Type 2 Diabetes Mellitus (T2DM) is a metabolic disorder characterized by chronic hyperglycemia, which develops as a consequence of peripheral insulin resistance and defective insulin secretion from pancreatic β-cells. A high calorie diet coupled with physical inactivity are known risk factors for the development of T2DM; however, these alone fail to account for the rapid rise of the disease. Recent attention has turned to the role of environmental pollutants in the development of metabolic diseases. PBDEs (polybrominated diphenyl ethers) are environmental pollutants that have been linked to the development of type 2 diabetes (T2D), however, the precise mechanisms are not clear. In particular, their direct effect on insulin secretion is unknown. In this study, we show that two PBDE congeners, BDE-47 and BDE-85, potentiate glucose-stimulated insulin secretion (GSIS) in INS-1 832/13 cells. This effect of BDE-47 and BDE-85 on GSIS was dependent on thyroid receptor (TR). Both BDE-47 and BDE-85 (10 μM) activated Akt during an acute exposure. The activation of Akt by BDE-47 and BDE-85 plays a role in their potentiation of GSIS, as pharmacological inhibition of PI3K, an upstream activator of Akt, significantly lowers GSIS compared to compounds alone. This study suggests that BDE-47 and BDE-85 directly act on pancreatic β-cells to stimulate GSIS, and that this effect is mediated by the thyroid receptor (TR) and Akt activation. This can cause the β-cells to oversecrete insulin, potentially leading to hyperinsulinemia, insulin resistance, and high blood glucose. In contrast to the potential diabetogenic effects of POPs, there are several naturally-derived compounds which accomplish just the opposite, exerting sensitizing effect on the peripheral tissues and sparing effect on β-cells. TQ, a natural occurring quinone and the main bioactive component of plant Nigella sativa, undergoes intracellular redox cycling and re-oxidizes NADH to NAD+. TQ administration (20 mg/kg/bw/day) to the Diet-Induced Obesity (DIO) mice reduced their diabetic phenotype by decreasing fasting blood glucose and fasting insulin levels, and improved glucose tolerance and insulin sensitivity as evaluated by oral glucose and insulin tolerance tests (OGTT and ITT). Furthermore, TQ decreased serum cholesterol levels and liver triglycerides, increased protein expression of phosphorylated Akt, decreased serum levels of inflammatory markers resistin and MCP-1, and decreased the NADH/NAD+ ratio. These changes were paralleled by an increase in phosphorylated SIRT-1 and AMPKα in liver and phosphorylated SIRT-1 in skeletal muscle. TQ also increased insulin sensitivity in insulin-resistant HepG2 cells via a SIRT-1-dependent mechanism These findings are consistent with the TQ-dependent re-oxidation of NADH to NAD+, which stimulates glucose and fatty acid oxidation and activation of SIRT-1-dependent pathways. Taken together, these results demonstrate that TQ ameliorates the diabetic phenotype in the DIO mouse model of type 2 diabetes.

No description available.

The objective of this thesis was to assess the environmental fate and transport of chemicals emitted from consumer products through the development and application of modelling tools. The following hypotheses were tested: i) Multimedia fate models can be applied in a multistage assessment process to emerging chemicals when limited knowledge exists to identify the likely environmental fate and to direct further research; ii) the indoor environment acts as a source of anthropogenic substances in consumer products to the outdoor environment; and iii) chemical removal pathways in the indoor environment are important for the fate of organic chemicals in densely populated areas. The thesis shows that a structured chemical fate assessment strategy can and should be applied at early stages of the evaluation of emerging chemicals to assess their fate and to direct further research. Multimedia fate models play a key role in this strategy. The three‐solubility approach is a simple, rapid method that can be used to estimate physical‐chemical properties for use in early stage evaluation (Paper I). Emissions in the indoor environment affect the urban fate of hydrophobic organic chemicals by providing additional removal pathways and prolonging urban chemical residence times compared to outdoor emissions (Paper III). Emissions of BDE 209, DINP and DEHP to Stockholm indoor air were estimated to be 0.1, 3.4 and 290 mg/capita year, respectively (Paper IV). The contribution of emissions indoors to outdoor air pollution varies between substances. For BDE 209, emissions in the indoor environment added 38 % to the mass entering Stockholm city with inflowing air. For Sweden, the indoor environment was estimated to account for 80 % of BDE 209 emissions to outdoor air (Papers II and IV). For the phthalates, outdoor emissions and/or background inflow are the dominant sources to outdoor air pollution in Stockholm and the influence of the indoor environment is limited (Paper IV). / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript</p>

Los PBDEs son compuestos químicos orgánicos que se usan como retardantes de llama utilizados en una amplia sección de productos industriales y de consumo. Como consecuencia de su uso comercial, los niveles de PBDEs en el medioambiente se han incrementado en las últimas décadas. Uno de los congéneres mayoritarios encontrados en muestras biológicas es el BDE-99.La mayor parte de estudios experimentales realizados hasta el momento han evaluado los efectos de los PBDEs en el desarrollo de las crías tras una exposición prenatal/perinatal pero no en adultos. Todavía falta mucha información acerca de su toxicidad, sobre todo teniendo en cuenta que se ha descrito su comportamiento como disruptores endocrinos.Se desconoce hasta el momento los mecanismos a través de los cuales los PBDEs actúan. El daño celular inducido por algunos tóxicos y/o contaminantes ambientales se manifiesta con cambios en el estado oxidativo. Por ello, los daños a nivel fisiológico derivados de la exposición a BDE-99 podrían deberse a un desequilibrio en el balance de los agentes oxidantes y mecanismos antioxidantes, así como a una interacción en la respuesta hormonal.El objetivo de este trabajo es evaluar los efectos de la exposición oral a BDE-99 sobre la función cognitiva y reproductiva en ratas macho adultas.En general, no se observan variaciones en el estado de los animales ni tampoco se aprecian alteraciones significativas en los tests de comportamiento realizados.En este estudio se observa que la exposición a BDE-99 en la edad adulta produce alteraciones en la morfología y la producción de esperma, así como alteraciones de la espermatogénesis en los túbulos seminíferos. Por otro lado se observa presencia de fagolisosomas en riñón a causa de la exposición a BDE-99. En todos los tejidos estudiados, el BDE-99 ha provocado cambios en los sistemas antioxidantes.El análisis bioquímico de orina revela cambios en actividades enzimáticas renales así como un incremento en la proteinuria. En sangre, las actividades de las transaminasas hepáticas también se alteran a causa del BDE-99. Además, se observa un descenso de los niveles de testosterona y su precursora la progesterona.Los resultados de esta tesis muestran que la exposición oral a BDE-99 provoca efectos tóxicos en ratas macho adultas que se manifiestan a través de un desequilibrio en el estado oxidativo y hormonal. Estas variaciones causan una alteración únicamente en la respuesta fisiológica reproductiva. / Polybrominated diphenyl ethers (PBDEs) are used as flame retardant additives in a variety of consumer products. Brominated diphenyl ether congener BDE-99 is ubiquitous in the environment and is regarded as one of the most persistent congeners present in wildlife and humans. Experimental studies have evaluated BDE-99 effects on development and reproduction due to pre and perinatal exposure but not in adults. Moreover, previous studies have indicated effects on hormone homeostasis. Although, little is known about their potential toxicological properties.On the other hand, the mechanism through which BDE-99 causes these effects is not well elucidated. This study hypothesized that adverse physiological effects derived from BDE-99 exposure could be due to an imbalance between oxidant agents and antioxidant mechanisms as well as to an hormonal interaction.The aim of the present study was to evaluate the effects of oral BDE-99 exposure on cognitive and reproductive function in adult male rats.In general terms, no alterations on neurodevelopment tests execution were observed. BDE-99 adult exposure caused alterations in sperm morphology, sperm production as well as alterations in seminiferous tubules. Moreover, phagolysosomes in kidney were observed due to BDE-99 administration. In all studied tissues, BDE-99 caused variations in the antioxidant system.Urine biochemical analysis showed changes in renal enzymatic activities and an increase in protein content. In blood, hepatic transaminase activities were also altered by BDE-99 exposure. In addition, testosterone and progesterone levels were decreased.This doctoral thesis shows that oral BDE-99 exposure causes toxic effects in adult male rats that become apparent through an imbalance in oxidative and hormonal status. These variations cause an alteration in the reproductive function.

Quantum chemical calculations at the gradient-corrected (BP86) density-functional calculations with various basis sets (SVP, TZVPP) have been carried out for Mo(CO)4 complexes of Nheterocyclic carbene and analogues-NHEMe (called tetrylenes) with E = C, Si, Ge, Sn, Pb. The equilibrium structures of complexes [Mo(CO)4-NHEMe] (Mo4-NHEMe) exhibit an interesting trend which the lightest adduct Mo4-NHCMe has a trigonal bipyramidal coordination mode where the ligand NHCMe occupies an equatorial position. In contrast, the heavier species from Mo4-NHSiMe to Mo4-NHPbMe possess a square pyramidal structure where the ligands from NHSiMe to NHPbMe occupy a basal position. The slighter complexes Mo4-NHEMe possess end-on-bonded NHEMe ligands when E = C, Si, Ge with the bending angles, α, are 180° whereas the heavier adducts Mo4-NHSnMe and Mo4-NHPbMe exhibit strongly side-on-bonded ligands which the bending angle, α become more acute. The trend of the bond dissociations energies-De [kcal/mol] (BDEs) for the Mo-E bonds is Mo4-NHCMe > Mo4-NHSiMe > Mo4-NHGeMe > Mo4-NHSnMe > Mo4-NHPbMe. Bonding analysis shows that the Mo-E bonds have a significant contribution from (CO)4Mo ← NHEMe π-donation. This is because the energy levels of the π-type donor orbitals of Mo4-NHCMe − Mo4-NHPbMe are higher lying than the σ-type donor orbitals. The NHEMe ligands in Mo4- NHEMe are strong electron donors. This review intends to provide a comprehensive data for plant biology research in the future. / Tính toán hóa lượng tử sử dụng lý thuyết phiếm hàm mật độ kết hợp điều chỉnh gradient (BP86) từ các bộ hàm cơ sở khác nhau (SVP, TZVPP) được thực hiện cho việc tính toán lý thuyết của phức giữa Mo(CO)4 và phối tử N-heterocyclic carbene và các phức tương tự NHEMe (gọi là tetrylenes) với E = C, Si, Ge, Sn, Pb. Cấu trúc của phức [Mo(CO)4-NHEMe] (Mo4-NHEMe) thể hiện sự khác biệt khá thú vị từ Mo4-NHCMe đến Mo4-NHPbMe, phức Mo4-NHCMe có cấu trúc phối trí lưỡng tháp tam giác trong đó phối tử NHCMe chiếm ở vị trí xích đạo. Ngược lại, những phức có phân tử khối lớn hơn từ Mo4-NHSiMe đến Mo4-NHPbMe lại có cấu trúc tháp vuông và các phối tử từ NHSiMe đến NHPbMe chiếm vị trí cạnh (basal – cạnh hướng về bốn đỉnh của đáy vuông). Các cấu trúc của phức Mo4-NHEMe cho thấy các phối tử NHEMe với E = C-Ge tạo với phân tử Mo(CO)4 một góc thẳng α =180.0°, ngược lại, các phức nặng hơn Mo4-NHEMe thì phối tử NHEMe với E = Sn, Pb liên kết với phân tử Mo(CO)4 tạo góc cong và góc cong, α, càng trở nên nhọn hơn khi nguyên tử khối của E càng lớn. Năng lượng phân ly liên kết của liên kết Mo- E giảm dần: Mo4-NHCMe > Mo4-NHSiMe > Mo4-NHGeMe > Mo4-NHSnMe > Mo4-NHPbMe. Phân tích liên kết Mo-E cho thấy có sự đóng góp đáng kể của sự cho liên kết π (CO)4Mo ← NHEMe. Điều này có thể do mức năng lượng của orbital π-cho của Mo4-NHCMe − Mo4-NHPbMe nằm cao hơn orbital σ-cho. Từ kết quả tính toán có thể kết luận rằng phối tử NHEMe trong phức Mo4- NHEMe là chất cho điện tử mạnh. Kết quả nghiên cứu lý thuyết về hệ phức Mo4-NHEMe lần đầu tiên cung cấp một cơ sở dữ liệu hoàn chỉnh cho các nghiên cứu về sinh học thực vật trong tương lai.

Quantum chemical calculations at BP86/TZVPP//BP86/SVP have been carried out for the Nheterocylic carbene and analogues complexes (tetrylene) [(CO)4W-NHE] (W4-NHE) with E = C – Pb. The tetrylene complexes W4-NHE possess end-on-bonded NHE ligands (E = C, Si), while for E = Ge and Sn, they possess slightly side-on-bonded ligands. The strongest side-on-bonded ligand when E = Pb has a bending angle of 102.9°. The trend of the bond dissociations energies (BDEs) for the W-E bond is W4-NHC > W4-NHSi > W4-NHGe > W4-NHSn > W4-NHPb. Analysis of the bonding situation suggests that the NHE ligands in W4-NHE are strong σ-donors and weak π-donors. This is because the tetrylenes have only one lone-pair orbital available for donation. The polarization of the W-E bond and the hybridization at atom E explain the trend in the bond strength of the tetrylene complexes W4-NHE. The W-E bonds of the heavier systems W4-NHE are strongly polarized toward atom E giving rise to rather weak electrostatic attraction with the tungsten atom which is the main source for the decreasing trend of the bond energies. The theoretical calculations suggest that transition-metal complexes tetrylenes [(CO)4W-{NHE}] (E = C – Pb) should be synthetically accessible compounds with tetrylenes NHE act as two-electron-donor ligands in complexes. / Phân tích cấu trúc và bản chất liên kết hóa học của hợp chất với kim loại chuyển tiếp chứa phối tử N-heterocyclic carbene và các đồng đẳng (tetrylene) [(CO)4W–NHE] (W4-NHE) với E = C – Pb sử dụng tính toán hóa lượng tử ở mức BP86/TZVPP//BP86/SVP. Cấu trúc của phức W4-NHE cho thấy các phối tử NHE với E = C, Si tạo với phân tử W(CO)4 một góc thẳng α = 180,0°, trong khi đó các phức W4-NHE thì phối tử NHE với E = Ge – Pb tạo liên kết với nhóm W(CO)4 một góc cong α < 180,0° và góc cong càng trở nên nhọn hơn khi E = Pb (α = 102.9°). Năng lượng phân ly liên kết của liên kết W-E giảm dần: W4-NHC > W4-NHSi > W4-NHGe > W4-NHSn > W4-NHPb. Tính toán hóa lượng tử trong phức [(CO)4W-{NHE}] (E = C – Pb) cho thấy phối tử tetrylene là chất cho electron. Điều này có thể do phối tử tetrylene chỉ giữ lại một cặp electron tại nguyên tử E để đóng vai trò là chất cho điện tử. Độ bền liên kết của phức W4-NHE được giải thích nhờ vào độ phân cực của liên kết W-E và sự lai hóa của nguyên tử trung tâm E. Nguyên nhân chính làm giảm dần năng lượng liên kết là do liên kết W-E của các phức nặng hơn W4-NHE bị phân cực mạnh về phía nguyên tử E dẫn đến lực hút tĩnh điện với nguyên tử W yếu dần. Hệ phức nghiên cứu được coi là hợp chất điển hình cho các nghiên cứu thực nghiệm.

Les PBDEs appartiennent à la famille des retardateurs de flamme bromés, substances massivement utilisés ces dernières décennies. Ces molécules sont aujourd’hui retrouvées de façon ubiquitaire dans l’environnement extérieur et intérieur. L’Homme est exposé à ces polluants par le biais de l’alimentation et de l’ingestion/inhalation de poussières ménagères ou industrielles contaminées. Leurs propriétés lipophiles et leur persistance sont à l’origine de leur bioaccumulation dans les matrices abiotiques et biologiques (lait, sérum…). Les travaux de recherche de cette thèse ont eu pour objectif d’évaluer l’impact d’une exposition à un polluant environnemental toxique et très répandu, le BDE-99, administré dans des conditions reflétant l’exposition humaine. Ainsi, les effets d’une administration de longue durée à des doses réalistes de BDE-99 (0,15, 1,5 et 15 µg/kg/j) ont été évalués au plan neurocomportemental et physiologique chez le rat mâle de souche Sprague-Dawley. Aucune altération de l’activité, de l’anxiété et des fonctions cognitives n’a été mise en évidence que les animaux aient été traités à l’âge adulte, à partir du sevrage ou à partir du 8ème jour de vie postnatale. Les seules variations comportementales significatives observées ont été des troubles transitoires de la coordination locomotrice ainsi qu’un retard d’une journée de l’ouverture des yeux chez les animaux traités avec le BDE-99 depuis l’âge de 8 jours. Au plan physiologique, aucune variation significative de l’évolution pondérale, des prises hydrique et alimentaire ainsi que du poids de plusieurs organes (foie, cerveau, reins, rate et thymus) n’a été observée quelle que soit la dose de BDE-99 administrée et la période d’exposition considérée. Ces résultats montrent donc que ce polluant administré chez le rat à des doses réalistes, reflétant celles auxquelles l’Homme est réellement exposé, n’est pas à même d’induire une toxicité neurocomportementale que les animaux aient contaminés à l’âge adulte ou bien lors de différentes phases du développement postnatal. Le fait d’avoir utilisé des doses correspondantes au niveau d’exposition environnemental est sans aucun doute à la base des discordances observées entre les résultats de ce travail et ceux des études publiées par ailleurs, soulignant ainsi la nécessité de réaliser des modèles d’exposition les plus pertinents possibles de la réalité humaine pour pouvoir conclure au mieux quant au risque lié à cette famille de contaminants pour la santé humaine. / PBDEs belong to flame retardants, substances heavily used in recent decades. These molecules are now found ubiquitously in the environment outside and inside. Humans are exposed to these pollutants through diet and ingestion/inhalation of household dust or contaminated industrial dust. Their lipophilic properties and their persistence are the cause of their bioaccumulation in abiotic and biological matrices (milk, serum ...). The research works of this thesis was aimed to assess the impact of exposure to a toxic environmental pollutant and very prevalent, BDE-99, administered in conditions reflecting the human exposure. Thus, the effects of long-term exposure to realistic doses of BDE-99 (0.15, 1.5 and 15 µg/kg/day) were evaluated in terms neurobehavioral and physiological in male Sprague-Dawley rats. No alteration of the activity, anxiety and cognitive function has been highlighted that the animals were treated in adulthood, from weaning or from the 8th day of postnatal life. The only significant behavioral variations observed were transient locomotor coordination disorders and a delay of one day of eye opening in animals treated with BDE-99 from the age of 8 days. On a physiological level, no significant variation in body weight change, food and water consumption and weight of several organs (liver, brain, kidneys, spleen and thymus) was observed whatever the dose of BDE-99 administered and the exposure period considered. These results show that this pollutant administered to rats at realistic doses, reflecting those to which humans are actually exposed, is not able to induce neurobehavioral toxicity that the animal are contaminated in adulthood or at different phases of postnatal development. The fact to have used corresponding the level of environmental exposure is undoubtedly the basis of discrepancies observed between the results of this work and those of the published studies elsewhere, underscoring the necessity to realize exposure models the most possible relevant in order to able to conclude at best about risk associated with this family of contaminants to human health.

La fonctionnalisation post-polymérisation ou post-fonctionnalisation est une technique qui permet d’apporter des propriétés spécifiques à des polymères dont les caractéristiques intrinsèques sont limitées pour une application donnée. Parmi les différentes stratégies de post-fonctionnalisation, une des plus courantes est le greffage radicalaire en milieu fondu par extrusion réactive (T > 160 °C). Dans ce type de procédé, un précurseur de radicaux appelé agent de greffage est utilisé afin de greffer des unités fonctionnelles sur les chaines de polymère. A ce jour, ce sont les radicaux à base de peroxydes qui sont employés. Cependant, ces derniers engendrent souvent des réactions de réticulation de chaines qui réduisent l’efficacité du processus. Afin de surmonter ces inconvénients, il est alors important de développer de nouvelles structures pertinentes. Dans ce contexte, les travaux de recherche que nous avons entrepris dans cette thèse concernent la conception et l’étude de nouveaux agents de greffage dérivés d’acétoxyphtalimide (NAPI) pour la post-fonctionnalisation de polymères. Afin d’atteindre ces objectifs, notre démarche a été basée sur une approche multidisciplinaire comportant une étude théorique par modélisation moléculaire et une approche expérimentale incluant la synthèse et l’étude de réactivité des nouvelles structures. Par la suite, des essais de post-fonctionnalisation de polyéthylène, de polyamide ainsi que de poly(acide lactique) par ces nouveaux agents de greffage ont été réalisés. Ces essais ont montré des résultats prometteurs à l’utilisation de ces nouveaux composés par rapport aux peroxydes dans les systèmes d’extrusion. / Post-functionalization is a technique which allows to introduce specific properties to polymers whose intrinsic characteristics are limited for a defined application. It has become an appropriate tool to answer the strong demand for performance materials that is constantly growing. Among the post-functionalization methods, one of the most exploited is the radical grafting of the polymers in the molten state by reactive extrusion (T> 160 ° C). In this type of process, a radical precursor called grafting agent is used to graft functional units (monomers) onto the polymer backbone. In this context, the conventional grafting agents used in extrusion are peroxides. However, the radicals generated by peroxide compounds often lead to side reactions, particularly crosslinking reactions of the polymer chains which limit the efficiency of the process. Thus, finding a new family of grafting agents remains a challenge to optimize these extrusion systems. In this research work, the main objective is to use new grafting agents based on acetoxyphthalimide (NAPI) for extrusion. To reach this goal, our strategy is based on a multidisciplinary approach which presents a theoretical study by chemical modeling and an experimental approach by the synthesis and the reactivity study of the targeted structures. To validate the concept, polyethylene, polyamide and polylactic acid post-functionalization tests through these new grafting agents have been carried out. The results obtained have shown that these NAPI derivatives are efficient to graft monomers and to reduce the crosslinking reaction compared to peroxide agents.

Made available in DSpace on 2014-12-17T14:56:21Z (GMT). No. of bitstreams: 1 AdersonCP.pdf: 441948 bytes, checksum: 3ac355b4df6f67d2c5c0a9bb8f35c95a (MD5) Previous issue date: 2006-08-30 / Bayesian networks are powerful tools as they represent probability distributions as graphs. They work with uncertainties of real systems. Since last decade there is a special interest in learning network structures from data. However learning the best network structure is a NP-Hard problem, so many heuristics algorithms to generate network structures from data were created. Many of these algorithms use score metrics to generate the network model. This thesis compare three of most used score metrics. The K-2 algorithm and two pattern benchmarks, ASIA and ALARM, were used to carry out the comparison. Results show that score metrics with hyperparameters that strength the tendency to select simpler network structures are better than score metrics with weaker tendency to select simpler network structures for both metrics (Heckerman-Geiger and modi&#64257;ed MDL). Heckerman-Geiger Bayesian score metric works better than MDL with large datasets and MDL works better than Heckerman-Geiger with small datasets. The modi&#64257;ed MDL gives similar results to Heckerman-Geiger for large datasets and close results to MDL for small datasets with stronger tendency to select simpler network structures / Redes Bayesianas s?o poderosas ferramentas de representa??o gr?&#64257;ca de distribui??es de probabilidade. Tais redes manipulam incertezas existentes em sistemas do mundo real. A partir da ?ltima d?cada, especial interesse no aprendizado de sua estrutura a partir de um conjunto de dados. Entretanto, o aprendizado da estrutura ? um problema NP-Dif?cil, o que gerou a cria??o de Algoritmos heur?sticos de busca. Muitos desses Algoritmos s?o baseados em m?tricas de pontua??o para estimar o modelo. Este trabalho procura comparar tr?s das m?tricas mais utilizadas. Para gerar os resul tados foram utilizadas as redes ASIA e ALARM, que s?o dois dos benchmarks padr?es e o Algoritmo de busca K-2. A m?trica Bayesiana Heckerman-Geiger com hiperpar?metros que di&#64257;cultam a gera??o de arestas apresentam melhores resultados que ?quelas que &#64258;exibilizam a gera??o de arestas, acontecendo o mesmo com a m?trica MDL modi&#64257;cada. A compara??o das duas m?tricas mostrou que a m?trica Bayesiana ? superior ? m?trica MDL com grandes conjuntos de dados e inferior, caso contr?rio. A modi&#64257;ca??o na m?trica MDL resultou em estruturas mais pr?ximas ?s apresentadas pela MDL para um conjunto reduzido de dados e mais pr?ximas ? Heckerman-Geiger para um grande conjunto de dados, quando seus par?metros restrigem a cria??o de arestas

Quantum chemical calculations at the gradient-corrected (BP86) density-functional calculations with various basis sets (SVP, TZVPP) have been carried out for Mo(CO)4 complexes of Nheterocyclic carbene and analogues-NHEMe (called tetrylenes) with E = C, Si, Ge, Sn, Pb. The equilibrium structures of complexes [Mo(CO)4-NHEMe] (Mo4-NHEMe) exhibit an interesting trend which the lightest adduct Mo4-NHCMe has a trigonal bipyramidal coordination mode where the ligand NHCMe occupies an equatorial position. In contrast, the heavier species from Mo4-NHSiMe to Mo4-NHPbMe possess a square pyramidal structure where the ligands from NHSiMe to NHPbMe occupy a basal position. The slighter complexes Mo4-NHEMe possess end-on-bonded NHEMe ligands when E = C, Si, Ge with the bending angles, α, are 180° whereas the heavier adducts Mo4-NHSnMe and Mo4-NHPbMe exhibit strongly side-on-bonded ligands which the bending angle, α become more acute. The trend of the bond dissociations energies-De [kcal/mol] (BDEs) for the Mo-E bonds is Mo4-NHCMe > Mo4-NHSiMe > Mo4-NHGeMe > Mo4-NHSnMe > Mo4-NHPbMe. Bonding analysis shows that the Mo-E bonds have a significant contribution from (CO)4Mo ← NHEMe π-donation. This is because the energy levels of the π-type donor orbitals of Mo4-NHCMe − Mo4-NHPbMe are higher lying than the σ-type donor orbitals. The NHEMe ligands in Mo4- NHEMe are strong electron donors. This review intends to provide a comprehensive data for plant biology research in the future. / Tính toán hóa lượng tử sử dụng lý thuyết phiếm hàm mật độ kết hợp điều chỉnh gradient (BP86) từ các bộ hàm cơ sở khác nhau (SVP, TZVPP) được thực hiện cho việc tính toán lý thuyết của phức giữa Mo(CO)4 và phối tử N-heterocyclic carbene và các phức tương tự NHEMe (gọi là tetrylenes) với E = C, Si, Ge, Sn, Pb. Cấu trúc của phức [Mo(CO)4-NHEMe] (Mo4-NHEMe) thể hiện sự khác biệt khá thú vị từ Mo4-NHCMe đến Mo4-NHPbMe, phức Mo4-NHCMe có cấu trúc phối trí lưỡng tháp tam giác trong đó phối tử NHCMe chiếm ở vị trí xích đạo. Ngược lại, những phức có phân tử khối lớn hơn từ Mo4-NHSiMe đến Mo4-NHPbMe lại có cấu trúc tháp vuông và các phối tử từ NHSiMe đến NHPbMe chiếm vị trí cạnh (basal – cạnh hướng về bốn đỉnh của đáy vuông). Các cấu trúc của phức Mo4-NHEMe cho thấy các phối tử NHEMe với E = C-Ge tạo với phân tử Mo(CO)4 một góc thẳng α =180.0°, ngược lại, các phức nặng hơn Mo4-NHEMe thì phối tử NHEMe với E = Sn, Pb liên kết với phân tử Mo(CO)4 tạo góc cong và góc cong, α, càng trở nên nhọn hơn khi nguyên tử khối của E càng lớn. Năng lượng phân ly liên kết của liên kết Mo- E giảm dần: Mo4-NHCMe > Mo4-NHSiMe > Mo4-NHGeMe > Mo4-NHSnMe > Mo4-NHPbMe. Phân tích liên kết Mo-E cho thấy có sự đóng góp đáng kể của sự cho liên kết π (CO)4Mo ← NHEMe. Điều này có thể do mức năng lượng của orbital π-cho của Mo4-NHCMe − Mo4-NHPbMe nằm cao hơn orbital σ-cho. Từ kết quả tính toán có thể kết luận rằng phối tử NHEMe trong phức Mo4- NHEMe là chất cho điện tử mạnh. Kết quả nghiên cứu lý thuyết về hệ phức Mo4-NHEMe lần đầu tiên cung cấp một cơ sở dữ liệu hoàn chỉnh cho các nghiên cứu về sinh học thực vật trong tương lai.