Radiogenic isotope record of Arctic Ocean circulation and weathering inputs of the past 15 million years

Lead (Pb), neodymium (Nd), and strontium (Sr) isotopic analyses were carried out on sediment leachates (reflecting the isotope composition of past seawater) and digests of the bulk residues (reflecting detrital continental inputs) of Integrated Ocean Drilling Program (IODP) Leg 302 and core PS2185 from the Lomonosov Ridge (Arctic Ocean). Our records are interpreted to reflect changes in continental erosion and oceanic circulation, driven predominantly by tectonic forcing on million-year timescales in the older (pre-2 Ma) part of the record and by climatic forcing of weathering and erosion of the Eurasian continental margin on thousand-year timescales in the younger (post-2 Ma) part. These data, covering the past ~15 Ma, show that continental inputs to the central Arctic Ocean have been more closely linked to glacial and hydrological processes occurring on the Eurasian margin than on continental North America and Greenland. The constancy of the detrital input signatures supports the early existence of an Arctic sea ice cover, whereas the major initiation of Northern Hemisphere glaciation at 2.7 Ma appears to have had little impact on the weathering regime of the Eurasian continental margin.

(Table 1) Ratio of hydroxy-GDGT vs. the total core GDGT was calculated based on the detection of hydroxy-GDGT

Hydroxylated glycerol dialkyl glycerol tetraethers (hydroxy-GDGTs) were detected in marine sediments of diverse depositional regimes and ages. Mass spectrometric evidence, complemented by information gleaned from two-dimensional (2D) 1H-13C nuclear magnetic resonance (NMR) spectroscopy on minute quantities of target analyte isolated from marine sediment, allowed us to identify one major compound as a monohydroxy-GDGT with acyclic biphytanyl moieties (OH-GDGT-0). NMR spectroscopic and mass spectrometric data indicate the presence of a tertiary hydroxyl group suggesting the compounds are the tetraether analogues of the widespread hydroxylated archaeol derivatives that have received great attention in geochemical studies of the last two decades. Three other related compounds were assigned as acyclic dihydroxy-GDGT (2OH-GDGT-0) and monohydroxy-GDGT with one (OH-GDGT-1) and two cyclopentane rings (OH-GDGT-2). Based on the identification of hydroxy-GDGT core lipids, a group of previously reported unknown intact polar lipids (IPLs), including the ubiquitously distributed H341-GDGT (Lipp J. S. and Hinrichs K. -U. (2009) Structural diversity and fate of intact polar lipids in marine sediments. Geochim. Cosmochim. Acta 73, 6816-6833), and its analogues were tentatively identified as glycosidic hydroxy-GDGTs. In addition to marine sediments, we also detected hydroxy-GDGTs in a culture of Methanothermococcus thermolithotrophicus. Given the previous finding of the putative polar precursor H341-GDGT in the planktonic marine crenarchaeon Nitrosopumilus maritimus, these compounds are synthesized by representatives of both cren- and euryarchaeota. The ubiquitous distribution and apparent substantial abundance of hydroxy-GDGT core lipids in marine sediments (up to 8% of total isoprenoid core GDGTs) point to their potential as proxies.

Sediment and pore water chemistry of cores 214 and 755 recovered during Meteor M72/1 and POSEIDON cruise POS317/2, northwestern Black Sea

High-resolution sedimentary records of major and minor elements (Al, Ba, Ca, Sr, Ti), total organic carbon (TOC), and profiles of pore water constituents (SO42-, CH4, Ca2+, Ba2+, Mg2+, alkalinity) were obtained for two gravity cores (core 755, 501 m water depth and core 214, 1686 m water depth) from the northwestern Black Sea. The records were examined in order to gain insight into the cycling of Ba in anoxic marine sediments characterized by a shallow sulfate-methane transition (SMT) as well as the applicability of barite as a primary productivity proxy in such a setting. The Ba records are strongly overprinted by diagenetic barite (BaSO4) precipitation and remobilization; authigenic Ba enrichments were found at both sites at and slightly above the current SMT. Transport reaction modeling was applied to simulate the migration of the SMT during the changing geochemical conditions after the Holocene seawater intrusion into the Black Sea. Based on this, sediment intervals affected by diagenetic Ba redistribution were identified. Results reveal that the intense overprint of Ba and Baxs (Ba excess above detrital average) strongly limits its correlation to primary productivity. These findings have implications for other modern and ancient anoxic basins, such as sections covering the Oceanic Anoxic Events for which Ba is frequently used as a primary productivity indicator. Our study also demonstrates the limitations concerning the use of Baxs as a tracer for downward migrations of the SMT: due to high sedimentation rates at the investigated sites, diagenetic barite fronts are buried below the SMT within a relatively short period. Thus, 'relict' barite fronts would only be preserved for a few thousands of years, if at all.

Structural and Biochemical Dissection of the Trehalose Biosynthetic Complex in Pathogenic Fungi

Trehalose is a non-reducing disaccharide essential for pathogenic fungal survival and virulence. The biosynthesis of trehalose requires the trehalose-6-phosphate synthase, Tps1, and trehalose-6-phosphate phosphatase, Tps2. More importantly, the trehalose biosynthetic pathway is absent in mammals, conferring this pathway as an ideal target for antifungal drug design. However, lack of germane biochemical and structural information hinders antifungal drug design against these targets.

In this dissertation, macromolecular X-ray crystallography and biochemical assays were employed to understand the structures and functions of proteins involved in the trehalose biosynthetic pathway. I report here the first eukaryotic Tps1 structures from Candida albicans (C. albicans) and Aspergillus fumigatus (A. fumigatus) with substrates or substrate analogs. These structures reveal the key residues involved in substrate binding and catalysis. Subsequent enzymatic assays and cellular assays highlight the significance of these key Tps1 residues in enzyme function and fungal stress response. The Tps1 structure captured in its transition-state with a non-hydrolysable inhibitor demonstrates that Tps1 adopts an “internal return like” mechanism for catalysis. Furthermore, disruption of the trehalose biosynthetic complex formation through abolishing Tps1 dimerization reveals that complex formation has regulatory function in addition to trehalose production, providing additional targets for antifungal drug intervention.

I also present here the structure of the Tps2 N-terminal domain (Tps2NTD) from C. albicans, which may be involved in the proper formation of the trehalose biosynthetic complex. Deletion of the Tps2NTD results in a temperature sensitive phenotype. Further, I describe in this dissertation the structures of the Tps2 phosphatase domain (Tps2PD) from C. albicans, A. fumigatus and Cryptococcus neoformans (C. neoformans) in multiple conformational states. The structures of the C. albicans Tps2PD -BeF3-trehalose complex and C. neoformans Tps2PD(D24N)-T6P complex reveal extensive interactions between both glucose moieties of the trehalose involving all eight hydroxyl groups and multiple residues of both the cap and core domains of Tps2PD. These structures also reveal that steric hindrance is a key underlying factor for the exquisite substrate specificity of Tps2PD. In addition, the structures of Tps2PD in the open conformation provide direct visualization of the conformational changes of this domain that are effected by substrate binding and product release.

Last, I present the structure of the C. albicans trehalose synthase regulatory protein (Tps3) pseudo-phosphatase domain (Tps3PPD) structure. Tps3PPD adopts a haloacid dehydrogenase superfamily (HADSF) phosphatase fold with a core Rossmann-fold domain and a α/β fold cap domain. Despite lack of phosphatase activity, the cleft between the Tps3PPD core domain and cap domain presents a binding pocket for a yet uncharacterized ligand. Identification of this ligand could reveal the cellular function of Tps3 and any interconnection of the trehalose biosynthetic pathway with other cellular metabolic pathways.

Combined, these structures together with significant biochemical analyses advance our understanding of the proteins responsible for trehalose biosynthesis. These structures are ready to be exploited to rationally design or optimize inhibitors of the trehalose biosynthetic pathway enzymes. Hence, the work described in this thesis has laid the groundwork for the design of Tps1 and Tps2 specific inhibitors, which ultimately could lead to novel therapeutics to treat fungal infections.

Boron isotope and B/Ca ratios of planktonic foraminifera

Here a new analytical methodology is described for measuring the isotopic composition of boron in foraminifera using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). This new approach is fast (~10 samples analysed in duplicate per analytical session) and accurate (to better than 0.25 per mil at 95% confidence) with acceptable sample size requirements (1-3 mg of carbonate). A core top calibration of several common planktic and two benthic species from geographically widespread localities shows a very close agreement between the isotopic composition measured by MC-ICPMS and the isotopic composition of B(OH)-4 in seawater (as predicted using the recently measured isotopic equilibrium factor of 1.0272) at the depth of habitat. A down core and core top investigation of boron concentration (B/Ca ratio) shows that the partition coefficient is influenced by [CO2-3] complicating the application of this proxy. Nevertheless, it is demonstrated that these two proxies can be used to fully constrain the carbonate system of surface water in the Caribbean Sea (ODP Site 999A) over the last 130 kyr. This reconstruction shows that during much of the Holocene and the last interglacial period surface water at Site 999A was in equilibrium with the atmosphere with respect to CO2. During the intervening colder periods although the surface water pCO2 was lower than the Holocene, it was a minor to significant source of CO2 to the atmosphere possibly due to either an expansion of the eastern equatorial Atlantic upwelling zone, or a more local expansion of coastal upwelling in the southern Caribbean. Such reorganisation of the oceanic carbonate system in favour of a larger source of CO2 to the atmosphere from the equatorial ocean may require mechanisms responsible for lowering atmospheric CO2 during glacial periods to be more efficient than previously supposed.

Opinion: Can coalescent models explain deep divergences in the diatoms and argue for the acceptance of paraphyletic taxa at all taxonomic hierarchies?

Although ancestral polymorphisms and incomplete lineage sorting are commonly used at the population level, increasing reports of these models have been invoked and tested to explain deep radiations. Hypotheses are put forward for ancestral polymorphisms being the likely reason for paraphyletic taxa at the class level in the diatoms based on an ancient rapid radiation of the entire groups. Models for ancestral deep coalescence are invoked to explain paraphyly and molecular evolution at the class level in the diatoms. Other examples at more recent divergences are also documented. Discussion as to whether or not paraphyletic groups seen in the diatoms at all taxonomic levels should be recognized is provided. The continued use of the terms centric and pennate diatoms is substantiated with additional evidence produced to support their use in diatoms both as descriptive terms for both groups and as taxonomic groups for the latter because new morphological evidence from the auxospores justifies the formal classification of the basal and core araphids as new subclasses of pennate diatoms in the Class Bacillariophyceae. Keys for higher levels of the diatoms showing how the terms centrics and araphid diatoms can be defined are provided.

Opinion: Can coalescent models explain deep divergences in the diatoms and argue for the acceptance of paraphyletic taxa at all taxonomic hierarchies?

Although ancestral polymorphisms and incomplete lineage sorting are commonly used at the population level, increasing reports of these models have been invoked and tested to explain deep radiations. Hypotheses are put forward for ancestral polymorphisms being the likely reason for paraphyletic taxa at the class level in the diatoms based on an ancient rapid radiation of the entire groups. Models for ancestral deep coalescence are invoked to explain paraphyly and molecular evolution at the class level in the diatoms. Other examples at more recent divergences are also documented. Discussion as to whether or not paraphyletic groups seen in the diatoms at all taxonomic levels should be recognized is provided. The continued use of the terms centric and pennate diatoms is substantiated with additional evidence produced to support their use in diatoms both as descriptive terms for both groups and as taxonomic groups for the latter because new morphological evidence from the auxospores justifies the formal classification of the basal and core araphids as new subclasses of pennate diatoms in the Class Bacillariophyceae. Keys for higher levels of the diatoms showing how the terms centrics and araphid diatoms can be defined are provided.

Tegument Glycoproteins and Cathepsins of Newly Excysted Juvenile Fasciola hepatica Carry Mannosidic and Paucimannosidic N-glycans

Recently, the prevalence of Fasciola hepatica in some areas has increased considerably and the availability of a vaccine to protect livestock from infection would represent a major advance in tools available for controlling this disease. To date, most vaccine-target discovery research on this parasite has concentrated on proteomic and transcriptomic approaches whereas little work has been carried out on glycosylation. As the F. hepatica tegument (Teg) may contain glycans potentially relevant to vaccine development and the Newly Excysted Juvenile (NEJ) is the first lifecycle stage in contact with the definitive host, our work has focused on assessing the glycosylation of the NEJTeg and identifying the NEJTeg glycoprotein repertoire. After in vitro excystation, NEJ were fixed and NEJTeg was extracted. Matrix-assisted laser desorption ionisation-time of flight-mass spectrometry (MALDI-TOF-MS) analysis of released N-glycans revealed that oligomannose and core-fucosylated truncated N-glycans were the most dominant glycan types. By lectin binding studies these glycans were identified mainly on the NEJ surface, together with the oral and ventral suckers. NEJTeg glycoproteins were affinity purified after targeted biotinylation of the glycans and identified using liquid chromatography and tandem mass spectrometry (LC-MS/MS). From the total set of proteins previously identified in NEJTeg, eighteen were also detected in the glycosylated fraction, including the F. hepatica Cathepsin B3 (FhCB3) and two of the Cathepsin L3 (FhCL3) proteins, among others. To confirm glycosylation of cathepsins, analysis at the glycopeptide level by LC-ESI-ion-trap-MS/MS with collision-induced dissociation (CID) and electron-transfer dissociation (ETD) was carried out. We established that cathepsin B1 (FhCB1) on position N80, and FhCL3 (BN1106_s10139B000014, scaffold10139) on position N153, carry unusual paucimannosidic Man2GlcNAc2 glycans. To our knowledge, this is the first description of F. hepatica NEJ glycosylation and the first report of N-glycosylation of F. hepatica cathepsins. The significance of these findings for immunological studies and vaccine development is discussed.

Photoionization of Co+ and electron-impact excitation of Co2 + using the Dirac R-matrix method

Modelling of massive stars and supernovae (SNe) plays a crucial role in understanding galaxies. From this modelling we can derive fundamental constraints on stellar evolution, mass-loss processes, mixing, and the products of nucleosynthesis. Proper account must be taken of all important processes that populate and depopulate the levels (collisional excitation, de-excitation, ionization, recombination, photoionization, bound–bound processes). For the analysis of Type Ia SNe and core collapse SNe (Types Ib, Ic and II) Fe group elements are particularly important. Unfortunately little data is currently available and most noticeably absent are the photoionization cross-sections for the Fe-peaks which have high abundances in SNe. Important interactions for both photoionization and electron-impact excitation are calculated using the relativistic Dirac atomic R-matrix codes (DARC) for low-ionization stages of Cobalt. All results are calculated up to photon energies of 45 eV and electron energies up to 20 eV. The wavefunction representation of Co III has been generated using GRASP0 by including the dominant 3d⁷, 3d⁶[4s, 4p], 3p⁴3d⁹ and 3p⁶3d⁹ configurations, resulting in 292 fine structure levels. Electron-impact collision strengths and Maxwellian averaged effective collision strengths across a wide range of astrophysically relevant temperatures are computed for Co III. In addition, statistically weighted level-resolved ground and metastable photoionization cross-sections are presented for Co II and compared directly with existing work.

Pass-through of International food prices to domestic ination during and after the great recession: evidence from a set of Latin American economies

We examined how international food price shocks have impacted local ination processes in Brazil, Chile, Colombia, Mexico, and Peru in the past decade -- Using impulse-response analysis coming from cointegrated VARs, we wind that international food ination shocks take from one to six quarters to pass through to domestic head-line ination, depending on the country -- In addition, by calculating the elasticity of local prices to an international food price shock, we found that this pass-through is not complete -- We also take a closer look at how this type of shock affects local food and core prices separately, and asses the possibility second round effects over core ination stemming from the shock -- We wind that a transmission to headline prices does occur, and that part of the transmission is associated with rising core prices both directly and through possible second round effects, which implies a role for monetary policy when such a shock takes place -- This is especially relevant given that international food prices have recently been on an upward trend after falling considerably during the Great Recession

Experimental and diagnostic protocol for the physical component of the CMIP6 Ocean Model Intercomparison Project (OMIP)

The Ocean Model Intercomparison Project (OMIP) aims to provide a framework for evaluating, understanding, and improving the ocean and sea-ice components of global climate and earth system models contributing to the Coupled Model Intercomparison Project Phase 6 (CMIP6). OMIP addresses these aims in two complementary manners: (A) by providing an experimental protocol for global ocean/sea-ice models run with a prescribed atmospheric forcing, (B) by providing a protocol for ocean diagnostics to be saved as part of CMIP6. We focus here on the physical component of OMIP, with a companion paper (Orr et al., 2016) offering details for the inert chemistry and interactive biogeochemistry. The physical portion of the OMIP experimental protocol follows that of the interannual Coordinated Ocean-ice Reference Experiments (CORE-II). Since 2009, CORE-I (Normal Year Forcing) and CORE-II have become the standard method to evaluate global ocean/sea-ice simulations and to examine mechanisms for forced ocean climate variability. The OMIP diagnostic protocol is relevant for any ocean model component of CMIP6, including the DECK (Diagnostic, Evaluation and Characterization of Klima experiments), historical simulations, FAFMIP (Flux Anomaly Forced MIP), C4MIP (Coupled Carbon Cycle Climate MIP), DAMIP (Detection and Attribution MIP), DCPP (Decadal Climate Prediction Project), ScenarioMIP (Scenario MIP), as well as the ocean-sea ice OMIP simulations. The bulk of this paper offers scientific rationale for saving these diagnostics.

OMIP contribution to CMIP6: experimental and diagnostic protocol for the physical component of the Ocean Model Intercomparison Project

The Ocean Model Intercomparison Project (OMIP) is an endorsed project in the Coupled Model Intercomparison Project Phase 6 (CMIP6). OMIP addresses CMIP6 science questions, investigating the origins and consequences of systematic model biases. It does so by providing a framework for evaluating (including assessment of systematic biases), understanding, and improving ocean, sea-ice, tracer, and biogeochemical components of climate and earth system models contributing to CMIP6. Among the WCRP Grand Challenges in climate science (GCs), OMIP primarily contributes to the regional sea level change and near-term (climate/decadal) prediction GCs. OMIP provides (a) an experimental protocol for global ocean/sea-ice models run with a prescribed atmospheric forcing; and (b) a protocol for ocean diagnostics to be saved as part of CMIP6. We focus here on the physical component of OMIP, with a companion paper (Orr et al., 2016) detailing methods for the inert chemistry and interactive biogeochemistry. The physical portion of the OMIP experimental protocol follows the interannual Coordinated Ocean-ice Reference Experiments (CORE-II). Since 2009, CORE-I (Normal Year Forcing) and CORE-II (Interannual Forcing) have become the standard methods to evaluate global ocean/sea-ice simulations and to examine mechanisms for forced ocean climate variability. The OMIP diagnostic protocol is relevant for any ocean model component of CMIP6, including the DECK (Diagnostic, Evaluation and Characterization of Klima experiments), historical simulations, FAFMIP (Flux Anomaly Forced MIP), C4MIP (Coupled Carbon Cycle Climate MIP), DAMIP (Detection and Attribution MIP), DCPP (Decadal Climate Prediction Project), ScenarioMIP, HighResMIP (High Resolution MIP), as well as the ocean/sea-ice OMIP simulations.

Dynamic mechanical-thermal, microstructural and mechanical analysis of ultra-light polymer-metal composites: influence of forming

A really particular and innovative metal-polymer sandwich material is Hybrix. Hybrix is a product developed and manufactured by Lamera AB, Gothenburg, Sweden. This innovative hybrid material is composed by two relatively thin metal layers if compared to the core thickness. The most used metals are aluminum and stainless steel and are separated by a core of nylon fibres oriented perpendicularly to the metal plates. The core is then completed by adhesive layers applied at the PA66-metal interface that once cured maintain the nylon fibres in position. This special material is very light and formable. Moreover Hybrix, depending on the specific metal which is used, can achieve a good corrosion resistance and it can be cut and punched easily. Hybrix architecture itself provides extremely good bending stiffness, damping properties, insulation capability, etc., which again, of course, change in magnitude depending in the metal alloy which is used, its thickness and core thickness. For these reasons nowadays it shows potential for all the applications which have the above mentioned characteristic as a requirement. Finally Hybrix can be processed with tools used in regular metal sheet industry and can be handled as solid metal sheets. In this master thesis project, pre-formed parts of Hybrix were studied and characterized. Previous work on Hybrix was focused on analyze its market potential and different adhesive to be used in the core. All the tests were carried out on flat unformed specimens. However, in order to have a complete description of this material also the effect of the forming process must be taken into account. Thus the main activities of the present master thesis are the following: Dynamic Mechanical-Thermal Analysis (DMTA) on unformed Hybrix samples of different thickness and on pre-strained Hybrix samples, pure epoxy adhesive samples analysis and finally moisture effects evaluation on Hybrix composite structure.

Exploring Calling Work Orientation: Construct Clarity and Organizational Implications

Employees maintain a personal view toward their work, which can be referred to as their work orientation. Some employees view their work as their life’s purpose (i.e., calling work orientation) and they tend to be 1) prosocially motivated, 2) derive meaning from work, and 3) feel that their purpose is from beyond the self. The purpose of the current dissertation was to differentiate calling work orientation from other similar workplace constructs, to investigate the most common covariates of calling work orientation, and to empirically test two possible moderators of the relationship between calling work orientation and work-related outcomes of job satisfaction, job performance, and work engagement. Two independent samples were collected for the purpose of testing hypotheses: data were collected from 520 working students and from 520 non-student employees. Participants from the student sample were recruited at Florida International University, and participants from the employee sample were recruited via the Amazon Mechanical Turk website. Participants from the student sample answered demographic questions and responded to self-report measures of job satisfaction, job performance, work engagement, spirituality, meaningful work, prosocial motivation, and work orientation. The procedure was similar for the employee sample, but their survey also included measures of counterproductive work behaviors, organizational citizenship behaviors, conscientiousness, and numerical ability. Additionally, employees were asked whether they would be willing to have a direct supervisor, peer, co-worker, client, or subordinate rate their job performance. Hierarchical regression findings suggest calling work orientation was predictive of overall job performance above and beyond two common predictors of performance, conscientiousness and numerical ability. The results for the covariate analyses provided evidence that prosocial motivation, meaningful work, and spirituality do play a significant role in the development of an employees’ work orientation. Perceived career opportunities moderated the relationship between calling work orientation and job performance for the employee sample. Core self-evaluations moderated the relationship between calling work orientation and job performance, and core self-evaluations moderated the relationship between calling work orientation and work engagement. Collectively, findings from the current study highlight the benefits of examining work orientation in the prediction of workplace outcomes.

Engineered zeolitic materials: synthesis and application

Les zéolithes étant des matériaux cristallins microporeux ont démontré leurs potentiels et leur polyvalence dans un nombre très important d’applications. Les propriétés uniques des zéolithes ont poussé les chercheurs à leur trouver constamment de nouvelles utilités pour tirer le meilleur parti de ces matériaux extraordinaires. Modifier les caractéristiques des zéolithes classiques ou les combiner en synergie avec d’autres matériaux se trouvent être deux approches viables pour trouver encore de nouvelles applications. Dans ce travail de doctorat, ces deux approches ont été utilisées séparément, premièrement avec la modification morphologique de la ZSM-12 et deuxièmement lors de la formation des matériaux de type coeur/coquille (silice mésoporeuses@silicalite-1). La ZSM-12 est une zéolithe à haute teneur en silice qui a récemment attiré beaucoup l’attention par ses performances supérieures dans les domaines de l’adsorption et de la catalyse. Afin de synthétiser la ZSM-12 avec une pureté élevée et une morphologie contrôlée, la cristallisation de la zéolithe ZSM-12 a été étudiée en détail en fonction des différents réactifs chimiques disponibles (agent directeur de structure, types de silicium et source d’aluminium) et des paramètres réactionnels (l’alcalinité, ratio entre Na, Al et eau). Les résultats présentés dans cette étude ont montré que, contrairement à l’utilisation du structurant organique TEAOH, en utilisant un autre structurant, le MTEAOH, ainsi que le Al(o-i-Pr)3, cela a permis la formation de monocristaux ZSM-12 monodisperses dans un temps plus court. L’alcalinité et la teneur en Na jouent également des rôles déterminants lors de ces synthèses. Les structures de types coeur/coquille avec une zéolithe polycristalline silicalite-1 en tant que coquille, entourant un coeur formé par une microsphère de silice mésoporeuse (tailles de particules de 1,5, 3 et 20-45 μm) ont été synthétisés soit sous forme pure ou chargée avec des espèces hôtes métalliques. Des techniques de nucléations de la zéolithe sur le noyau ont été utilisées pour faire croitre la coquille de façon fiable et arriver à former ces matériaux. C’est la qualité des produits finaux en termes de connectivité des réseaux poreux et d’intégrité de la coquille, qui permet d’obtenir une stéréosélectivité. Ceci a été étudié en faisant varier les paramètres de synthèse, par exemple, lors de prétraitements qui comprennent ; la modification de surface, la nucléation, la calcination et le nombre d’étapes secondaires de cristallisation hydrothermale. En fonction de la taille du noyau mésoporeux et des espèces hôtes incorporées, l’efficacité de la nucléation se révèle être influencée par la technique de modification de surface choisie. En effet, les microsphères de silice mésoporeuses contenant des espèces métalliques nécessitent un traitement supplémentaire de fonctionnalisation chimique sur leur surface externe avec des précurseurs tels que le (3-aminopropyl) triéthoxysilane (APTES), plutôt que d’utiliser une modification de surface avec des polymères ioniques. Nous avons également montré que, selon la taille du noyau, de deux à quatre traitements hydrothermaux rapides sont nécessaires pour envelopper totalement le noyau sans aucune agrégation et sans dissoudre le noyau. De tels matériaux avec une enveloppe de tamis moléculaire cristallin peuvent être utilisés dans une grande variété d’applications, en particulier pour de l’adsorption et de la catalyse stéréo-sélective. Ce type de matériaux a été étudié lors d’une série d’expériences sur l’adsorption sélective du glycérol provenant de biodiesel brut avec des compositions différentes et à des températures différentes. Les résultats obtenus ont été comparés à ceux utilisant des adsorbants classiques comme par exemple du gel de sphères de silice mésoporeux, des zéolithes classiques, silicalite-1, Si-BEA et ZSM-5(H+), sous forment de cristaux, ainsi que le mélange physique de ces matériaux références, à savoir un mélange silicalite-1 et le gel de silice sphères. Bien que le gel de sphères de silice mésoporeux ait montré une capacité d’adsorption de glycérol un peu plus élevée, l’étude a révélé que les adsorbants mésoporeux ont tendance à piéger une quantité importante de molécules plus volumineuses, telles que les « fatty acid methyl ester » (FAME), dans leur vaste réseau de pores. Cependant, dans l’adsorbant à porosité hiérarchisée, la fine couche de zéolite silicalite-1 microporeuse joue un rôle de membrane empêchant la diffusion des molécules de FAME dans les mésopores composant le noyau/coeur de l’adsorbant composite, tandis que le volume des mésopores du noyau permet l’adsorption du glycérol sous forme de multicouches. Finalement, cette caractéristique du matériau coeur/coquille a sensiblement amélioré les performances en termes de rendement de purification et de capacité d’adsorption, par rapport à d’autres adsorbants classiques, y compris le gel de silice mésoporeuse et les zéolithes.