АКТУАЛЬНЫЕ ПРОБЛЕМЫ КАЧЕСТВА ХИМИЧЕСКОГО АНАЛИЗА

Analytical chemistry and its three segments: fundamental science, chemical analysis and analytical control are associated with the determination of the chemical composition, which must be performed with the required accuracy. Inaccurate or erroneous results of chemical analysis can lead to negative and sometimes tragic consequences. The accuracy of the results is an integral part and a consequence of a whole range of measures to assure the quality of chemical analysis. Current article discusses the main elements of the quality system of chemical analysis and the current trends in solving urgent problems in this area. The first stage of the analytical process requires a clear understanding and documentation of the requirements on the part of the customer. A particular attention is paid to the contribution to the analysis uncertainty of the sampling. The principle of choosing an analytical method is considered, which is based on the type of sample, matrix, measured value etc. Approaches to the validation or certification of the methods and / or their verifications are generalized. It is shown that the basis for the validation of chemical analysis methods is the assessment of uncertainty. It is noted that this is not only a formalized procedure, but also methodologically competent support of the research process of developing an analysis method in terms of cleaning the analytical signal, ways to identify and eliminate sources of its distortion, and the choice of approaches to constructing the calibration dependencies and standard samples. Attention is drawn to the problem of the current state of education in analytical chemistry.Keywords: chemical analysis, quality, metrological traceability, uncertainty, reference materials. DOI: http://dx.doi.org/10.15826/analitika.2021.25.4.005Vasilisa Borisovna Baranovskaya1, Maria Yurievna Medvedevskikh2,  Yury Alexandrovich Karpov1 1Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,Leninskij prospect, 31, Moscow, 119991, Russian Federation2Ural Scientific Research Institute for Metrology - Affiliated branch of the D.I. Mendeleyev Institute for Metrology, 4, Krasnoarmeyskaya str., Ekaterinburg,  620075, Russian FederationАналитическая химия и ее три сегмента (фундаментальная наука, химический анализ и аналитический контроль) связаны  с определением химического состава, которое должно быть выполнено с необходимой точностью. Неточные или ошибочные результаты химического анализа способны привести к негативным, а порой и трагическим последствиям. Точность результатов является неотъемлемой частью и следствием целого комплекса мероприятий по обеспечению качества химического анализа. В данной статье рассмотрены основные элементы системы качества химического анализа и современные тенденции в решении актуальных проблем этой области. Жизненный цикл аналитического процесса охватывает этапы от постановки задачи химического анализа до ее реализации. На первом этапе необходимо четкое понимание и документирование требований со стороны заказчика, наличие ресурсов, наличие методов, устранение всех неясностей и непонимания до начала работ. Особое внимание в статье уделено вкладу в неопределенность анализа стадии пробоотбора. Чтобы этот этап не искажал значимо конечный результат, процедура пробоотбора должна быть детально описана и метрологически оценена. Рассмотрен принцип выбора аналитического метода, который опирается на: вид пробы, матрицу и измеряемую величину; используемое оборудование; пределы обнаружения и границы определяемых содержаний; селективность; потенциальные метрологические характеристики; продолжительность; стоимость и др. Обобщены подходы к валидации  или аттестации методик и/или ее верификации в зависимости от задач, связанных с разработкой нестандартной методики или модификацией стандартизованной. Показано, что основой валидации методик химического анализа является оценка неопределенности. Отмечено, что это не только формализованная процедура, но и методически грамотное сопровождение научно-исследовательского процесса разработки метода анализа в части  очистки аналитического сигнала, способов выявления и устранения источников его искажения,  выбора подходов к построению градуировочных зависимостей, стандартных образцов. Обращено внимание на проблему текущего состояния образования в области аналитической химии.Ключевые слова. Химический анализ, качество, метрологическая прослеживаемость, неопределенность, стандартные образцыDOI: http://dx.doi.org/10.15826/analitika.2021.25.4.00

Heat Treatment Condition Influence on Novokuibyshevsk Vacuum Residue Component Composition

The article presents the information about thermal degradation of Novokuibyshevsk vacuum residue and change of products composition during this process. The optimal conditions for the thermal destruction of vacuum residue components were established. The regularities of material balance composition change, Sgeneral were determined depending on cracking conditions. The basic directions of resin-asphaltene component transformations were identified, changes in their structural-group parameters in the process of initiated cracking were analyzed. Conducting of Novokuibyshevsk vacuum residue thermolysis leads to deep resins-asphaltenes average molecules structure characteristic changes. Developed alkyl and naphthenic moieties, which are presented in initial molecule, undergo degradation, amount of structural blocks in resins and asphaltenes molecules reduces, their average size decreases. Also the reduction in total content of the rings (saturated and aromatic) was established in average structural unit, at the same time decrease of rings substitution and length of the aliphatic fragments can be observed. In general the process of vacuum residue thermal cracking causes partial degradation of saturated (aliphatic and naphthenic) fragments and, partially, aromatic rings, which contain heteroatomic elements

Effect of aliskiren on post-discharge outcomes among diabetic and non-diabetic patients hospitalized for heart failure: insights from the ASTRONAUT trial

Aims The objective of the Aliskiren Trial on Acute Heart Failure Outcomes (ASTRONAUT) was to determine whether aliskiren, a direct renin inhibitor, would improve post-discharge outcomes in patients with hospitalization for heart failure (HHF) with reduced ejection fraction. Pre-specified subgroup analyses suggested potential heterogeneity in post-discharge outcomes with aliskiren in patients with and without baseline diabetes mellitus (DM). Methods and results ASTRONAUT included 953 patients without DM (aliskiren 489; placebo 464) and 662 patients with DM (aliskiren 319; placebo 343) (as reported by study investigators). Study endpoints included the first occurrence of cardiovascular death or HHF within 6 and 12 months, all-cause death within 6 and 12 months, and change from baseline in N-terminal pro-B-type natriuretic peptide (NT-proBNP) at 1, 6, and 12 months. Data regarding risk of hyperkalaemia, renal impairment, and hypotension, and changes in additional serum biomarkers were collected. The effect of aliskiren on cardiovascular death or HHF within 6 months (primary endpoint) did not significantly differ by baseline DM status (P = 0.08 for interaction), but reached statistical significance at 12 months (non-DM: HR: 0.80, 95% CI: 0.64-0.99; DM: HR: 1.16, 95% CI: 0.91-1.47; P = 0.03 for interaction). Risk of 12-month all-cause death with aliskiren significantly differed by the presence of baseline DM (non-DM: HR: 0.69, 95% CI: 0.50-0.94; DM: HR: 1.64, 95% CI: 1.15-2.33; P < 0.01 for interaction). Among non-diabetics, aliskiren significantly reduced NT-proBNP through 6 months and plasma troponin I and aldosterone through 12 months, as compared to placebo. Among diabetic patients, aliskiren reduced plasma troponin I and aldosterone relative to placebo through 1 month only. There was a trend towards differing risk of post-baseline potassium ≥6 mmol/L with aliskiren by underlying DM status (non-DM: HR: 1.17, 95% CI: 0.71-1.93; DM: HR: 2.39, 95% CI: 1.30-4.42; P = 0.07 for interaction). Conclusion This pre-specified subgroup analysis from the ASTRONAUT trial generates the hypothesis that the addition of aliskiren to standard HHF therapy in non-diabetic patients is generally well-tolerated and improves post-discharge outcomes and biomarker profiles. In contrast, diabetic patients receiving aliskiren appear to have worse post-discharge outcomes. Future prospective investigations are needed to confirm potential benefits of renin inhibition in a large cohort of HHF patients without D

Search for dark matter produced in association with bottom or top quarks in √s = 13 TeV pp collisions with the ATLAS detector

A search for weakly interacting massive particle dark matter produced in association with bottom or top quarks is presented. Final states containing third-generation quarks and miss- ing transverse momentum are considered. The analysis uses 36.1 fb−1 of proton–proton collision data recorded by the ATLAS experiment at √s = 13 TeV in 2015 and 2016. No significant excess of events above the estimated backgrounds is observed. The results are in- terpreted in the framework of simplified models of spin-0 dark-matter mediators. For colour- neutral spin-0 mediators produced in association with top quarks and decaying into a pair of dark-matter particles, mediator masses below 50 GeV are excluded assuming a dark-matter candidate mass of 1 GeV and unitary couplings. For scalar and pseudoscalar mediators produced in association with bottom quarks, the search sets limits on the production cross- section of 300 times the predicted rate for mediators with masses between 10 and 50 GeV and assuming a dark-matter mass of 1 GeV and unitary coupling. Constraints on colour- charged scalar simplified models are also presented. Assuming a dark-matter particle mass of 35 GeV, mediator particles with mass below 1.1 TeV are excluded for couplings yielding a dark-matter relic density consistent with measurements

Multidifferential study of identified charged hadron distributions in ZZ-tagged jets in proton-proton collisions at s=\sqrt{s}=13 TeV

Jet fragmentation functions are measured for the first time in proton-proton collisions for charged pions, kaons, and protons within jets recoiling against a $Z$ boson. The charged-hadron distributions are studied longitudinally and transversely to the jet direction for jets with transverse momentum 20 $< p_{\textrm{T}} < 100$ GeV and in the pseudorapidity range $2.5 < \eta < 4$. The data sample was collected with the LHCb experiment at a center-of-mass energy of 13 TeV, corresponding to an integrated luminosity of 1.64 fb$^{-1}$. Triple differential distributions as a function of the hadron longitudinal momentum fraction, hadron transverse momentum, and jet transverse momentum are also measured for the first time. This helps constrain transverse-momentum-dependent fragmentation functions. Differences in the shapes and magnitudes of the measured distributions for the different hadron species provide insights into the hadronization process for jets predominantly initiated by light quarks.Comment: All figures and tables, along with machine-readable versions and any supplementary material and additional information, are available at https://cern.ch/lhcbproject/Publications/p/LHCb-PAPER-2022-013.html (LHCb public pages

Study of the B−→Λc+Λˉc−K−B^{-} \to \Lambda_{c}^{+} \bar{\Lambda}_{c}^{-} K^{-} decay

The decay $B^{-} \to \Lambda_{c}^{+} \bar{\Lambda}_{c}^{-} K^{-}$ is studied in proton-proton collisions at a center-of-mass energy of $\sqrt{s}=13$ TeV using data corresponding to an integrated luminosity of 5 $\mathrm{fb}^{-1}$ collected by the LHCb experiment. In the $\Lambda_{c}^+ K^{-}$ system, the $\Xi_{c}(2930)^{0}$ state observed at the BaBar and Belle experiments is resolved into two narrower states, $\Xi_{c}(2923)^{0}$ and $\Xi_{c}(2939)^{0}$, whose masses and widths are measured to be $$m(\Xi_{c}(2923)^{0}) = 2924.5 \pm 0.4 \pm 1.1 \,\mathrm{MeV}, \\ m(\Xi_{c}(2939)^{0}) = 2938.5 \pm 0.9 \pm 2.3 \,\mathrm{MeV}, \\ \Gamma(\Xi_{c}(2923)^{0}) = \phantom{000}4.8 \pm 0.9 \pm 1.5 \,\mathrm{MeV},\\ \Gamma(\Xi_{c}(2939)^{0}) = \phantom{00}11.0 \pm 1.9 \pm 7.5 \,\mathrm{MeV},$$ where the first uncertainties are statistical and the second systematic. The results are consistent with a previous LHCb measurement using a prompt $\Lambda_{c}^{+} K^{-}$ sample. Evidence of a new $\Xi_{c}(2880)^{0}$ state is found with a local significance of $3.8\,\sigma$, whose mass and width are measured to be $2881.8 \pm 3.1 \pm 8.5\,\mathrm{MeV}$ and $12.4 \pm 5.3 \pm 5.8 \,\mathrm{MeV}$, respectively. In addition, evidence of a new decay mode $\Xi_{c}(2790)^{0} \to \Lambda_{c}^{+} K^{-}$ is found with a significance of $3.7\,\sigma$. The relative branching fraction of $B^{-} \to \Lambda_{c}^{+} \bar{\Lambda}_{c}^{-} K^{-}$ with respect to the $B^{-} \to D^{+} D^{-} K^{-}$ decay is measured to be $2.36 \pm 0.11 \pm 0.22 \pm 0.25$, where the first uncertainty is statistical, the second systematic and the third originates from the branching fractions of charm hadron decays.Comment: All figures and tables, along with any supplementary material and additional information, are available at https://cern.ch/lhcbproject/Publications/p/LHCb-PAPER-2022-028.html (LHCb public pages

Measurement of the ratios of branching fractions R(D∗)\mathcal{R}(D^{*}) and R(D0)\mathcal{R}(D^{0})

The ratios of branching fractions $\mathcal{R}(D^{*})\equiv\mathcal{B}(\bar{B}\to D^{*}\tau^{-}\bar{\nu}_{\tau})/\mathcal{B}(\bar{B}\to D^{*}\mu^{-}\bar{\nu}_{\mu})$ and $\mathcal{R}(D^{0})\equiv\mathcal{B}(B^{-}\to D^{0}\tau^{-}\bar{\nu}_{\tau})/\mathcal{B}(B^{-}\to D^{0}\mu^{-}\bar{\nu}_{\mu})$ are measured, assuming isospin symmetry, using a sample of proton-proton collision data corresponding to 3.0 fb${ }^{-1}$ of integrated luminosity recorded by the LHCb experiment during 2011 and 2012. The tau lepton is identified in the decay mode $\tau^{-}\to\mu^{-}\nu_{\tau}\bar{\nu}_{\mu}$. The measured values are $\mathcal{R}(D^{*})=0.281\pm0.018\pm0.024$ and $\mathcal{R}(D^{0})=0.441\pm0.060\pm0.066$, where the first uncertainty is statistical and the second is systematic. The correlation between these measurements is $\rho=-0.43$. Results are consistent with the current average of these quantities and are at a combined 1.9 standard deviations from the predictions based on lepton flavor universality in the Standard Model.Comment: All figures and tables, along with any supplementary material and additional information, are available at https://cern.ch/lhcbproject/Publications/p/LHCb-PAPER-2022-039.html (LHCb public pages