Soil organic matter (SOM) is the largest terrestrial pool of organic carbon (C), and potential carbon-climate feedbacks involving SOM decomposition could exacerbate anthropogenic climate change. Despite the importance of SOM in the global C cycle, our understanding of the controls on SOM stabilization and decomposition is still developing, and as such, SOM dynamics are a source of major uncertainty in current Earth system models (ESMs), which reduces the effectiveness of these models in predicting the efficacy of climate change mitigation strategies. To improve our understanding of controls on SOM decomposition at scales relevant to such modeling efforts, A and upper B horizon soil samples from 22 National Ecological Observatory Network (NEON) sites spanning the conterminous U.S. were incubated for 52 weeks under conditions representing site-specific mean summer temperature and horizon-specific field capacity (-33 kPa) water potential. Cumulative CO2 respired was periodically measured and normalized by soil organic C content to obtain cumulative specific respiration (CSR). A two-pool decomposition model was fitted to the CSR data to calculate decomposition rates of fast- (kfast) and slow-cycling pools (kslow). Post-LASSO best subsets multiple linear regression was used to construct horizon-specific models of significant predictors for CSR, kfast, and kslow. Significant predictors for all three response variables consisted mostly of proximal factors related to clay-sized fraction mineralogy and SOM composition. Non-crystalline minerals and lower SOM lability negatively affected CSR for both A and B horizons. Significant predictors for decomposition rates varied by horizon and pool. B horizon decomposition rates were positively influenced by nitrogen (N) availability, while an index of pyrogenic C had a negative effect on kfast in both horizons. These results reinforce the recognized need to explicitly represent SOM stabilization via interactions with non-crystalline minerals in ESMs, and they also suggest that increased N inputs could enhance SOM decomposition in the subsoil, highlighting another mechanism beyond shifts in temperature and precipitation regimes that could alter SOM decomposition rates. / Master of Science / Soils contain a large amount of carbon (C) in the form of soil organic matter (SOM), and there is the potential for the increased decomposition of SOM due to warmer temperatures to cause climate change to become worse through the release of additional CO₂ into the atmosphere. However, we still do not know exactly what is most important for predicting how vulnerable SOM is to decomposition at continental scales, and this results in a substantial amount of uncertainty in Earth system models used to predict climate change. To address this question, the proportion of organic C decomposed in soil samples from the topsoil and subsoil from 22 sites across the conterminous U.S. was monitored over the course of a year under optimal moisture conditions and at site-specific summer temperature. Additionally, a mathematical model was fitted to the proportion of organic C decomposed over time to estimate decomposition rates of a quickly decomposing pool of SOM and a slowly decomposing pool of SOM. The proportion of organic C decomposed and decomposition rates were related to soil and site properties using multiple linear regression to find which soil and site properties were most important for predicting these response variables. The type of clay-sized mineral and SOM chemical composition were found to be important predictors of the proportion of organic C decomposed for both topsoil and subsoil samples. The important predictors for decomposition rates varied by pool and by topsoil vs. subsoil. For subsoil decomposition rates, it was found that a greater availability of nitrogen (N) increased decomposition rates, and in the quickly decomposing pool, it was found that fire-derived organic matter slowed decomposition rates. The results of this study showed the general importance of local factors for controlling SOM decomposition. Specifically, it showed that the type of clay-sized mineral present at a site needs to be considered as well as the fact that N might increase SOM decomposition in the subsoil.

Los materiales autosanables son materiales con la capacidad de reparar sus daños de forma autónoma o con ayuda mínima de estímulos externos. En el campo de la construcción, el desarrollo de elementos autosanables aumentará la durabilidad de las estructuras y reducirá las acciones de mantenimiento y reparación. Los elementos de hormigón armado presentan frecuentemente pequeñas fisuras (< 0.3 mm), no relevantes mecánicamente, pero que pueden suponer un punto de entrada para agentes agresivos. El hormigón tiene una cierta capacidad de autosanación, capaz de cerrar pequeñas fisuras, producida principalmente por la hidratación continuada y la carbonatación. Estudios recientes han intentado mejorar dicha capacidad y diseñar productos específicos para conseguirla. Estos productos incluyen, entre otros, aditivos cristalinos, agentes micro o macroencapsulados, e incluso el uso de bacterias. Los aditivos cristalinos (CA) son un tipo de aditivo para hormigón que se considera que aporta propiedades de autosanación. No obstante, la falta de conocimiento sobre su comportamiento limita su uso. Además, los métodos para evaluar la autosanación en hormigones no están estandarizados todavía. Esto complica la realización de un análisis crítico de los diferentes productos y métodos de evaluación propuestos en la literatura. Para responder a esta falta de conocimiento, los objetivos de esta tesis son: 1) estudiar y proponer procedimientos experimentales para evaluar los fenómenos de autosanación en hormigón y, 2) evaluar experimentalmente las mejoras producidas al introducir aditivos cristalinos. Esta tesis incluye como ensayos para la determinación de la autosanación: la evaluación del cierre de fisuras, la permeabilidad al agua, flexión a tres puntos y absorción capilar. Además, se han realizado varias campañas experimentales para validar los ensayos propuestos. Posteriormente, estos ensayos se han utilizado para analizar la influencia de varios parámetros, incluyendo entre otros: presencia de aditivos cristalinos, nivel de daño, tiempo necesario para el sanado, composición del hormigón y condiciones de sanado. Finalmente, se analizan los efectos producidos al añadir aditivos cristalinos en hormigón en la fluidez, resistencia e hidratación. Los resultados muestran que el cierre de fisuras es un ensayo eficaz y sencillo para evaluar la autosanación. Sin embargo, la orientación de la fisura durante el sanado ha resultado ser de gran importancia, y no considerar este aspecto puede llevar a conclusiones engañosas. El ensayo de permeabilidad al agua propuesto en este trabajo presenta una buena estabilidad y es fácil de implementar en laboratorios. Además, las relaciones obtenidas entre los parámetros de fisura y la permeabilidad del agua han confirmado la relación cúbica indicada en la literatura. Este trabajo muestra que analizar la eficiencia de autosanado mediante el cierre de fisuras puede llevar a una sobreestimación de la capacidad de sanación, comparada con los resultados obtenidos mediante permeabilidad. Los ensayos de sorptividad resultaron fáciles de implementar, sin embargo, los resultados obtenidos mostraron una alta dispersión y sensibilidad a las variaciones en las fisuras producidas durante el proceso de prefisuración. En cuanto a la evaluación de la recuperación mecánica, los resultados muestran que la evolución de las propiedades del hormigón con el tiempo es un parámetro que debe considerarse, especialmente en fisuras de edades tempranas. En este trabajo se ha obtenido que los aditivos cristalinos potencian las reacciones de autosanación, pero tienen una capacidad limitada. La proximidad de los CA a la industria es un punto positivo para su inclusión como un nuevo tipo de aditivo de hormigón. Sin embargo, los resultados obtenidos en esta tesis indican que se necesitan más análisis para determinar sus efectos completos en hormigón, especialmente con respect / Self-healing materials are materials with the capability to repair their damage autonomously or with minimal help from an external stimulus. In the construction field, the development of self-healing elements will increase the durability of structures and reduce their maintenance and repair actions. Reinforced concrete elements frequently suffer small cracks (< 0.3 mm), not relevant mechanically, but they can be an entrance point for aggressive agents. Concrete has a natural self-healing capability able to seal small cracks, produced by the continuing hydration and carbonation processes. Recent studies have attempted to improve that healing capability and to design specific products to achieve it. These products include, among others: crystalline admixtures, micro- or macro-encapsulated agents, and even the use of bacteria. Crystalline admixtures (CA) are a concrete admixture that is claimed to provide self-healing properties. However, the lack of knowledge on their behavior and self-healing properties limits their usage. In addition, the methods to evaluate the self-healing capability of mortar and concrete are not standardized yet. This complicates the performance of a critical analysis of the different self-healing products and evaluation methods found in the literature. In order to answer to this lack of knowledge, the objectives of this thesis are: 1) to study and propose experimental procedures in order to evaluate self-healing in concrete and, 2) to evaluate experimentally the self-healing enhancements produced when introducing crystalline admixtures. This thesis includes the following tests for the determination of the self-healing: the evaluation of crack closing, water permeability, three point bending tests and capillary absorption test. In addition, several experimental campaigns have been performed with the objective of validating the proposed tests. Afterwards, these methods have been used to analyze the influence of several parameters, including among others: the presence of crystalline admixtures, the damage extent, healing time needed, concrete composition and healing conditions. Finally, the effects that crystalline admixtures produce in concrete are analyzed in terms of slump, strength and hydration. The results show that crack closing is an effective and simple method to evaluate self-healing. However, the orientation of the crack during healing is of great importance, and disregarding this aspect may lead to misleading conclusions. The water permeability method proposed in this work has good stability and it is easy to implement in concrete laboratories. Moreover, the relations obtained between crack parameters and water permeability confirmed the cubic relation, as reported in the literature. This work shows that analyzing healing efficiency by means of crack closing tends to overestimate self-healing if compared with the results obtained by means of water permeability. Sorptivity analysis tests were easy to implement, however, the results obtained in this work showed high dispersion and sensitivity to the variations of the cracks introduced during the precracking process. Regarding the evaluation of mechanical recoveries, the results show that the evolution of concrete properties with time is a parameter of importance that, therefore, should be considered, especially for early age cracks. In this work, crystalline admixtures have been reported as an enhancer of self-healing reactions, but with a limited capacity of enhancement. The proximity of CA to the industry is a positive point to their inclusion as a new type of admixture for concrete. However, the results obtained in this thesis indicate further analyses are needed to determine their full effects on concrete, especially regarding self-healing. / Els materials autosanables són materials amb la capacitat de reparar els seus danys de forma autònoma o amb ajuda mínima d'estímuls externs. En el camp de la construcció, el desenvolupament d'elements autosanables augmentarà la durabilitat de les estructures i reduirà les accions de manteniment i reparació. Els elements de formigó armat presenten freqüentment fissures menudes (< 0.3 mm), no rellevants des del punt de vista mecànic, però poden suposar un punt d'entrada per a agents agressius. El formigó té una capacitat de autosanació capaç de tancar fissures menudes, produïda principalment per la hidratació continuada i la carbonatació. Estudis recents han intentat millorar eixa capacitat i dissenyar productes específics per aconseguir-la. Aquests productes inclouen, entre d'altres, additius cristal·lins, agents micro- o macroencapsulats, i fins i tot l'ús de bacteris. Els additius cristal·lins (CA) són un tipus d'additiu reductor per formigó que es considera que proporciona propietats de autosanació. No obstant, la manca de coneixement sobre el seu comportament limita el seu ús. A més, els mètodes per avaluar la autosanació de formigons encara no estan estandarditzats. Açò complica la realització d'una anàlisi crítica dels diferents productes i mètodes d'avaluació proposats a la literatura. Per respondre a aquesta manca de coneixement, els objectius d'aquesta tesi són: 1) estudiar i proposar procediments experimentals per avaluar els fenòmens d'autosanació en formigó i, 2) avaluar experimentalment les millores produïdes en introduir additius cristal·lins. Aquesta tesi inclou com assajos per a la determinació de l'autosanació: l'avaluació del tancament de fissures, la permeabilitat a l'aigua, flexió a tres punts i absorció capil·lar. A més, s'han realitzat diverses campanyes experimentals per validar els assajos proposats. Posteriorment, aquests assajos s'han utilitzat per analitzar la influència de diversos paràmetres: presència d'additius cristal·lins, nivell de dany, temps necessari per a la sanació, composició del formigó i condicions de sanació. Finalment, s'analitzen els efectes produïts en afegir additius cristal·lins en formigó en fluïdesa, resistència i hidratació. Els resultats mostren que el tancament de fissures és un assaig eficaç i senzill per avaluar l'autosanació. No obstant això, l'orientació de la fissura durant la sanació ha resultat ser de gran importància, i no considerar aquest aspecte pot portar a conclusions enganyoses. L'assaig de permeabilitat a l'aigua proposat presenta una bona estabilitat i és fàcil d'implementar en laboratoris. A més, les relacions obtingudes entre els paràmetres de fissura i la permeabilitat a l'aigua han confirmat la relació cúbica de la literatura. Aquest treball mostra que analitzar l'eficiència de l'autosanació amb el tancament de fissures pot sobreestimar la capacitat de sanació, comparada amb els resultats obtinguts-dues mitjançant permeabilitat a l'aigua. Els assajos de sorptivitat van resultar fàcils d'implementar, però, els resultats obtinguts en aquest treball van mostrar una alta dispersió i sensibilitat a les variacions en les fissures produïdes durant el procés de prefissuració. Pel que fa a l'avaluació de la recuperació mecànica, els resultats mostren que l'evolució de les propietats del formigó amb el temps és un paràmetre d'importància que, per tant, s'ha de considerar, especialment per fissures primerenques. En aquest treball s'ha obtingut que els additius cristal·lins potencien les reaccions d'autosanació, però tenen una capacitat limitada. La proximitat dels CA a la indústria és un punt positiu per a la seva inclusió com un nou tipus d'additiu de formigó. Tanmateix, els resultats obtinguts en aquesta tesi indiquen que calen més anàlisis per determinar els seus efectes complets en formigó, especialment pel que fa a l'autosanació. / Roig Flores, M. (2018). Self-healing concrete: efficiency evaluation and enhancement with crystalline admixtures [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/100082

No / The terahertz frequency spectrum of pentaerythritol tetranitrate (PETN) is calculated using Discover[1] with the COMPASS[2] force field, CASTEP[3] and PWscf.[4] The calculations are compared to each other and to terahertz spectra (0.3-3 THz) of crystalline PETN recorded at 4 K. A number of analysis methods are used to characterise the calculated normal modes.

No / Bulk crystallisation of protein therapeutic molecules towards their controlled drug delivery is of interest to the biopharmaceutical industry. The complexity of biotherapeutic molecules is likely to lead to complex material properties of crystals in the solid state and to complex transitions. This complexity is explored using batch crystallised lysozyme as a model. The effects of drying and milling on the solid-state transformations of lysozyme crystals were monitored using differential scanning calorimetry (DSC), X-ray powder diffraction (XRPD), FT-Raman, and enzymatic assay. XRPD was used to characterise crystallinity and these data supported those of crystalline lysozyme which gave a distinctive DSC thermogram. The apparent denaturation temperature (Tm) of the amorphous lysozyme was ∼201 °C, while the Tm of the crystalline form was ∼187 °C. Raman spectra supported a more α-helix rich structure of crystalline lysozyme. This structure is consistent with reduced cooperative unit sizes compared to the amorphous lysozyme and is consistent with a reduction in the Tm of the crystalline form. Evidence was obtained that milling also induced denaturation in the solid-state, with the denatured lysozyme showing no thermal transition. The denaturation of the crystalline lysozyme occurred mainly through its amorphous form. Interestingly, the mechanical denaturation of lysozyme did not affect its biological activity on dissolution. Lysozyme crystals on drying did not become amorphous, while milling-time played a crucial role in the crystalline-amorphous-denatured transformations of lysozyme crystals. DSC is shown to be a key tool to monitor quantitatively these transformations.

Yes / The association of the arene ruthenium metallacycle [Ru4(p-cymene)4(bpe)2(donq)2][DOS]4 (bpe = 1,2-bis(4-pyridyl)ethylene, donq = 5,8-dioxydo-1,4-naphtoquinonato, DOS = dodecyl sulfate) with pyrenyl-functionalized poly(arylester) dendrimers bearing cyanobiphenyl end-groups is reported. The supramolecular dendritic systems display mesomorphic properties as revealed by polarized optical microscopy, differential scanning calorimetry and small-angle X-ray scattering measurements. The multicomponent nature of the dendrimers and of the corresponding host–guest supramolecules (i.e., end-group mesogens, dendritic core, pyrene unit, aliphatic spacers, and metallacycle) leads to the formation of highly segregated mesophases with a complex multilayered structure due to the tendency of the various constitutive building-blocks to separate in different organized zones. The pyrenyl dendrimers exhibit a multilayered smectic A-like phase, thereafter referred to as LamSmA phase to emphasize this unaccustomed morphology. As for the corresponding Ru4–metallacycle adducts, they self-organize into a multicontinuous thermotropic cubic phase with the Im3̅m space group symmetry. This represents a unique example of liquid-crystalline behavior observed for such large and complex supramolecular host–guest assemblies. Models of their supramolecular organizations within both mesophases are proposed. / R.D. thanks the Swiss National Science Foundation (Grant No 200020-140298) for financial support.

Yes / Properties of a matter are intrinsically dependent upon the internal arrangement of molecules in the solid state. Therefore, knowledge of 3-dimensional structure of the matter is prerequisite for structure-property correlations and design of functional materials. Over the past century, X-ray crystallography has evolved as a method of choice for accurate determination of molecular structure at atomic resolution. The structural information obtained from crystallographic analysis paved the way for rapid development in electronic devices, mineralogy, geosciences, materials science, pharmaceuticals, etc. Knowledge of the structural information of active pharmaceutical ingredients (APIs) is prerequisite for rational drug design and synthesis of new chemical entities for development as new medicines. Over the past two decades, X-ray crystallography has played a key role in the design of pharmaceutical cocrystals-crystalline solids containing an API and one or more of pharmaceutically acceptable coformers. These materials have proved promising for fine-tuning several important properties of APIs. This short review highlights the history of crystallography, early breakthroughs, and the role of crystallography in understanding physicochemical properties of pharmaceutical cocrystals. / S. Aitipamula gratefully acknowledges the financial support from the Institute of Chemical and Engineering Sciences of A*STAR (Agency for Science, Technology and Research), Singapore. V. R. Vangala thanks Royal Society of Chemistry for Researcher Mobility Grant (2015/17).

The articulation of frame and skin forms the space concertedly. The project, stemming from this assertion, searches, explores and articulates the intricate relationship between structure, skin and space as prominent elements of architecture. / Master of Architecture

Yes / By controlling the crystallization behavior of poly(lactic acid) (PLA) in the presence of a hydrazide nucleating agent (HNA), PLA-HNA foams with enhanced microcellular structures were prepared via supercritical CO2 foaming. It was found that HNA can self-assemble into fibrillar networks, inducing the crystallization of PLA on their surface, and "shish-kebab"crystalline structures with high crystallinity formed, which can be maintained during the whole foaming process. Incorporation of HNA promoted the formation of gt conformers, improved the amount of dissolved CO2, hindered the escape of CO2, and increased the viscoelasticity of PLA. Compared with neat PLA foam, for PLA-HNA foam, the average cell diameter decreased obviously, from 64.39 to 6.59 μm, while the cell density increased up to nearly three orders of magnitudes, from 6.82 × 106 to 4.44 × 109 cells/cm3. Moreover, lots of fibrillar structures appeared and entangled with each other on the cell wall of the foam. By forming such dense micropores and enhanced fibrillar structures, PLA foam was highly reinforced with significantly improved compressive strength. / This research was financially supported by National Natural Science Foundation of China (grant no. 51773122) and State Key Laboratory of Polymer Materials Engineering (grant no. sklpme2019-2-21).

Continuous personal dust monitors (CPDMs) are widely used to monitor respirable coal mine dust (RCMD) to reduce miners' exposures, but they are unable to directly assess respirable crystalline silica (RCS) concentrations, which are linked to the recent rise of respiratory diseases among coal miners. This incompatibility is due to the composition of the CPDM's internal filter stub. The stub consists of a fibrous borosilicate filter attached to a polypropylene (PP) backing and a polytetrafluoroethylene (PTFE) binder, which interferes with standard analytical techniques. This study developed a method for indirect analysis of dust collected on the CPDM filter stub using portable direct-on-filter Fourier Transform infrared spectroscopy (DOF-FTIR) to rapidly quantify quartz, the primary analyte of silica in coal mines. The research consisted of four studies that developed and evaluated a three-step process for dust recovery, deposition, and analysis. These studies investigated techniques for separating dust from the CPDM filter media, compared mechanisms for dust deposition onto various substrates, and assessed the ability of FTIR and scanning electron microscopy with energy dispersive X-ray (SEM-EDX) to analyze the mineral characteristics of recovered dust. The resulting method involves submerging CPDM filter stubs in 5 mL of isopropyl alcohol (IPA) and shaking them for 1 minute, followed by deposition of the dust onto a 25-mm polyvinyl chloride (PVC) filter using a syringe-based system. The PVC filter was then scanned at four 8-mm offset locations at 90° intervals from the center. Evaluating this method using field and lab-generated CPDM filter stubs revealed low dust recovery from the stubs. It was also observed that results tended to underpredict the quartz mass as the total sample mass increased. Though adjustments for recovery can be made using a scale and the method can be limited to lower mass samples, more efforts can be made to investigate better dust recovery and improve quartz determination of the samples to increase confidence in the method. / Doctor of Philosophy / To reduce respiratory diseases among coal miners, US regulation requires dust sampling in underground coal mines to monitor the total respirable coal mine dust (RCMD) concentration miners are exposed to using a specific device, the continuous personal dust monitor (CPDM). However, the CPDM cannot be used to directly differentiate the characteristics of the dust, particularly silica, which is particularly hazardous. To do this, a method to indirectly analyze the dust collected on the CPDM's internal filter stub has been evaluated using a three-step method to recover the dust, deposit the dust onto a different filter type, and then analyze the dust using a spectrometer to determine the silica mass. Four studies were performed to develop the full method. These studies investigated how dust can be recovered from filters, how to deposit dust onto another filter, and how to then analyze the dust to determine its characteristics. This was done using multiple methods to determine the optimum three-step method to quantify the silica mass in the recovered dust. The studies ultimately developed a method involving submerging the CPDM filter stub in 5 mL of isopropyl alcohol (IPA) and shaking it for 1 minute to dislodge the dust. Then, the recovered dust was deposited on a 25-mm polyvinyl chloride (PVC) filter using a syringe. After deposition, the PVC filter was finally scanned at four 8-mm offset locations at 90° intervals from the center of the filter. These scans were then used to determine the silica mass. After testing this three-step method on field and lab-generated CPDM filter stubs, results showed low dust recovery from the stubs. It was also observed that results tended to underpredict the silica mass as the total RCMD mass increased. Although the dust left behind on the filter can be determined using a scale and the method can be limited to samples with smaller masses to avoid underpredicting the quartz mass, more work can be done to improve dust recovery, improve the silica determination, and put more confidence in the method.

Foram determinadas as estruturas cristalinas de três 3-fenil-2- izoxazolin-5-ona-4-benzilideno substituídas com potencial atividade antiinflamatória, a partir dos dados difratométricos de raios-X, usando os Métodos Diretos. O refinamento foi obtido pelo método dos Mínimos Quadrados. O composto C16H11NO2 cristalizou no sistema cristalino monoclínico, grupo espacial P21/a, a = 11,786(5) Å, b = 5,745(1) Å, c = 17,862(5) Å, ß = 95,988(5)º, Z = 4, V = 1202,8(12) Å3 . O composto C17H13NO3 cristalizou no sistema cristalino ortorrômbico, grupo espacial Pna21, a = 11,652(5) Å, b = 6,000(5) Å, c = 19,542(5) Å, Z = 4, V = 1366,2(13) Å3. O composto C17H13NO4 cristalizou no sistema cristalino ortorrômbico, grupo espacial Pcab, a = 10,6983(9) Å, b = 12,6111(8) Å, c = 20,926(2) Å, Z = 8, V = 2823,3(4) Å3. Em todas as estruturas verificou-se semelhança estrutural para com a fenilbutazona. / The crystal structures of three substituted 3-phenyl-2- isoxazolin-5-one-4-benzilidene with potential biological activities have been determined from diffractometric X ray data using the Direct Method. The refinement has been obtained through the least squares method. The compound C16H11NO2 crystallized in the monoclinic crystal system, space group P21/a, a = 11,786(5) Å, b = 5,745(1) Å, c = 17,862(5) Å, ß = 5,988(5)º, Z = 4, V = 1202,8(12) Å3. The compound C17H13NO3 belongs to the orthorhombic crystal system, space group Pna21, a = 11,652(5) Å, b = 6,000(5) Å, c = 19,542(5) Å, Z = 4, V = 1366,2(13) Å3. The compound C17H13NO4 crystallized in the orthorhombic crystal system, space group Pcab, a = 10,6983(9) Å, b = 12,6111(8) Å, c = 20,926(2) Å, Z = 8, V = 2823,3(4) Å3. All these structures show structural similarities to the phenylbutazone.