UMA INVESTIGAÇÃO BASEADA EM PROVAS DOS RELATÓRIOS DO CERT-IN SOBRE CIBERAMEAÇAS NO SECTOR DA SAÚDE

The pandemic underscored the significance of a digital health system. Healthcare sector has become one of the most important infrastructures since then. Undoubtedly, the digital health is the ultimate way to ensure accessibility, inclusiveness and delivery of healthcare services in an affordable and efficient manner. However, rising cyber-threat is one of the biggest concerns for healthcare organizations. The data breach incidents on Indian Council of Medical Research and on Covid-19 vaccine database in 2023 highlight the utter need to address the issue. To mitigate such incidents, India has established Computer Emergency and Response Team (CERT-In) which has been endowed with primary responsibility to prevent, treat, respond and report such threats. Although, CERT-In is responsible to report any cyber-incident but there is no information concerning the affected organizations and on frequency and severity of such cyber-incidents.  It is doubtful as to how any authority is supposed to respond in lack of data or policy makers formulate a comprehensive framework to deal with the issue. CERT-In faces challenges in accurately reporting cyber incidents and contain discrepancies compared to other organizations' data and lacking detailed incident information. This research aims to analyze government records and secondary sources to understand the cyber-threat landscape, particularly in the healthcare industry.  Using normative and comparative methods, it suggests measures which can be adopted by CERT-In based on assessments of U.S. and E.U. reporting practices. Findings stress the need for improved reporting practices and transparency in cybersecurity assessments to enhance data accuracy and completeness, urging policymakers and stakeholders to take action against cyber threats. A pandemia ressaltou a importância de um sistema de saúde digital. Desde então, o setor de saúde se tornou uma das infraestruturas mais importantes. Sem dúvida, a saúde digital é a melhor maneira de garantir a acessibilidade, a inclusão e a prestação de serviços de saúde de forma acessível e eficiente. Entretanto, a crescente ameaça cibernética é uma das maiores preocupações das organizações de saúde. Os incidentes de violação de dados no Conselho Indiano de Pesquisa Médica e no banco de dados de vacinas contra a Covid-19 em 2023 destacam a necessidade absoluta de resolver o problema. Para mitigar esses incidentes, a Índia criou a Equipe de Emergência e Resposta a Computadores (CERT-In), que tem a responsabilidade principal de prevenir, tratar, responder e relatar essas ameaças. Embora o CERT-In seja responsável por relatar qualquer incidente cibernético, não há informações sobre as organizações afetadas e sobre a frequência e a gravidade desses incidentes cibernéticos. É duvidoso como qualquer autoridade deve responder à falta de dados ou como os formuladores de políticas devem formular uma estrutura abrangente para lidar com o problema. O CERT-In enfrenta desafios para relatar com precisão os incidentes cibernéticos e contém discrepâncias em relação aos dados de outras organizações, além de não ter informações detalhadas sobre os incidentes. Esta pesquisa tem como objetivo analisar registros governamentais e fontes secundárias para entender o cenário de ameaças cibernéticas, especialmente no setor de saúde. Usando métodos normativos e comparativos, ela sugere medidas que podem ser adotadas pelo CERT-In com base em avaliações das práticas de notificação dos EUA e da UE. Os resultados enfatizam a necessidade de melhores práticas de relatório e transparência nas avaliações de segurança cibernética para aumentar a precisão e a integridade dos dados, incentivando os formuladores de políticas e as partes interessadas a tomar medidas contra as ameaças cibernéticas

Détermination et calcul premiers principes, par la méthode PAW/GIPAW, de paramètres RMN de fluorures inorganiques

Cette thèse porte sur la détermination et la modélisation, par la méthode PAW/GIPAW (Gauge Including Projector Augmented Waves), de paramètres RMN de fluorures inorganiques. Dans la première partie, une corrélation entre valeurs expérimentales de déplacements chimiques isotropes (diso) de 19F et de constantes d'écran isotropes (iso) de F calculées de fluorures binaires, dont les attributions sont triviales, est établie. Elle permet de prédire les spectres RMN de 19F avec une bonne précision. Les paramètres quadripolaires de ces fluorures sont aussi déterminés et calculés. Dans la seconde partie, la linéarité entre valeurs expérimentales de diso de 19F et valeurs calculées de iso de 19F permet une attribution non ambigüe des raies RMN de 19F de NbF5 et TaF5. Par contre, pour trois des quatre composés MF4 étudiés (b-ZrF4, HfF4, CeF4, ThF4), caractérisés par des gammes de valeurs de diso de 19F plus petites, les corrélations médiocres entre valeurs de diso et de siso de 19F ne le permettent pas. Enfin, NaAsF6 et KPF6 qui présentent des valeurs élevées de couplage 1J 19F-X et des transitions de phase à des températures proches de l'ambiante sont étudiés par DTA ou DSC et diffraction des rayons X sur poudre et RMN du solide multinucléaire à température variable. Les structures de a- et b-NaAsF6 sont déterminées. KPF6 adopte une structure de haute symétrie désordonnée à température ambiante mais les tentatives de détermination des positions atomiques des deux premières phases basse température sont restées vaines. Ce travail souligne les potentialités et quelques limites de cette méthode ainsi que l'attention qui doit être prêtée aux effets des optimisations.This thesis focuses on the determination and the modeling, by the PAW/GIPAW (Gauge Including Projector Augmented Waves) method, of NMR parameters in inorganic fluorides. In the first part, a correlation between experimental 19F isotropic chemical shift (diso) and calculated 19F isotropic shieldings (siso) of binary fluorides with obvious assignments is established that allows to predict 19F NMR spectra with a good accuracy. The quadrupolar parameters of these fluorides are also determined and calculated. In the second part, a complete and unambiguous assignment of the 19F NMR lines of NbF5 and TaF5 is obtained, ensured by the linearity between experimental 19F diso values and calculated 19F siso values. On the other hand, for the studied MF4 (b-ZrF4, HfF4, CeF4, ThF4) compounds, characterized by smaller 19F diso ranges, except for ThF4, the poor correlations between experimental 19F diso and calculated 19F siso values prevent us to propose an assignment of the 19F NMR lines. In the last part, NaAsF6 and KPF6, exhibiting large 19F-X 1J-coupling and phase transitions at temperatures close to room temperature (RT) are investigated by DTA or DSC and variable temperature X-ray powder diffraction and multinuclear solid-state NMR. The structures of a- and b-NaAsF6 are determined. KPF6 adopts a disordered high symmetry structure at RT. Unfortunately, attempts to determine the atomic positions of the two first low temperature phases remain unsuccessful. This work highlights the potentialities and some limitations of this method as well as the care that must be taken when dealing with optimized structures.LE MANS-BU Sciences (721812109) / SudocSudocFranceF

NMR parameters in alkali, alkaline earth and rare earth fluorides from first principle calculations

19F isotropic chemical shifts for alkali, alkaline earth and rare earth of column 3 basic fluorides are measured and the corresponding isotropic chemical shieldings are calculated using the GIPAW method. When using PBE exchange correlation functional for the treatment of the cationic localized empty orbitals of Ca2+, Sc3+ (3d) and La3+ (4f), a correction is needed to accurately calculate 19F chemical shieldings. We show that the correlation between experimental isotropic chemical shifts and calculated isotropic chemical shieldings established for the studied compounds allows to predict 19F NMR spectra of crystalline compounds with a relatively good accuracy. In addition, we experimentally determine the quadrupolar parameters of 25Mg in MgF2 and calculate the electric field gradient of 25Mg in MgF2 and 139La in LaF3 using both PAW and LAPW methods. The orientation of the EFG components in the crystallographic frame, provided by DFT calculations, is analysed in term of electron densities. It is shown that consideration of the quadrupolar charge deformation is essential for the analysis of slightly distorted environments or highly irregular polyhedra.Comment: 18 pages, 8 figures, 4 tables and ES

Détermination et calcul premiers principes, par la méthode PAW/GIPAW, de paramètres RMN de fluorures inorganiques

This thesis focuses on the determination and the modeling, by the PAW/GIPAW (Gauge Including Projector Augmented Waves) method, of NMR parameters in inorganic fluorides. In the first part, a correlation between experimental 19F isotropic chemical shift (diso) and calculated 19F isotropic shieldings (siso) of binary fluorides with obvious assignments is established that allows to predict 19F NMR spectra with a good accuracy. The quadrupolar parameters of these fluorides are also determined and calculated. In the second part, a complete and unambiguous assignment of the 19F NMR lines of NbF5 and TaF5 is obtained, ensured by the linearity between experimental 19F diso values and calculated 19F siso values. On the other hand, for the studied MF4 (b-ZrF4, HfF4, CeF4, ThF4) compounds, characterized by smaller 19F diso ranges, except for ThF4, the poor correlations between experimental 19F diso and calculated 19F siso values prevent us to propose an assignment of the 19F NMR lines. In the last part, NaAsF6 and KPF6, exhibiting large 19F-X 1J-coupling and phase transitions at temperatures close to room temperature (RT) are investigated by DTA or DSC and variable temperature X-ray powder diffraction and multinuclear solid-state NMR. The structures of a- and b-NaAsF6 are determined. KPF6 adopts a disordered high symmetry structure at RT. Unfortunately, attempts to determine the atomic positions of the two first low temperature phases remain unsuccessful. This work highlights the potentialities and some limitations of this method as well as the care that must be taken when dealing with optimized structures.Cette thèse porte sur la détermination et la modélisation, par la méthode PAW/GIPAW (Gauge Including Projector Augmented Waves), de paramètres RMN de fluorures inorganiques. Dans la première partie, une corrélation entre valeurs expérimentales de déplacements chimiques isotropes (diso) de 19F et de constantes d'écran isotropes (iso) de F calculées de fluorures binaires, dont les attributions sont triviales, est établie. Elle permet de prédire les spectres RMN de 19F avec une bonne précision. Les paramètres quadripolaires de ces fluorures sont aussi déterminés et calculés. Dans la seconde partie, la linéarité entre valeurs expérimentales de diso de 19F et valeurs calculées de iso de 19F permet une attribution non ambigüe des raies RMN de 19F de NbF5 et TaF5. Par contre, pour trois des quatre composés MF4 étudiés (b-ZrF4, HfF4, CeF4, ThF4), caractérisés par des gammes de valeurs de diso de 19F plus petites, les corrélations médiocres entre valeurs de diso et de siso de 19F ne le permettent pas. Enfin, NaAsF6 et KPF6 qui présentent des valeurs élevées de couplage 1J 19F-X et des transitions de phase à des températures proches de l'ambiante sont étudiés par DTA ou DSC et diffraction des rayons X sur poudre et RMN du solide multinucléaire à température variable. Les structures de a- et b-NaAsF6 sont déterminées. KPF6 adopte une structure de haute symétrie désordonnée à température ambiante mais les tentatives de détermination des positions atomiques des deux premières phases basse température sont restées vaines. Ce travail souligne les potentialités et quelques limites de cette méthode ainsi que l'attention qui doit être prêtée aux effets des optimisations

NbF5 and TaF5: Assignment of F-19 NMR resonances and chemical bond analysis from GIPAW calculations

International audienceThe 19F isotropic chemical shifts (δiso) of two isomorphic compounds, NbF5 and TaF5, which involve six nonequivalent fluorine sites, have been experimentally determined from the reconstruction of 1D 19F MAS NMR spectra. In parallel, the corresponding 19F chemical shielding tensors have been calculated using the GIPAW method for both experimental and DFT-optimized structures. Furthermore, the [M4F20] units of NbF5 and TaF5 being held together by van der Waals interactions, the relevance of Grimme corrections to the DFT optimization processes has been evaluated. However, the semi-empirical dispersion correction term introduced by such a method does not show any significant improvement. Nonetheless, a complete and convincing assignment of the 19F NMR lines of NbF5 and TaF5 is obtained, ensured by the linearity between experimental 19F δiso values and calculated 19F isotropic chemical shielding σiso values. The effects of the geometry optimizations have been carefully analyzed, confirming among other matters, the inaccuracy of the experimental structure of NbF5. The relationships between the fluorine chemical shifts, the nature of the fluorine atoms (bridging or terminal), the position of the terminal ones (opposite or perpendicular to the bridging ones), the fluorine charges, the ionicity and the length of the M-F bonds have been established. Additionally, for three of the 19F NMR lines of NbF5, distorted multiplets, arising from 1J-coupling and residual dipolar coupling between the 19F and 93Nb nuclei, were simulated yielding to values of 93Nb-19F 1J-coupling for the corresponding fluorine sites

NMR parameters in column 13 metal fluoride compounds (AlF3, GaF3, InF3 and TlF) from first principle calculations

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Structural Investigation of α- and β-Sodium Hexafluoroarsenate, NaAsF₆, by Variable Temperature X-ray Powder Diffraction and Multinuclear Solid-State NMR, and DFT Calculations

We report the phase transition between the α- and β-phases of NaAsF₆ monitored by DTA, variable temperature ¹⁹F solid-state NMR and temperature controlled X-ray powder diffraction (XRPD) as well as their crystalline structures determined from XRPD data. The structural type of β-NaAsF₆ has been determined thanks to ¹⁹F and ⁷⁵As solid-state NMR experiments. ¹⁹F, ²³Na, and ⁷⁵As NMR parameters, including ¹⁹F–⁷⁵As ¹<i>J</i> coupling, have been measured for both phases. The ¹⁹F, ²³Na, and ⁷⁵As solid-state NMR investigations are in full agreement with both crystalline structures from a qualitative point of view. Chemical shielding tensors have been calculated from the gauge including projector augmented wave approach. The electric field gradient tensors of ²³Na and ⁷⁵As have been calculated in α-NaAsF₆ from the all-electrons method and the projector augmented-wave approach. Two difficulties were encountered: the libration of the rigid and regular AsF₆^– anions in the β-phase, highlighted by the atomic anisotropic displacement parameters for F, which leads to erroneous shortened As–F bond length, and the overestimation of the As–F bond length with the PBE functional used in the density functional theory calculations. We show that both difficulties can be overcome by full optimization and rescaling of the cell parameters of the crystalline structures. Additionally, a linear correlation is observed between experimental ²³Na δ_iso values and calculated ²³Na σ_iso values from previously reported data and from our own measurements and calculations