical properties on the mono- to trifluoromethanol, CH_3–<i>x</i>F_<i>x</i>OH, and fluoromethyl hydroperoxide, CH_3–<i>x</i>F_<i>x</i>OOH (1 ≤ <i>x</i> ≤ 3), are determined by CBS-QB3, CBS-APNO, and G4 calculations. Entropy, <i>S</i>°₂₉₈, and heat capacities, <i>C_p</i>(<i>T</i>)’s (300 ≤ <i>T</i>/K ≤ 1500) from vibration, translation, and external rotation contributions are calculated on the basis of the vibration frequencies and structures obtained from the B3LYP/6-31+G­(d,p) density functional method. Potential barriers for the internal rotations are also calculated from this method and used to calculate hindered rotor contributions to <i>S</i>°₂₉₈ and <i>C_p</i>(<i>T</i>)’s using direct integration over energy levels of the internal rotational potentials. Standard enthalpies of formation, Δ_f<i>H</i>°₂₉₈ (units in kcal mol^–1) are CH₂FOOH (−83.7), CHF₂OOH (−138.1), CF₃OOH (−193.6), CH₂FOO^• (−44.9), CHF₂OO^• (−99.6), CF₃OO^• (−153.8), CH₂FOH (−101.9), CHF₂OH (−161.6), CF₃OH (−218.1), CH₂FO^• (−49.1), CHF₂O^• (−97.8), CF₃O^• (−150.5), CH₂F^• (−7.6), CHF₂^• (−58.8), and CF₃^• (−112.6). Bond dissociation energies for the R–OOH, RO–OH, ROO–H, R–OO^•, RO–O^•, R–OH, RO–H, R–O^•, and R–H bonds are determined and compared with methyl hydroperoxide to observe the trends from added fluoro substitutions. Enthalpy of formation for the fluoro-hydrocarbon oxygen groups C/F/H₂/O, C/F₂/H/O, C/F₃/O, are derived from the above fluorinated methanol and fluorinated hydroperoxide species for use in Benson’s Group Additivity. It was determined that fluorinated peroxides require interaction terms O/CH₂F/O, O/CHF₂/O, and O/CF₃/O, as opposed to the common (O/C/O) group in hydrocarbons, resulting from interactions of the peroxide oxygen with the fluorines. Hydrogen bond dissociation increment (HBI) groups are also developed

Thermochemical Properties Enthalpy, Entropy, and Heat Capacity of C1–C4 Fluorinated Hydrocarbons: Fluorocarbon Group Additivity

Enthalpies of formation for 14 C2–C4 fluorinated hydrocarbons were calculated with nine popular ab initio and density functional theory methods: B3LYP, CBS-QB3, CBS-APNO, M06, M06-2X, ωB97X, G4, G4­(MP2)-6X, and W1U via several series of isodesmic reactions. The recommended ideal gas phase Δ<i>H</i>_<i>f</i>298^° (kcal mol^–1) values calculated in this study are the following: −65.4 for CH₃CH₂F; −70.2 for CH₃CH₂CH₂F; −75.3 for CH₃CHFCH₃; −75.2 for CH₃CH₂CH₂CH₂F; −80.3 for CH₃CHFCH₂CH₃; −108.1 for CH₂F₂; −120.9 for CH₃CHF₂; −125.8 for CH₃CH₂CHF₂; −133.3 for CH₃CF₂CH₃; −166.7 for CHF₃; −180.5 for CH₃CF₃; −185.5 for CH₃CH₂CF₃; −223.2 for CF₄; and −85.8 for (CH₃)₃CF. Entropies (<i>S</i>₂₉₈^° in cal mol^–1 K^–1) were estimated using B3LYP/6-31+G­(d,p) computed frequencies and geometries. Rotational barriers were determined and hindered internal rotational contributions for <i>S</i>₂₉₈^°, and <i>C</i>_<i>p</i>(<i>T</i>) were calculated using the rigid rotor harmonic oscillator approximation, with direct integration over energy levels of the intramolecular rotation potential energy curve. Thermochemical properties for the fluorinated carbon groups C/C/F/H₂, C/C₂/F/H, C/C/F₂/H, C/C₂/F₂, and C/C/F₃ were derived from the above target fluorocarbons. Previously published enthalpies and groups for 1,2-difluoroethane, 1,1,2-trifluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,2-pentafluoroethane, 2-fluoro-2-methylpropane that were previously determined via work reaction schemes are revised using updated reference species values. Standard deviations are compared for the calculation methods

Study on essential drug use status and its influencing factors among cerebral infarction inpatients in county level hospitals of Anhui Province, China

<div><p>Background and purpose</p><p>Drug costs is one of the main components of hospitalization expenditure for cerebral infarction inpatients. In China, the National Essential Medicine System (NEMS) was created to relieve the heavy drug-cost burden for patients. The objective of this study was to investigate essential drug-use status and its influencing factors among cerebral infarction inpatients in county-level hospitals of Anhui province, China.</p><p>Methods</p><p>Three county-level hospitals were selected through a multi-stage cluster random sampling method. The hospitalization cost data of cerebral infarction inpatients in the three hospitals were extracted from the Anhui provincial information platform of the New Rural Cooperative Insurance System (NCMS), and whether the proportion of essential drug cost in the total drug cost reached the median value of 33.05% which was set as the evaluation index for essential drug-use status. Questionnaires for hospitals and physicians were designed and given to them to assess influencing factors.</p><p>Results</p><p>We retrieved the cost data of 2,189 inpatients from the NCMS platform and investigated 51 corresponding physicians in total. The drug costs accounted for 52.6% of the total hospitalization cost, and essential drug costs alone accounted for 37.0% of the total drug costs. The essential drug-cost proportion was high among physicians with a higher recognition degree on NEMS, older age, lower final academic degree, longer work experience and lower professional title. Married physicians and those with tight organizational affiliation also prescribed more essential drugs.</p><p>Conclusions</p><p>Increasing the proportion of essential drugs was an effective way to reduce the disease burden for cerebral infarction patients. Perfecting the NEMS, increasing government investment, reinforcing education and propaganda, and formulating relevant incentive and restrictive mechanisms were all effective ways to promote and increase the number of essential drug prescriptions written by physicians.</p></div

Additional file 2 of The expression pattern of immune-related genes and characterization of tumor immune microenvironment: predicting prognosis and immunotherapeutic effects in cutaneous melanoma

Additional file 2: Supplementary Figure 2. The correlation of IRGscore with tumor mutation burden

Additional file 1 of The expression pattern of immune-related genes and characterization of tumor immune microenvironment: predicting prognosis and immunotherapeutic effects in cutaneous melanoma

Additional file 1: Supplementary Figure 1. The workflow of this study and consensus matrixes of screened genes

General and relevant business data of the three hospitals in 2015.

<p>General and relevant business data of the three hospitals in 2015.</p

Multifactor analysis of the elements that affected essential drug cost proportion.

<p>Multifactor analysis of the elements that affected essential drug cost proportion.</p

Physician’s recognition score on the supporting degree from patients, hospitals, government to the EMS and its effect.

<p>Physician’s recognition score on the supporting degree from patients, hospitals, government to the EMS and its effect.</p

A new data assimilation method for high-dimensional models

<div><p>In the variational data assimilation (VarDA), the typical way for gradient computation is using the adjoint method. However, the adjoint method has many problems, such as low accuracy, difficult implementation and considerable complexity, for high-dimensional models. To overcome these shortcomings, a new data assimilation method based on dual number automatic differentiation (AD) is proposed. The important advantages of the method lies in that the coding of the tangent-linear/adjoint model is no longer necessary and that the value of the cost function and its corresponding gradient vector can be obtained simultaneously through only one forward computation in dual number space. The numerical simulations for data assimilation are implemented for a typical nonlinear advection equation and a parabolic equation. The results demonstrate that the new method can reconstruct the initial conditions of the high-dimensional nonlinear dynamical system conveniently and accurately. Additionally, the estimated initial values can converge to the true values quickly, even if noise is present in the observations.</p></div