Synthesis of gold(I)-trifluoromethyl complexes and their role in generating spectroscopic evidence for a gold(I)-difluorocarbene species

We thank the Ghent University (IoF), the Special Research Fund (BOF) starting (SPN, CSJC) and advanced (SPN, KVH) grants and Research Foundation Flanders (FWO) (fellowship to SVB and grant to CSJC and KVH) for funding.Readily-prepared and bench-stable [Au(CF3)(NHC)] compounds were synthesized using new methodologies, starting from [Au(OH)(NHC)], [Au(Cl)(NHC)] or [Au(L)(NHC)]HF2 precursors (NHC = N-heterocyclic carbene). The mechanism of formation of these species was investigated. Consequently, a new and straightforward strategy for the mild and selective cleavage of a single carbon-fluorine bond from [Au(CF3)(NHC)] complexes was attempted and found to be reversible in the presence of an additional nucleophilic fluoride source. This straightforward technique has led to the unprecedented spectroscopic observation of a gold(I)-NHC difluorocarbene species.PostprintPeer reviewe

Simple synthetic routes to carbene-M-amido (M=Cu, Ag, Au) complexes for luminescence and photocatalysis applications

The development of novel and operationally simple synthetic routes to carbene-metal-amido (CMA) complexes of copper, silver and gold relevant for photonic applications are reported. A mild base and sustainable solvents allow all reactions to be conducted in air and at room temperature, leading to high yields of the targeted compounds even on multigram scales. The effect of various mild bases on the N−H metallation was studied in silico and experimentally, while a mechanochemical, solvent-free synthetic approach was also developed. Our photophysical studies on [M(NHC)(Cbz)] (Cbz=carbazolyl) indicate that the occurrence of fluorescent or phosphorescent states is determined primarily by the metal, providing control over the excited state properties. Consequently, we demonstrate the potential of the new CMAs beyond luminescence applications by employing a selected CMA as a photocatalyst. The exemplified synthetic ease is expected to accelerate the applications of CMAs in photocatalysis and materials chemistry

A pattern-search-based inverse method

Uncertainty in model predictions is caused to a large extent by the uncertainty in model parameters, while the identification of model parameters is demanding because of the inherent heterogeneity of the aquifer. A variety of inverse methods has been proposed for parameter identification. In this paper we present a novel inverse method to constrain the model parameters (hydraulic conductivities) to the observed state data (hydraulic heads). In the method proposed we build a conditioning pattern consisting of simulated model parameters and observed flow data. The unknown parameter values are simulated by pattern searching through an ensemble of realizations rather than optimizing an objective function. The model parameters do not necessarily follow a multi-Gaussian distribution, and the nonlinear relationship between the parameter and the response is captured by the multipoint pattern matching. The algorithm is evaluated in two synthetic bimodal aquifers. The proposed method is able to reproduce the main structure of the reference fields, and the performance of the updated model in predicting flow and transport is improved compared with that of the prior model.The authors gratefully acknowledge the financial support from the Ministry of Science and Innovation, project CGL2011-23295. The first author also acknowledges the scholarship provided by the China Scholarship Council (CSC [2007] 3020). The authors would like to thank Gregoire Mariethoz (University of New South Wales) and Philippe Renard (University of Neuchatel) for their enthusiastic help in answering questions about the direct sampling algorithm. Gregoire Mariethoz and two anonymous reviewers are also thanked for their comments during the reviewing process, which helped improving the final paper.Zhou ., H.; Gómez-Hernández, JJ.; Li ., L. (2012). A pattern-search-based inverse method. Water Resources Research. 48(3):1-17. https://doi.org/10.1029/2011WR011195S117483Alcolea, A., & Renard, P. (2010). Blocking Moving Window algorithm: Conditioning multiple-point simulations to hydrogeological data. Water Resources Research, 46(8). doi:10.1029/2009wr007943Alcolea, A., Carrera, J., & Medina, A. (2006). Pilot points method incorporating prior information for solving the groundwater flow inverse problem. Advances in Water Resources, 29(11), 1678-1689. doi:10.1016/j.advwatres.2005.12.009Arpat, G. B., & Caers, J. (2007). Conditional Simulation with Patterns. Mathematical Geology, 39(2), 177-203. doi:10.1007/s11004-006-9075-3Caers , J. 2002 Geostatistical history matching under training-image based geological model constraintsCaers, J. (2003). Efficient gradual deformation using a streamline-based proxy method. Journal of Petroleum Science and Engineering, 39(1-2), 57-83. doi:10.1016/s0920-4105(03)00040-8Caers, J., & Hoffman, T. (2006). The Probability Perturbation Method: A New Look at Bayesian Inverse Modeling. Mathematical Geology, 38(1), 81-100. doi:10.1007/s11004-005-9005-9Capilla, J. E., & Llopis-Albert, C. (2009). Gradual conditioning of non-Gaussian transmissivity fields to flow and mass transport data: 1. Theory. Journal of Hydrology, 371(1-4), 66-74. doi:10.1016/j.jhydrol.2009.03.015Carrera, J., & Neuman, S. P. (1986). Estimation of Aquifer Parameters Under Transient and Steady State Conditions: 1. Maximum Likelihood Method Incorporating Prior Information. Water Resources Research, 22(2), 199-210. doi:10.1029/wr022i002p00199Chen, Y., & Zhang, D. (2006). Data assimilation for transient flow in geologic formations via ensemble Kalman filter. Advances in Water Resources, 29(8), 1107-1122. doi:10.1016/j.advwatres.2005.09.007Christiansen, L., Binning, P. J., Rosbjerg, D., Andersen, O. B., & Bauer-Gottwein, P. (2011). Using time-lapse gravity for groundwater model calibration: An application to alluvial aquifer storage. Water Resources Research, 47(6). doi:10.1029/2010wr009859De Marsily, G., Delay, F., Gonçalvès, J., Renard, P., Teles, V., & Violette, S. (2005). Dealing with spatial heterogeneity. Hydrogeology Journal, 13(1), 161-183. doi:10.1007/s10040-004-0432-3Deutsch, C. V., & Tran, T. T. (2002). FLUVSIM: a program for object-based stochastic modeling of fluvial depositional systems. Computers & Geosciences, 28(4), 525-535. doi:10.1016/s0098-3004(01)00075-9Dubuisson, M.-P., & Jain, A. K. (s. f.). A modified Hausdorff distance for object matching. Proceedings of 12th International Conference on Pattern Recognition. doi:10.1109/icpr.1994.576361Emsellem, Y., & De Marsily, G. (1971). An Automatic Solution for the Inverse Problem. Water Resources Research, 7(5), 1264-1283. doi:10.1029/wr007i005p01264Evensen, G. (2003). The Ensemble Kalman Filter: theoretical formulation and practical implementation. Ocean Dynamics, 53(4), 343-367. doi:10.1007/s10236-003-0036-9Falivene, O., Cabello, P., Arbués, P., Muñoz, J. A., & Cabrera, L. (2009). A geostatistical algorithm to reproduce lateral gradual facies transitions: Description and implementation. Computers & Geosciences, 35(8), 1642-1651. doi:10.1016/j.cageo.2008.12.003Fernàndez-Garcia, D., Illangasekare, T. H., & Rajaram, H. (2005). Differences in the scale dependence of dispersivity and retardation factors estimated from forced-gradient and uniform flow tracer tests in three-dimensional physically and chemically heterogeneous porous media. Water Resources Research, 41(3). doi:10.1029/2004wr003125Feyen, L., & Caers, J. (2006). Quantifying geological uncertainty for flow and transport modeling in multi-modal heterogeneous formations. Advances in Water Resources, 29(6), 912-929. doi:10.1016/j.advwatres.2005.08.002Fu, J., & Gómez-Hernández, J. J. (2008). A Blocking Markov Chain Monte Carlo Method for Inverse Stochastic Hydrogeological Modeling. Mathematical Geosciences, 41(2), 105-128. doi:10.1007/s11004-008-9206-0Jaime Gómez-Hernánez, J., Sahuquillo, A., & Capilla, J. (1997). Stochastic simulation of transmissivity fields conditional to both transmissivity and piezometric data—I. Theory. Journal of Hydrology, 203(1-4), 162-174. doi:10.1016/s0022-1694(97)00098-xGuardiano, F. B., & Srivastava, R. M. (1993). Multivariate Geostatistics: Beyond Bivariate Moments. Geostatistics Tróia ’92, 133-144. doi:10.1007/978-94-011-1739-5_12Harbaugh , A. W. E. R. Banta M. C. Hill M. G. McDonald 2000 MODFLOW-2000, the U.S. Geological Survey modular ground-water model-User guide to modularization concepts and the ground-water flow process Reston, Va.Hendricks Franssen, H. J., & Kinzelbach, W. (2008). Real-time groundwater flow modeling with the Ensemble Kalman Filter: Joint estimation of states and parameters and the filter inbreeding problem. Water Resources Research, 44(9). doi:10.1029/2007wr006505Franssen, H.-J. H., Gómez-Hernández, J., & Sahuquillo, A. (2003). Coupled inverse modelling of groundwater flow and mass transport and the worth of concentration data. Journal of Hydrology, 281(4), 281-295. doi:10.1016/s0022-1694(03)00191-4Henrion, V., Caumon, G., & Cherpeau, N. (2010). ODSIM: An Object-Distance Simulation Method for Conditioning Complex Natural Structures. Mathematical Geosciences, 42(8), 911-924. doi:10.1007/s11004-010-9299-0Hoeksema, R. J., & Kitanidis, P. K. (1984). An Application of the Geostatistical Approach to the Inverse Problem in Two-Dimensional Groundwater Modeling. Water Resources Research, 20(7), 1003-1020. doi:10.1029/wr020i007p01003Hoeksema, R. J., & Kitanidis, P. K. (1985). Analysis of the Spatial Structure of Properties of Selected Aquifers. Water Resources Research, 21(4), 563-572. doi:10.1029/wr021i004p00563Hu, L. Y. (2000). Mathematical Geology, 32(1), 87-108. doi:10.1023/a:1007506918588Hu, L. Y., & Chugunova, T. (2008). Multiple-point geostatistics for modeling subsurface heterogeneity: A comprehensive review. Water Resources Research, 44(11). doi:10.1029/2008wr006993Huysmans, M., & Dassargues, A. (2009). Application of multiple-point geostatistics on modelling groundwater flow and transport in a cross-bedded aquifer (Belgium). Hydrogeology Journal, 17(8), 1901-1911. doi:10.1007/s10040-009-0495-2Jafarpour, B., & Khodabakhshi, M. (2011). A Probability Conditioning Method (PCM) for Nonlinear Flow Data Integration into Multipoint Statistical Facies Simulation. Mathematical Geosciences, 43(2), 133-164. doi:10.1007/s11004-011-9316-yJournel, A., & Zhang, T. (2006). The Necessity of a Multiple-Point Prior Model. Mathematical Geology, 38(5), 591-610. doi:10.1007/s11004-006-9031-2Kerrou, J., Renard, P., Hendricks Franssen, H.-J., & Lunati, I. (2008). Issues in characterizing heterogeneity and connectivity in non-multiGaussian media. Advances in Water Resources, 31(1), 147-159. doi:10.1016/j.advwatres.2007.07.002Kwa, Franz, M. O., & Scholkopf, B. (2005). Iterative kernel principal component analysis for image modeling. IEEE Transactions on Pattern Analysis and Machine Intelligence, 27(9), 1351-1366. doi:10.1109/tpami.2005.181Kitanidis, P. K. (2007). On stochastic inverse modeling. Geophysical Monograph Series, 19-30. doi:10.1029/171gm04Kitanidis, P. K., & Vomvoris, E. G. (1983). A geostatistical approach to the inverse problem in groundwater modeling (steady state) and one-dimensional simulations. Water Resources Research, 19(3), 677-690. doi:10.1029/wr019i003p00677Li, L., Zhou, H., Hendricks Franssen, H. J., & Gómez-Hernández, J. J. (2011). Groundwater flow inverse modeling in non-MultiGaussian media: performance assessment of the normal-score Ensemble Kalman Filter. Hydrology and Earth System Sciences Discussions, 8(4), 6749-6788. doi:10.5194/hessd-8-6749-2011Li, L., Zhou, H., & Gómez-Hernández, J. J. (2011). Transport upscaling using multi-rate mass transfer in three-dimensional highly heterogeneous porous media. Advances in Water Resources, 34(4), 478-489. doi:10.1016/j.advwatres.2011.01.001Li, L., Zhou, H., & Gómez-Hernández, J. J. (2011). A comparative study of three-dimensional hydraulic conductivity upscaling at the macro-dispersion experiment (MADE) site, Columbus Air Force Base, Mississippi (USA). Journal of Hydrology, 404(3-4), 278-293. doi:10.1016/j.jhydrol.2011.05.001Mariethoz, G., Renard, P., & Straubhaar, J. (2010). The Direct Sampling method to perform multiple-point geostatistical simulations. Water Resources Research, 46(11). doi:10.1029/2008wr007621Mariethoz, G., Renard, P., & Caers, J. (2010). Bayesian inverse problem and optimization with iterative spatial resampling. Water Resources Research, 46(11). doi:10.1029/2010wr009274Neuman, S. P. (1973). Calibration of distributed parameter groundwater flow models viewed as a multiple-objective decision process under uncertainty. Water Resources Research, 9(4), 1006-1021. doi:10.1029/wr009i004p01006Oliver, D. S., Cunha, L. B., & Reynolds, A. C. (1997). Markov chain Monte Carlo methods for conditioning a permeability field to pressure data. Mathematical Geology, 29(1), 61-91. doi:10.1007/bf02769620RamaRao, B. S., LaVenue, A. M., De Marsily, G., & Marietta, M. G. (1995). Pilot Point Methodology for Automated Calibration of an Ensemble of conditionally Simulated Transmissivity Fields: 1. Theory and Computational Experiments. Water Resources Research, 31(3), 475-493. doi:10.1029/94wr02258Rubin, Y., Chen, X., Murakami, H., & Hahn, M. (2010). A Bayesian approach for inverse modeling, data assimilation, and conditional simulation of spatial random fields. Water Resources Research, 46(10). doi:10.1029/2009wr008799Strebelle, S. (2002). Mathematical Geology, 34(1), 1-21. doi:10.1023/a:1014009426274Suzuki, S., & Caers, J. (2008). A Distance-based Prior Model Parameterization for Constraining Solutions of Spatial Inverse Problems. Mathematical Geosciences, 40(4), 445-469. doi:10.1007/s11004-008-9154-8Wen, X. H., Capilla, J. E., Deutsch, C. V., Gómez-Hernández, J. J., & Cullick, A. S. (1999). A program to create permeability fields that honor single-phase flow rate and pressure data. Computers & Geosciences, 25(3), 217-230. doi:10.1016/s0098-3004(98)00126-5Zhang, T., Switzer, P., & Journel, A. (2006). Filter-Based Classification of Training Image Patterns for Spatial Simulation. Mathematical Geology, 38(1), 63-80. doi:10.1007/s11004-005-9004-xZhou, H., Gómez-Hernández, J. J., Hendricks Franssen, H.-J., & Li, L. (2011). An approach to handling non-Gaussianity of parameters and state variables in ensemble Kalman filtering. Advances in Water Resources, 34(7), 844-864. doi:10.1016/j.advwatres.2011.04.014Zhou, H., Li, L., Hendricks Franssen, H.-J., & Gómez-Hernández, J. J. (2011). Pattern Recognition in a Bimodal Aquifer Using the Normal-Score Ensemble Kalman Filter. Mathematical Geosciences, 44(2), 169-185. doi:10.1007/s11004-011-9372-

Does Sedimentology have a role in the energy transition? A proposal

El proyecto SOSGAS tiene por objeto calibrar el impacto de la heterogeneidad sedimentaria inherente a formaciones fluviales y deltaicas en el geo-almacenamiento sostenible de CO2 y H2 verde. Se han seleccionado 6 ejemplos mesozoicos y cenozoicos en la Meseta Ibérica, la Cuenca del Ebro y la Cuenca de Graus-Tremp a los que se aplica el flujo de trabajo OBO. Con esta base de datos de afloramiento y subsuelo se construyen modelos estáticos 3D de distribución de facies reservorio y sello y de propiedades petrofísicas, y finalmente se simula la inyección de los fluidos. Diferentes hipótesis de conectividad entre litofacies porosas y de distribución de los sellos conducen a diferentes escenarios de dinámica de fluidos y de entrampamiento. Con este proyecto iniciamos una línea de investigación que permitirá evaluar la validez de la sedimentología para contribuir al reto social de la transición energética.The SOSGAS project aims to gauge the impact of sedimentary heterogeneity inherent to fluvial and deltaic formations on the sustainability of a possible geo-storage of CO2 and green H2. 6 Mesozoic and Cenozoic examples have been selected in the Iberian Meseta, the Ebro Basin and the Graus-Tremp Basin to which the OBO workflow is applied. Using this outcrop and subsurface database, 3D static models are constructed to reproduce the distribution of reservoir and seal facies and petrophysical properties, and finally fluid injection is simulated. Different hypotheses of connectivity of porous lithofacies and seal distribution lead to different scenarios of fluid flow dynamics and trapping. With this project, we are initiating a line of research that will make it possible to assess the validity of sedimentology in contributing to the social challenge of the energy transition.Grants PID2022-140850OB-C21 and PID2022-140850OB-C22 funded by MCIN/AEI/10.13039/501100011033/ and by “ERDF A way of making Europe”. REPSOL EP, CEPSA EP, ENAGAS, SLB, AGGEP, the MS2022-17 contract -NextGenerationEU- and the groups RNM369 (PAI) and 2021SGR00076 (GC) are also grateful

IL-12 and GM-CSF in DNA/MVA Immunizations against HIV-1 CRF12_BF Nef Induced T-Cell Responses With an Enhanced Magnitude, Breadth and Quality

In Argentina, the HIV epidemic is characterized by the co-circulation of subtype B and BF recombinant viral variants. Nef is an HIV protein highly variable among subtypes, making it a good tool to study the impact of HIV variability in the vaccine design setting. We have previously reported a specific cellular response against NefBF with low cross-reactivity to NefB in mice. The aim of this work was to analyze whether the co-administration of IL-12 and GM-CSF, using DNA and MVA vaccine vectors, could improve the final cellular response induced. Mice received three DNA priming doses of a plasmid that express NefBF plus DNAs expressing IL-12 and/or GM-CSF. Afterwards, all the groups were boosted with a MVAnefBF dose. The highest increase in the magnitude of the NefBF response, compared to that induced in the control was found in the IL-12 group. Importantly, a response with higher breadth was detected in groups which received IL-12 or GM-CSF, evidenced as an increased frequency of recognition of homologous (BF) and heterologous (B) Nef peptides, as well as a higher number of other Nef peptide pools representing different viral subtypes. However, these improvements were lost when both DNA cytokines were simultaneously administered, as the response was focused against the immunodominant peptide with a detrimental response towards subdominant epitopes. The pattern of cytokines secreted and the specific-T-cell proliferative capacity were improved in IL-12 and IL-12+GM-CSF groups. Importantly IL-12 generated a significant higher T-cell avidity against a B heterologous peptide

T-Cell Immune Responses Against Env from CRF12_BF and Subtype B HIV-1 Show High Clade-Specificity that Can Be Overridden by Multiclade Immunizations

BACKGROUND: The extreme genetic diversity of the human immunodeficiency virus type 1 (HIV-1) poses a daunting challenge to the generation of an effective AIDS vaccine. In Argentina, the epidemic is characterized by the high prevalence of infections caused by subtype B and BF variants. The aim of this study was to characterize in mice the immunogenic and antigenic properties of the Env protein from CRF12_BF in comparison with clade B, employing prime-boost schemes with the combination of recombinant DNA and vaccinia virus (VV) vectors. METHODOLOGY/PRINCIPAL FINDINGS: As determined by ELISPOT from splenocytes of animals immunized with either EnvBF or EnvB antigens, the majority of the cellular responses to Env were found to be clade-specific. A detailed peptide mapping of the responses reveal that when there is cross-reactivity, there are no amino acid changes in the peptide sequence or were minimal and located at the peptide ends. In those cases, analysis of T cell polifunctionality and affinity indicated no differences with respect to the cellular responses found against the original homologous sequence. Significantly, application of a mixed immunization combining both clades (B and BF) induced a broader cellular response, in which the majority of the peptides targeted after the single clade vaccinations generated a positive response. In this group we could also find significant cellular and humoral responses against the whole gp120 protein from subtype B. CONCLUSIONS/SIGNIFICANCE: This work has characterized for the first time the immunogenic peptides of certain EnvBF regions, involved in T cell responses. It provides evidence that to improve immune responses to HIV there is a need to combine Env antigens from different clades, highlighting the convenience of the inclusion of BF antigens in future vaccines for geographic regions where these HIV variants circulate

Low-coordinate first-row transition metal complexes in catalysis and small molecule activation

Enforcing unusually low coordination numbers on transition metals with sterically demanding ligands has long been an area of interest for chemists. Historically, the synthesis of these challenging molecules has helped to elucidate fundamental principles of bonding and reactivity. More recently, there has been a move towards exploiting these highly reactive complexes to achieve a range of transformations using cheap, earth-abundant metals. In this Perspective, we will highlight selected examples of transition metal complexes with low coordination numbers that have been used in catalysis and the activation of small molecules featuring strong bonds (N2, CO2, and CO)

Disease-specific and general health-related quality of life in newly diagnosed prostate cancer patients: The Pros-IT CNR study

Background: The National Research Council (CNR) prostate cancer monitoring project in Italy (Pros-IT CNR) is an observational, prospective, ongoing, multicentre study aiming to monitor a sample of Italian males diagnosed as new cases of prostate cancer. The present study aims to present data on the quality of life at time prostate cancer is diagnosed. Methods: One thousand seven hundred five patients were enrolled. Quality of life is evaluated at the time cancer was diagnosed and at subsequent assessments via the Italian version of the University of California Los Angeles-Prostate Cancer Index (UCLA-PCI) and the Short Form Health Survey (SF-12). Results: At diagnosis, lower scores on the physical component of the SF-12 were associated to older ages, obesity and the presence of 3+ moderate/severe comorbidities. Lower scores on the mental component were associated to younger ages, the presence of 3+ moderate/severe comorbidities and a T-score higher than one. Urinary and bowel functions according to UCLA-PCI were generally good. Almost 5% of the sample reported using at least one safety pad daily to control urinary loss; less than 3% reported moderate/severe problems attributable to bowel functions, and sexual function was a moderate/severe problem for 26.7%. Diabetes, 3+ moderate/severe comorbidities, T2 or T3-T4 categories and a Gleason score of eight or more were significantly associated with lower sexual function scores at diagnosis. Conclusions: Data collected by the Pros-IT CNR study have clarified the baseline status of newly diagnosed prostate cancer patients. A comprehensive assessment of quality of life will allow to objectively evaluate outcomes of different profile of care