Incorporation of 4d and 5d Transition Metal Cyanometallates into Magnetic Clusters and Materials.

The work presented herein describes efforts to synthesize and characterize new types of cyanide-bridged molecular materials encompassing both discrete clusters and extended solids. This investigation focused on the incorporation of anisotropic 4d and 5d transition metal ion building blocks into such materials. In this vein, systematic studies on the magnetic properties of families of these cyano-bridges species were conducted and these new materials represent a new addition to the field of cyanide chemistry incorporating for the first time the hexacyanometallates of [Ru(CN)6]3- and [Os(CN)6]3- into discrete molecules and extended networks. These compounds will serve as models for new theoretical studies in understanding the role of magnetic exchange interactions, both isotropic and anisotropic, in the study of nanomagnetic materials. Results were obtained from using the well known octacyanometallates of MoV and WV as building blocks for the synthesis and the magnetic investigation of both trigonal bipyramidal and pentadecanuclear clusters including the discovery of a new SMM. By expanding the research to previously unused hexacyanometallates, the synthesis and characterization of the first known examples of clusters based on hexacyanoosmate(III) and hexacyanoruthenate(III) building blocks and their use in preparing new theoretical models of magnetic species. A novel pair of clusters is further detailed in the study of the trigonal bipyramidal clusters of [Fe(tmphen)2]3[Os(CN)6]2 and [Fe(tmphen)2]3[Ru(CN)6]2 and an in depth study of the CTIST behavior of these clusters using Mossbauer spectroscopy, variable temperature crystallography, epr, and variable temperature IR measurements. Finally, this work discusses new magnetic Prussian Blue analogs prepared from the hexacyanoosmate(III) and hexacyanoruthenate(III) anions with a comparison to the trigonal bipyramidal clusters presented based on these hexacyanoosmate(III) and hexacyanoruthenate(III) building blocks

Reduction from sparse LPN to LPN, Dual Attack 3.0

The security of code-based cryptography relies primarily on the hardness of decoding generic linear codes. Until very recently, all the best algorithms for solving the decoding problem were information set decoders (ISD). However, recently a new algorithm called RLPN-decoding which relies on a completely different approach was introduced and it has been shown that RLPN outperforms significantly ISD decoders for a rather large range of rates. This RLPN decoder relies on two ingredients, first reducing decoding to some underlying LPN problem, and then computing efficiently many parity-checks of small weight when restricted to some positions. We revisit RLPN-decoding by noticing that, in this algorithm, decoding is in fact reduced to a sparse-LPN problem, namely with a secret whose Hamming weight is small. Our new approach consists this time in making an additional reduction from sparse-LPN to plain-LPN with a coding approach inspired by coded-BKW. It outperforms significantly the ISD's and RLPN for code rates smaller than 0.42. This algorithm can be viewed as the code-based cryptography cousin of recent dual attacks in lattice-based cryptography. We depart completely from the traditional analysis of this kind of algorithm which uses a certain number of independence assumptions that have been strongly questioned recently in the latter domain. We give instead a formula for the LPNs noise relying on duality which allows to analyze the behavior of the algorithm by relying only on the analysis of a certain weight distribution. By using only a minimal assumption whose validity has been verified experimentally we are able to justify the correctness of our algorithm. This key tool, namely the duality formula, can be readily adapted to the lattice setting and is shown to give a simple explanation for some phenomena observed on dual attacks in lattices in [DP23]

TRP channels and monoterpenes: Past and current leads on analgesic properties

The activation of the transient receptor potential (TRP) channels expressed by sensory neurons is essential to the transduction of thermal and mechanical sensory information. In the setting of chronic inflammatory conditions, the activation of the melastatin family member 8 (TRPM8), the TRP vanilloid 1 (TRPV1), and the TRP ankyrin 1 (TRPA1) is correlated with pain hypersensitivity reactions. Monoterpenes, among which pulegone and menthol, a major class of phytocompounds present in essential oils of medicinal plants, are known modulators of those TRP channels activity. In the present review, we correlate the monoterpene content of plants with their historical therapeutic properties. We then describe how monoterpenes exert their anti-inflammatory and antihyperalgesia effects through modulation of TRP channels activity. Finally, we discuss the importance and the potential of characterizing new plant extracts and reassessing studied plant extracts for the development of ethnopharmacology-based innovative treatments for chronic pain. This review suggests that monoterpene solutions, based on composition from traditional healing herbs, offer an interesting avenue for the development of new phytotherapeutic treatments to alleviate chronic inflammatory pain conditions

Rigorous Foundations for Dual Attacks in Coding Theory

Dual attacks aiming at decoding generic linear codes have been found recently to outperform for certain parameters information set decoding techniques which have been for $60$ years the dominant tool for solving this problem and choosing the parameters of code-based cryptosystems. However, the analysis of the complexity of these dual attacks relies on some unproven assumptions that are not even fully backed up with experimental evidence. These dual attacks can actually be viewed as the code-based analogue of dual attacks in lattice based cryptography. Here too, dual attacks have been found out those past years to be strong competitors to primal attacks and a controversy has emerged whether similar heuristics made for instance on the independence of certain random variables really hold. We will show that the dual attacks in coding theory can be studied by providing in a first step a simple alternative expression of the fundamental quantity used in these dual attacks. We then show that this expression can be studied without relying on independence assumptions whatsoever. This study leads us to discover that there is indeed a problem with the latest and most powerful dual attack introduced in the recent Asiacrypt 2022 paper Statistical decoding 2.0: Reducing Decoding to LPN (RLPN) and that for the parameters chosen in this algorithm there are indeed false candidates which are produced and which are not predicted by the analysis provided there which relies on independence assumptions. We then suggest a slight modification of this algorithm consisting in a further verification step, analyze it thoroughly, provide experimental evidence that our analysis is accurate and show that the complexity claims made in RLPN are indeed valid for this modified algorithm. This approach provides a simple methodology for studying rigorously dual attacks which could turn out to be useful for further developing the subject

Reduction from sparse LPN to LPN, Dual Attack 3.0

The security of code-based cryptography relies primarily on the hardness of decoding generic linear codes. Until very recently, all the best algorithms for solving the decoding problem were information set decoders ($\mathsf{ISD}$). However, recently a new algorithm called RLPN-decoding which relies on a completely different approach was introduced and it has been shown that RLPN outperforms significantly $\mathsf{ISD}$ decoders for a rather large range of rates. This RLPN decoder relies on two ingredients, first reducing decoding to some underlying LPN problem, and then computing efficiently many parity-checks of small weight when restricted to some positions. We revisit RLPN-decoding by noticing that, in this algorithm, decoding is in fact reduced to a sparse-LPN problem, namely with a secret whose Hamming weight is small. Our new approach consists this time in making an additional reduction from sparse-LPN to plain-LPN with a coding approach inspired by $\mathsf{coded}$-$\mathsf{BKW}$. It outperforms significantly the $\mathsf{ISD}$\u27s and RLPN for code rates smaller than $0.42$. This algorithm can be viewed as the code-based cryptography cousin of recent dual attacks in lattice-based cryptography. We depart completely from the traditional analysis of this kind of algorithm which uses a certain number of independence assumptions that have been strongly questioned recently in the latter domain. We give instead a formula for the LPN noise relying on duality which allows to analyze the behavior of the algorithm by relying only on the analysis of a certain weight distribution. By using only a minimal assumption whose validity has been verified experimentally we are able to justify the correctness of our algorithm. This key tool, namely the duality formula, can be readily adapted to the lattice setting and is shown to give a simple explanation for some phenomena observed on dual attacks in lattices in [DP23]

Solvent-induced on/off switching of intramolecular electron transfer in a cyanide-bridged trigonal bipyramidal complex

A cyanide-bridged [Co3Fe2] cluster with trigonal bipyramidal geometry shows solvent-driven reversible on/off switching of its thermally induced electron-transfer-coupled spin transition (ETCST) behaviour

Statistical Decoding 2.0: Reducing Decoding to LPN

International audienceThe security of code-based cryptography relies primarily on the hardness of generic decoding with linear codes. The best generic decoding algorithms are all improvements of an old algorithm due to Prange: they are known under the name of information set decoders (ISD). A while ago, a generic decoding algorithm which does not belong to this family was proposed: statistical decoding. It is a randomized algorithm that requires the computation of a large set of parity-checks of moderate weight, and uses some kind of majority voting on these equations to recover the error. This algorithm was long forgotten because even the best variants of it performed poorly when compared to the simplest ISD algorithm. We revisit this old algorithm by using parity-check equations in a more general way. Here the parity-checks are used to get LPN samples with a secret which is part of the error and the LPN noise is related to the weight of the parity-checks we produce. The corresponding LPN problem is then solved by standard Fourier techniques. By properly choosing the method of producing these low weight equations and the size of the LPN problem, we are able to outperform in this way significantly information set decoders at code rates smaller than 0.3. It gives for the first time after 60 years, a better decoding algorithm for a significant range which does not belong to the ISD family

Analyse in vivo de l’activité anti-hyperalgésique de molécules innovantes

The treatment of pain is one of the major challenges of the 21st century, as the number of people suffering from chronic pain in the world exceeds 100 million. However, pain treatment is complex and medicine is currently extremely dependent on opiate-based analgesics, which have particularly severe side effects. Thus, in order to be able to continue managing pain, it is essential to develop alternatives treatments.In this context, the aim of my thesis work was to explore the analgesic potential of new innovative molecules targeting endogenous analgesic systems. During my thesis, I was able to characterise the anti-hyperalgesic potential of two innovative molecules, LIT-001, a molecule derived from the engineering of the oxytocin receptor, and pulegone, a monoterpene analogue of menthol, although it remains considerably understudied. The research was mainly based on an in vivo behavioural approach using an induced pain model.Le traitement des douleurs est l’un des enjeux important du 21ème siècle, en effet le nombre de personne souffrant de douleurs chroniques dans le monde dépasse les 100 millions. Cependant le traitement de ces douleurs est complexe et la médecine est aujourd’hui extrêmement dépendante des analgésiques dérivés des opiaces, qui ont pourtant des effets secondaires particulièrement délétères. Ainsi, pour continuer à traiter les douleurs il est essentiel de développer des traitements alternatifs. Dans ce contexte, mon travail de thèse a consisté à explorer le potentiel analgésique de nouvelles molécules innovantes ciblant les systèmes analgésiques endogènes. J’ai ainsi pendant ma thèse pu caractériser le potentiel anti-hyperalgésique de deux molécules innovantes, le LIT-001 une issue de l’ingénierie du récepteur de l’ocytocine et la pulégone, un monoterpène analogue du menthol et pourtant largement sous étudié. Cette recherche s’est principalement basé sur une approche comportementale in vivo basé sur un modèle de douleur induite

Analyse in vivo de l’activité anti-hyperalgésique de molécules innovantes

Le traitement des douleurs est l’un des enjeux important du 21ème siècle, en effet le nombre de personne souffrant de douleurs chroniques dans le monde dépasse les 100 millions. Cependant le traitement de ces douleurs est complexe et la médecine est aujourd’hui extrêmement dépendante des analgésiques dérivés des opiaces, qui ont pourtant des effets secondaires particulièrement délétères. Ainsi, pour continuer à traiter les douleurs il est essentiel de développer des traitements alternatifs. Dans ce contexte, mon travail de thèse a consisté à explorer le potentiel analgésique de nouvelles molécules innovantes ciblant les systèmes analgésiques endogènes. J’ai ainsi pendant ma thèse pu caractériser le potentiel anti-hyperalgésique de deux molécules innovantes, le LIT-001 une issue de l’ingénierie du récepteur de l’ocytocine et la pulégone, un monoterpène analogue du menthol et pourtant largement sous étudié. Cette recherche s’est principalement basé sur une approche comportementale in vivo basé sur un modèle de douleur induite.The treatment of pain is one of the major challenges of the 21st century, as the number of people suffering from chronic pain in the world exceeds 100 million. However, pain treatment is complex and medicine is currently extremely dependent on opiate-based analgesics, which have particularly severe side effects. Thus, in order to be able to continue managing pain, it is essential to develop alternatives treatments.In this context, the aim of my thesis work was to explore the analgesic potential of new innovative molecules targeting endogenous analgesic systems. During my thesis, I was able to characterise the anti-hyperalgesic potential of two innovative molecules, LIT-001, a molecule derived from the engineering of the oxytocin receptor, and pulegone, a monoterpene analogue of menthol, although it remains considerably understudied. The research was mainly based on an in vivo behavioural approach using an induced pain model

Fault growth analysis of the Gaoqing-Pingnan fault, Bohai Bay, China

Previous studies have suggested the growth of faults during the early Cenozoic within the Bohai Bay basin, China, was due to changes in plate tectonic stresses. The goal of this project was to analyze the Gaoqing-Pingnan fault growth in the Bohai Bay Basin, China, to shed insights on this geologically complex region. The fault has an abnormal zig-zag map-view geometry that shows abrupt strike changes along the fault. We seek to understand how the changes of strike along the fault could have developed. In order to answer this question a sedimentary basin analysis was performed of the region. Eight seismic lines and biostratigraphic wellbore data from 152 wells were used to interpret numerous stratigraphic horizons across the Gaoqing-Pingnan fault of Eocene to present-day ages. The fault throw of each horizon was measured across the fault on each seismic line and plotted in relation to the distance along the fault from west to east. The plot revealed a kinked fault distance-displacement relationship that was characteristic of fault linkage. In this model, two separate faults form, grow toward each other, and eventually merge into one unified fault. Understood within the context of the fault linkage model, each region of distinct strike along the Gaoqing-Pingnan fault was originally an independent, discrete fault. The point of change in fault strike can be attributed to later fault linkage zones. This understanding of the Gaoqing-Pingnan fault growth history may help shed light on the broader geologic events that impacted the Bohai Bay Basin. This project was completed with contributions from Yin Liu from China University of Petroleum.Earth and Atmospheric Sciences, Department ofHonors Colleg