Continuous symmetry of C60 fullerene and its derivatives

Conventionally, the Ih symmetry of fullerene C60 is accepted which is supported by numerous calculations. However, this conclusion results from the consideration of the molecule electron system, of its odd electrons in particular, in a close-shell approximation without taking the electron spin into account. Passing to the open-shell approximation has lead to both the energy and the symmetry lowering up to Ci. Seemingly contradicting to a high-symmetry pattern of experimental recording, particularly concerning the molecule electronic spectra, the finding is considered in the current paper from the continuous symmetry viewpoint. Exploiting both continuous symmetry measure and continuous symmetry content, was shown that formal Ci symmetry of the molecule is by 99.99% Ih. A similar continuous symmetry analysis of the fullerene monoderivatives gives a reasonable explanation of a large variety of their optical spectra patterns within the framework of the same C1 formal symmetry exhibiting a strong stability of the C60 skeleton.Comment: 11 pages. 5 figures. 6 table

Entanglement Measures for Single- and Multi-Reference Correlation Effects

Electron correlation effects are essential for an accurate ab initio description of molecules. A quantitative a priori knowledge of the single- or multi-reference nature of electronic structures as well as of the dominant contributions to the correlation energy can facilitate the decision regarding the optimum quantum chemical method of choice. We propose concepts from quantum information theory as orbital entanglement measures that allow us to evaluate the single- and multi-reference character of any molecular structure in a given orbital basis set. By studying these measures we can detect possible artifacts of small active spaces.Comment: 14 pages, 4 figure

Global hybrids from the semiclassical atom theory satisfying the local density linear response

We propose global hybrid approximations of the exchange-correlation (XC) energy functional which reproduce well the modified fourth-order gradient expansion of the exchange energy in the semiclassical limit of many-electron neutral atoms and recover the full local density approximation (LDA) linear response. These XC functionals represent the hybrid versions of the APBE functional [Phys. Rev. Lett. 106, 186406, (2011)] yet employing an additional correlation functional which uses the localization concept of the correlation energy density to improve the compatibility with the Hartree-Fock exchange as well as the coupling-constant-resolved XC potential energy. Broad energetical and structural testings, including thermochemistry and geometry, transition metal complexes, non-covalent interactions, gold clusters and small gold-molecule interfaces, as well as an analysis of the hybrid parameters, show that our construction is quite robust. In particular, our testing shows that the resulting hybrid, including 20\% of Hartree-Fock exchange and named hAPBE, performs remarkably well for a broad palette of systems and properties, being generally better than popular hybrids (PBE0 and B3LYP). Semi-empirical dispersion corrections are also provided.Comment: 12 pages, 4 figure

Comparative Analysis of B-Cell Receptor Repertoires Induced by Live Yellow Fever Vaccine in Young and Middle-Age Donors

Age-related changes can significantly alter the state of adaptive immune system and often lead to attenuated response to novel pathogens and vaccination. In present study we employed 5′RACE UMI-based full length and nearly error-free immunoglobulin profiling to compare plasma cell antibody repertoires in young (19–26 years) and middle-age (45–58 years) individuals vaccinated with a live yellow fever vaccine, modeling a newly encountered pathogen. Our analysis has revealed age-related differences in the responding antibody repertoire ranging from distinct IGH CDR3 repertoire properties to differences in somatic hypermutation intensity and efficiency and antibody lineage tree structure. Overall, our findings suggest that younger individuals respond with a more diverse antibody repertoire and employ a more efficient somatic hypermutation process than elder individuals in response to a newly encountered pathogen

Density functional theory

Density functional theory (DFT) finds increasing use in applications related to biological systems. Advancements in methodology and implementations have reached a point where predicted properties of reasonable to high quality can be obtained. Thus, DFT studies can complement experimental investigations, or even venture with some confidence into experimentally unexplored territory. In the present contribution, we provide an overview of the properties that can be calculated with DFT, such as geometries, energies, reaction mechanisms, and spectroscopic properties. A wide range of spectroscopic parameters is nowadays accessible with DFT, including quantities related to infrared and optical spectra, X-ray absorption and Mössbauer, as well as all of the magnetic properties connected with electron paramagnetic resonance spectroscopy except relaxation times. We highlight each of these fields of application with selected examples from the recent literature and comment on the capabilities and limitations of current methods

Benchmark thermochemistry of the C_nH_{2n+2} alkane isomers (n=2--8) and performance of DFT and composite ab initio methods for dispersion-driven isomeric equilibria

The thermochemistry of linear and branched alkanes with up to eight carbons has been reexamined by means of W4, W3.2lite and W1h theories. `Quasi-W4' atomization energies have been obtained via isodesmic and hypohomodesmotic reactions. Our best atomization energies at 0 K (in kcal/mol) are: 1220.04 n-butane, 1497.01 n-pentane, 1774.15 n-hexane, 2051.17 n-heptane, 2328.30 n-octane, 1221.73 isobutane, 1498.27 isopentane, 1501.01 neopentane, 1775.22 isohexane, 1774.61 3-methylpentane, 1775.67 diisopropyl, 1777.27 neohexane, 2052.43 isoheptane, 2054.41 neoheptane, 2330.67 isooctane, and 2330.81 hexamethylethane. Our best estimates for $\Delta H^\circ_{f,298K}$ are: -30.00 n-butane, -34.84 n-pentane, -39.84 n-hexane, -44.74 n-heptane, -49.71 n-octane, -32.01 isobutane, -36.49 isopentane, -39.69 neopentane, -41.42 isohexane, -40.72 3-methylpentane, -42.08 diisopropyl, -43.77 neohexane, -46.43 isoheptane, -48.84 neoheptane, -53.29 isooctane, and -53.68 hexamethylethane. These are in excellent agreement (typically better than 1 kJ/mol) with the experimental heats of formation at 298 K obtained from the CCCBDB and/or NIST Chemistry WebBook databases. However, at 0 K a large discrepancy between theory and experiment (1.1 kcal/mol) is observed for only neopentane. This deviation is mainly due to the erroneous heat content function for neopentane used in calculating the 0 K CCCBDB value. The thermochemistry of these systems, especially of the larger alkanes, is an extremely difficult test for density functional methods. A posteriori corrections for dispersion are essential. Particularly for the atomization energies, the B2GP-PLYP and B2K-PLYP double-hybrids, and the PW6B95 hybrid-meta GGA clearly outperform other DFT functionals.Comment: (J. Phys. Chem. A, in press

Functionally specialized human CD4+ T-cell subsets express physicochemically distinct TCRs

The organizational integrity of the adaptive immune system is determined by functionally discrete subsets of CD4+ T cells, but it has remained unclear to what extent lineage choice is influenced by clonotypically expressed T-cell receptors (TCRs). To address this issue, we used a high-throughput approach to profile the αβ TCR repertoires of human naive and effector/memory CD4+ T-cell subsets, irrespective of antigen specificity. Highly conserved physicochemical and recombinatorial features were encoded on a subset-specific basis in the effector/memory compartment. Clonal tracking further identified forbidden and permitted transition pathways, mapping effector/memory subsets related by interconversion or ontogeny. Public sequences were largely confined to particular effector/memory subsets, including regulatory T cells (Tregs), which also displayed hardwired repertoire features in the naive compartment. Accordingly, these cumulative repertoire portraits establish a link between clonotype fate decisions in the complex world of CD4+ T cells and the intrinsic properties of somatically rearranged TCRs

Особенности характеристик миокарда пациентов с острым инфарктом миокарда с подъемом сегмента ST и сахарным диабетом по данным магнитно-резонансной томографии сердца с контрастированием

Introduction. The presence of diabetes mellitus in patients with acute infarction significantly worsens short- and long-term prognosis, but the features of the course of the infarction in this category of patients have not been fully studied.Objective. To compare clinical, functional and structural myocardial characteristics of patients with acute ST-segment elevation myocardial infarction with and without diabetes mellitus.Materials and methods. The study included 91 patients with revascularized ST-segment elevation myocardial infarction (41 patients with diabetes mellitus). All patients underwent cardiac MRI with contrast, including myocardial T1 mapping, tissue analysis of left ventricular myocardium with determination of infarct zone, heterogeneous zone, edema zone, pre- and post-contrast T1 values, extracellular volume values of healthy myocardium and infarct zone.Results. The presence of diabetes in patients with AMI was associated with increased EDV LV: 153 ± 38 and 181 ± 58 ml (p = 0.007), increased ESV LV: 76 ml [54–93] and 87 ml [71–122] (p = 0.035). Infarct size was significantly larger in patients with diabetes than in those without diabetes: 37 ± 15 g (95% CI: 33–41) and 47 ± 21 g (95% CI: 40–53), p = 0.017. Patients with acute infarction and diabetes mellitus had higher extracellular volume values in both healthy myocardium: 24% [22–27] and 28% [24–30], p = 0.002, and in the infarct zone: 48% [40–58] and 58% [50–61], p = 0.016.Conclusions. In patients with ST-segment elevation myocardial infarction with diabetes mellitus, the infarct size, the edema area, and the value of the extracellular volume fraction both in the infarct area and in the preserved myocardium were larger than in patients without diabetes, which may underlie the development of myocardial dysfunction and further progression of heart failure.Введение. Наличие сахарного диабета (СД) у пациентов с острым инфарктом миокарда (ОИМ) существенно ухудшает краткосрочный и долгосрочный прогноз, однако особенности течения инфаркта у данной категории пациентов до конца не изучены.Цель. Сравнить клинические, функциональные и структурные характеристики миокарда пациентов с ОИМ с подъемом сегмента ST с СД и без СД.Материалы и методы. В исследование включен 91 пациент с реваскуляризированным острым инфарктом миокарда с подъемом сегмента ST (41 пациент с СД, 50 пациентов без СД). Всем пациентам выполнена МРТ сердца с контрастированием, в том числе Т1-картирование миокарда, проведен тканевой анализ миокарда левого желудочка с определением зоны инфаркта, гетерогенной зоны, зоны отека, значений до- и постконтрастного Т1, фракции внеклеточного объема здорового миокарда и инфарктной зоны.Результаты. Наличие СД у пациентов с ОИМ ассоциировалось с увеличенным конечным диастолическим объемом левого желудочка: 153 ± 38 и 181 ± 58 мл (р = 0,007), увеличенным конечным систолическим объемом левого желудочка: 76 мл [54–93] и 87 мл [71– 122] (р = 0,035). Размер инфаркта у пациентов с СД был достоверно больше, чем у пациентов без СД: 37 ± 15 г (95% ДИ 33–41) и 47 ± 21 г (95% ДИ 40–53), р = 0,017. У пациентов с ОИМ и СД фракция внеклеточного объема была выше и в здоровом миокарде: 24% [22–27] и 28% [24–30], р = 0,002, и в инфарктной зоне: 48% [40–58] и 58% [50–61], р = 0,016.Заключение. У пациентов с инфарктом миокарда с подъемом сегмента ST и СД размер инфаркта, зона отека, а также значение фракции внеклеточного объема как в зоне инфаркта, так и в сохранном миокарде были больше, чем у пациентов без СД, что может лежать в основе развития дисфункции миокарда и дальнейшего прогрессирования сердечной недостаточности