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Van der Waals (vdW) magnets both allow exploration of fundamental 2D physics and offer a route toward exploiting magnetism in next generation information technology, but vdW magnets with complex, noncollinear spin textures are currently rare. We report here the syntheses, crystal structures, magnetic properties and magnetic ground states of four bulk vdW metal-organic magnets (MOMs): FeCl2(pym), FeCl2(btd), NiCl2(pym), and NiCl2(btd), pym = pyrimidine and btd = 2,1,3-benzothiadiazole. Using a combination of neutron diffraction and bulk magnetometry we show that these materials are noncollinear magnets. Although only NiCl2(btd) has a ferromagnetic ground state, we demonstrate that low-field hysteretic metamagnetic transitions produce states with net magnetization in zero-field and high coercivities for FeCl2(pym) and NiCl2(pym). By combining our bulk magnetic data with diffuse scattering analysis and broken-symmetry density-functional calculations, we probe the magnetic superexchange interactions, which when combined with symmetry analysis allow us to suggest design principles for future noncollinear vdW MOMs. These materials, if delaminated, would prove an interesting new family of 2D magnets.
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Boar seminal plasma (SP) proteins were associated with differences on sperm resistance to cooling at 17°C. However, information about seminal plasma proteins in boars classified by capacity of semen preservation and in vivo fertility remains lacking. Thus, the objective was to evaluate the SP proteome in boars classified by capacity of semen preservation and putative biomarkers for fertility. The ejaculates from high-preservation (HP) showed higher progressive motility during all 5 days than the low-preservation (LP) boars. There was no difference for farrowing rate between ejaculates from LP (89.7%) and HP boars (88.4%). The LP boars presented lower total piglets born (14.0 ± 0.2) than HP (14.8 ± 0.2; p < 0.01). A total of 257 proteins were identified, where 184 were present in both classes of boar, and 41 and 32 were identified only in LP and HP boars, respectively. Nine proteins were differently expressed: five were more abundant in HP (SPMI, ZPBP1, FN1, HPX, and C3) and four in LP boars (B2M, COL1A1, NKX3-2, and MPZL1). The HP boars had an increased abundance of SP proteins related to sperm resistance and fecundation process which explains the better TPB. LP boars had a higher abundance of SP proteins associated with impaired spermatogenesis.
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Preservación de Semen , Semen , Porcinos , Animales , Masculino , Semen/metabolismo , Preservación de Semen/veterinaria , Proteómica , Inseminación Artificial , Espermatozoides , Fertilidad , Análisis de Semen , Proteínas de Plasma Seminal/metabolismo , Motilidad EspermáticaRESUMEN
The worldwide incidence of prediabetes/type 2 has continued to rise the last 40 years. In the same period, the mean daily energy intake has increased, and the quality of food has significantly changed. The chronic exposure of pancreatic ß-cells to calorie excess (excessive energy intake) and food additives may increase pancreatic insulin secretion, decrease insulin pulses and/or reduce hepatic insulin clearance, thereby causing chronic hyperinsulinemia and peripheral insulin resistance. Chronic calorie excess and hyperinsulinemia may promote lipogenesis, inhibit lipolysis and increase lipid storage in adipocytes. In addition, calorie excess and hyperinsulinemia can induce insulin resistance and contribute to progressive and excessive ectopic fat accumulation in the liver and pancreas by the conversion of excess calories into fat. The personal fat threshold hypothesis proposes that in susceptible individuals, excessive ectopic fat accumulation may eventually lead to hepatic insulin receptor resistance, the loss of pancreatic insulin secretion, hyperglycemia and the development of frank type 2 diabetes. Thus, type 2 diabetes seems (partly) to be caused by hyperinsulinemia-induced excess ectopic fat accumulation in the liver and pancreas. Increasing evidence further shows that interventions (hypocaloric diet and/or bariatric surgery), which remove ectopic fat in the liver and pancreas by introducing a negative energy balance, can normalize insulin secretion and glucose tolerance and induce the sustained biochemical remission of type 2 diabetes. This pathophysiological insight may have major implications and may cause a paradigm shift in the management of type 2 diabetes: avoiding/reducing ectopic fat accumulation in the liver and pancreas may both be essential to prevent and cure type 2 diabetes.
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Diabetes Mellitus Tipo 2 , Hiperinsulinismo , Hipernutrición , Humanos , Hiperinsulinismo/metabolismo , Hiperinsulinismo/complicaciones , Hiperinsulinismo/etiología , Diabetes Mellitus Tipo 2/metabolismo , Diabetes Mellitus Tipo 2/etiología , Hipernutrición/complicaciones , Resistencia a la Insulina , Tejido Adiposo/metabolismo , Animales , Hígado/metabolismo , Hígado/patología , Insulina/metabolismo , Páncreas/metabolismo , Páncreas/patologíaRESUMEN
BACKGROUND: In January 1972, Klaus Winter submitted his first paper on crassulacean acid metabolism (CAM) whilst still an undergraduate student in Darmstadt. During the subsequent half-century, he passed his Staatsexamensarbeit, obtained his Dr. rer. nat. summa cum laude and Dr. rer. nat. habil., won a Heinz Maier-Leibnitz Prize and a Heisenberg Fellowship, and has occupied positions in Germany, Australia, the USA and Panama. Now a doyen in CAM circles, and a Senior Staff Scientist at the Smithsonian Tropical Research Institute (STRI), he has published over 300 articles, of which about 44 % are about CAM. SCOPE: I document Winter's career, attempting to place his CAM-related scientific output and evolution in the context of factors that have influenced him as he and his science progressed from the 1970s to the 2020s.
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Metabolismo Ácido de las Crasuláceas , Humanos , AustraliaRESUMEN
BACKGROUND: Crassulacean acid metabolism (CAM) photosynthesis is a successful adaptation that has evolved often in angiosperms, gymnosperms, ferns and lycophytes. Present in ~5 % of vascular plants, the CAM diaspora includes all continents apart from Antarctica. Species with CAM inhabit most landscapes colonized by vascular plants, from the Arctic Circle to Tierra del Fuego, from below sea level to 4800 m a.s.l., from rainforests to deserts. They have colonized terrestrial, epiphytic, lithophytic, palustrine and aquatic systems, developing perennial, annual or geophyte strategies that can be structurally arborescent, shrub, forb, cladode, epiphyte, vine or leafless with photosynthetic roots. CAM can enhance survival by conserving water, trapping carbon, reducing carbon loss and/or via photoprotection. SCOPE: This review assesses the phylogenetic diversity and historical biogeography of selected lineages with CAM, i.e. ferns, gymnosperms and eumagnoliids, Orchidaceae, Bromeliaceae, Crassulaceae, Euphorbiaceae, Aizoaceae, Portulacineae (Montiaceae, Basellaceae, Halophytaceae, Didiereaceae, Talinaceae, Portulacaceae, Anacampserotaceae and Cactaceae) and aquatics. CONCLUSIONS: Most extant CAM lineages diversified after the Oligocene/Miocene, as the planet dried and CO2 concentrations dropped. Radiations exploited changing ecological landscapes, including Andean emergence, Panamanian Isthmus closure, Sundaland emergence and submergence, changing climates and desertification. Evidence remains sparse for or against theories that CAM biochemistry tends to evolve before pronounced changes in anatomy and that CAM tends to be a culminating xerophytic trait. In perennial taxa, any form of CAM can occur depending upon the lineage and the habitat, although facultative CAM appears uncommon in epiphytes. CAM annuals lack strong CAM. In CAM annuals, C3â +â CAM predominates, and inducible or facultative CAM is common.
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Metabolismo Ácido de las Crasuláceas , Fotosíntesis , Filogenia , Carbono/metabolismo , EcosistemaRESUMEN
BACKGROUND AND SCOPE: The growth of experimental studies of crassulacean acid metabolism (CAM) in diverse plant clades, coupled with recent advances in molecular systematics, presents an opportunity to re-assess the phylogenetic distribution and diversity of species capable of CAM. It has been more than two decades since the last comprehensive lists of CAM taxa were published, and an updated survey of the occurrence and distribution of CAM taxa is needed to facilitate and guide future CAM research. We aimed to survey the phylogenetic distribution of these taxa, their diverse morphology, physiology and ecology, and the likely number of evolutionary origins of CAM based on currently known lineages. RESULTS AND CONCLUSIONS: We found direct evidence (in the form of experimental or field observations of gas exchange, day-night fluctuations in organic acids, carbon isotope ratios and enzymatic activity) for CAM in 370 genera of vascular plants, representing 38 families. Further assumptions about the frequency of CAM species in CAM clades and the distribution of CAM in the Cactaceae and Crassulaceae bring the currently estimated number of CAM-capable species to nearly 7 % of all vascular plants. The phylogenetic distribution of these taxa suggests a minimum of 66 independent origins of CAM in vascular plants, possibly with dozens more. To achieve further insight into CAM origins, there is a need for more extensive and systematic surveys of previously unstudied lineages, particularly in living material to identify low-level CAM activity, and for denser sampling to increase phylogenetic resolution in CAM-evolving clades. This should allow further progress in understanding the functional significance of this pathway by integration with studies on the evolution and genomics of CAM in its many forms.
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Metabolismo Ácido de las Crasuláceas , Fotosíntesis , Humanos , Filogenia , Fotosíntesis/fisiología , Plantas/genética , Plantas/metabolismo , Planeta TierraRESUMEN
The metabolic syndrome is a cluster of overlapping conditions resulting in an increased incidence of type 2 diabetes, cardiovascular disease, and cancer. In the last few decades, prevalence of the metabolic syndrome in the Western world has reached epidemic proportions and this is likely due to alterations in diet and the environment as well as decreased physical activity. This review discusses how the Western diet and lifestyle (Westernization) has played an important etiological role in the pathogenesis of the metabolic syndrome and its consequences by exerting negative effects on activity of the insulin-insulin-like growth factor-I (insulin-IGF-I) system. It is further proposed that interventions that normalize/reduce activity of the insulin-IGF-I system may play a key role in the prevention and treatment of the metabolic syndrome. For successful prevention, limitation, and treatment of the metabolic syndrome, the focus should be primarily on changing our diets and lifestyle in accordance with our genetic make-up, formed in adaptation to Paleolithic diets and lifestyles during a period of several million years of human evolution. Translating this insight into clinical practice, however, requires not only individual changes in our food and lifestyle, starting in pediatric populations at a very young age, but also requires fundamental changes in our current health systems and food industry. Change is needed: primary prevention of the metabolic syndrome should be made a political priority. New strategies and policies should be developed to stimulate and implement behaviors encouraging the sustainable use of healthy diets and lifestyles to prevent the metabolic syndrome before it develops.
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Diabetes Mellitus Tipo 2 , Síndrome Metabólico , Niño , Humanos , Insulina , Factor I del Crecimiento Similar a la Insulina/metabolismo , Insulina Regular Humana , Transducción de SeñalRESUMEN
Background: Human teeth and nails have demonstrated similar factors genetically, embryologically, and morphologically. The fingernail form may be used as a post-extraction guide for selecting the tooth form. Aim: To evaluate the correlation between the maxillary left central incisor tooth form with the left index, middle, and ring fingernails in the Saudi Arabian population. Materials and Methods: A descriptive cross-sectional study with purposive sampling was done among 200 Saudi participants. The maxillary left central incisor and the left index, middle, and ring fingernail were scanned using an intraoral scanner. The 3D digital images were converted to 3D models. The tooth form (tooth length, tooth width, and tooth shape) and nail form (nail length, nail width, and nail shape) were measured using the CAD software. Pearson's correlation coefficient and T-test were used for statistical analysis (P < 0.05). Result: A significant correlation exists between tooth length and nail length, with a maximum correlation toward index nail length (P = 0.015). A significant correlation exists between tooth width and nail width, with a maximum correlation toward ring nail width (P = 0.002). A significant correlation exists between tooth length and nail length in females with a maximum correlation toward index nail length in females (P = 0.001). The mean percentage of similarity between tooth and nail shape (index, middle, and ring) in males and females shows a highly significant difference between them (P = 0.001). The results indicate that the tooth and nail shape are similar (70 to 90%) based on the criteria set by the software. Conclusion: A definite correlation exists between maxillary central incisor tooth form and fingernail form. The fingernail form may be used as a post-extraction guide for selecting the maxillary central incisor tooth form in the Saudi Arabian population.
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Incisivo , Uñas , Femenino , Masculino , Humanos , Arabia Saudita , Estudios Transversales , Programas InformáticosRESUMEN
The experimental realization of magnetic skyrmion crystals in centrosymmetric materials has been driven by theoretical understanding of how a delicate balance of anisotropy and frustration can stabilize topological spin structures in applied magnetic fields. Recently, the centrosymmetric material Gd_{2}PdSi_{3} was shown to host a field-induced skyrmion crystal, but the skyrmion stabilization mechanism remains unclear. Here, we employ neutron-scattering measurements on an isotopically enriched polycrystalline Gd_{2}PdSi_{3} sample to quantify the interactions that drive skyrmion formation. Our analysis reveals spatially extended interactions in triangular planes, and large ferromagnetic interplanar magnetic interactions that are modulated by the Pd/Si superstructure. The skyrmion crystal emerges from a zero-field helical magnetic order with magnetic moments perpendicular to the magnetic propagation vector, indicating that the magnetic dipolar interaction plays a significant role. Our experimental results establish an interaction space that can promote skyrmion formation, facilitating identification and design of centrosymmetric skyrmion materials.
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Competition among exchange interactions is able to induce novel spin correlations on a bipartite lattice without geometrical frustration. A prototype example is the spiral spin liquid, which is a correlated paramagnetic state characterized by subdimensional degenerate propagation vectors. Here, using spectral graph theory, we show that spiral spin liquids on a bipartite lattice can be approximated by a further-neighbor model on the corresponding line-graph lattice that is nonbipartite, thus broadening the space of candidate materials that may support the spiral spin liquid phases. As illustrations, we examine neutron scattering experiments performed on two spinel compounds, ZnCr_{2}Se_{4} and CuInCr_{4}Se_{8}, to demonstrate the feasibility of this new approach and expose its possible limitations in experimental realizations.
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In the dense metal-organic framework Na[Mn(HCOO)_{3}], Mn^{2+} ions (S=5/2) occupy the nodes of a "trillium" net. We show that the system is strongly magnetically frustrated: the Néel transition is suppressed well below the characteristic magnetic interaction strength; short-range magnetic order persists far above the Néel temperature; and the magnetic susceptibility exhibits a pseudo-plateau at 1/3-saturation magnetization. A simple model of nearest-neighbor Heisenberg antiferromagnetic and dipolar interactions accounts quantitatively for all observations, including an unusual 2-k magnetic ground state. We show that the relative strength of dipolar interactions is crucial to selecting this particular ground state. Geometric frustration within the classical spin liquid regime gives rise to a large magnetocaloric response at low applied fields that is degraded in powder samples as a consequence of the anisotropy of dipolar interactions.
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The behavioural rhythms of organisms are thought to be under strong selection, influenced by the rhythmicity of the environment. Such behavioural rhythms are well studied in isolated individuals under laboratory conditions, but free-living individuals have to temporally synchronize their activities with those of others, including potential mates, competitors, prey and predators. Individuals can temporally segregate their daily activities (for example, prey avoiding predators, subordinates avoiding dominants) or synchronize their activities (for example, group foraging, communal defence, pairs reproducing or caring for offspring). The behavioural rhythms that emerge from such social synchronization and the underlying evolutionary and ecological drivers that shape them remain poorly understood. Here we investigate these rhythms in the context of biparental care, a particularly sensitive phase of social synchronization where pair members potentially compromise their individual rhythms. Using data from 729 nests of 91 populations of 32 biparentally incubating shorebird species, where parents synchronize to achieve continuous coverage of developing eggs, we report remarkable within- and between-species diversity in incubation rhythms. Between species, the median length of one parent's incubation bout varied from 1-19 h, whereas period length-the time in which a parent's probability to incubate cycles once between its highest and lowest value-varied from 6-43 h. The length of incubation bouts was unrelated to variables reflecting energetic demands, but species relying on crypsis (the ability to avoid detection by other animals) had longer incubation bouts than those that are readily visible or who actively protect their nest against predators. Rhythms entrainable to the 24-h light-dark cycle were less prevalent at high latitudes and absent in 18 species. Our results indicate that even under similar environmental conditions and despite 24-h environmental cues, social synchronization can generate far more diverse behavioural rhythms than expected from studies of individuals in captivity. The risk of predation, not the risk of starvation, may be a key factor underlying the diversity in these rhythms.
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Charadriiformes/fisiología , Comportamiento de Nidificación/fisiología , Periodicidad , Conducta Predatoria , Animales , Evolución Biológica , Charadriiformes/clasificación , Ritmo Circadiano , Señales (Psicología) , Ambiente , Conducta Alimentaria , Femenino , Masculino , Fotoperiodo , Reproducción , Especificidad de la Especie , Inanición/veterinaria , Factores de Tiempo , Cigoto/crecimiento & desarrolloRESUMEN
Recent data suggests that (pre)diabetes onset is preceded by a period of hyperinsulinemia. Consumption of the "modern" Western diet, over-nutrition, genetic background, decreased hepatic insulin clearance, and fetal/metabolic programming may increase insulin secretion, thereby causing chronic hyperinsulinemia. Hyperinsulinemia is an important etiological factor in the development of metabolic syndrome, type 2 diabetes, cardiovascular disease, polycystic ovarian syndrome, and Alzheimer's disease. Recent data suggests that the onset of prediabetes and diabetes are preceded by a variable period of hyperinsulinemia. Emerging data suggest that chromic hyperinsulinemia is also a driving force for increased activation of the hypothalamic-adrenal-pituitary (HPA) axis in subjects with the metabolic syndrome, leading to a state of "functional hypercortisolism". This "functional hypercortisolism" by antagonizing insulin actions may prevent hypoglycemia. It also disturbs energy balance by shifting energy fluxes away from muscles toward abdominal fat stores. Synergistic effects of hyperinsulinemia and "functional hypercortisolism" promote abdominal visceral obesity and insulin resistance which are core pathophysiological components of the metabolic syndrome. It is hypothesized that hyperinsulinemia-induced increased activation of the HPA axis plays an important etiological role in the development of the metabolic syndrome and its consequences. Numerous studies have demonstrated reversibility of hyperinsulinemia with lifestyle, surgical, and pharmaceutical-based therapies. Longitudinal studies should be performed to investigate whether strategies that reduce hyperinsulinemia at an early stage are successfully in preventing increased activation of the HPA axis and the metabolic syndrome.
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Síndrome de Cushing , Diabetes Mellitus Tipo 2 , Síndrome Metabólico , Síndrome de Cushing/metabolismo , Diabetes Mellitus Tipo 2/metabolismo , Humanos , Sistema Hipotálamo-Hipofisario/metabolismo , Insulina/metabolismo , Insulina Regular Humana , Síndrome Metabólico/metabolismo , Obesidad/metabolismo , Sistema Hipófiso-Suprarrenal/metabolismoRESUMEN
Biological treatments such as enzyme-replacement therapies (ERT) can generate anti-drug antibodies (ADA), which may reduce drug efficacy and impact patient safety and consequently led to research to mitigate ADA responses. Transient low-dose methotrexate (TLD-MTX) as a prophylactic ITI regimen, when administered concurrently with ERT, induces long-lived reduction of ADA to recombinant human alglucosidase alfa (rhGAA) in mice. In current clinical practice, a prophylactic ITI protocol that includes TLD-MTX, rituximab and intravenous immunoglobulin (optional), successfully induced lasting control of ADA to rhGAA in high-risk, cross-reactive immunological material (CRIM)-negative infantile-onset Pompe disease (IOPD) patients. More recently, evaluation of TLD-MTX demonstrated benefit in CRIM-positive IOPD patients. To more clearly understand the mechanism for the effectiveness of TLD-MTX, non-targeted transcriptional and proteomic screens were conducted and revealed up-regulation of erythropoiesis signatures. Confirmatory studies showed transiently larger spleens by weight, increased spleen cellularity and that following an initial reduction of mature red blood cells (RBCs) in the bone marrow and blood, a significant expansion of Ter-119+ CD71+ immature RBCs was observed in spleen and blood of mice. Histology sections revealed increased nucleated cells, including hematopoietic precursors, in the splenic red pulp of these mice. This study demonstrated that TLD-MTX induced a transient reduction of mature RBCs in the blood and immature RBCs in the bone marrow followed by significant enrichment of immature, nucleated RBCs in the spleen and blood during the time of immune tolerance induction, which suggested modulation of erythropoiesis may be associated with the induction of immune tolerance to rhGAA.
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Diferenciación Celular/efectos de los fármacos , Proliferación Celular/efectos de los fármacos , Eritroblastos/efectos de los fármacos , Tolerancia Inmunológica/efectos de los fármacos , Metotrexato/administración & dosificación , Animales , Diferenciación Celular/genética , Diferenciación Celular/inmunología , Relación Dosis-Respuesta a Droga , Eritroblastos/citología , Eritroblastos/metabolismo , Eritrocitos/efectos de los fármacos , Eritrocitos/inmunología , Eritrocitos/metabolismo , Eritropoyesis/efectos de los fármacos , Eritropoyesis/genética , Eritropoyesis/inmunología , Femenino , Perfilación de la Expresión Génica/métodos , Humanos , Tolerancia Inmunológica/genética , Tolerancia Inmunológica/inmunología , Inmunosupresores/administración & dosificación , Inmunosupresores/inmunología , Metotrexato/inmunología , Ratones Endogámicos C57BL , Proteómica/métodos , Bazo/efectos de los fármacos , Bazo/inmunología , Bazo/metabolismo , alfa-Glucosidasas/administración & dosificaciónRESUMEN
We present a structural and magnetic study of two batches of polycrystalline LiNi0.8Mn0.1Co0.1O2 (commonly known as Li NMC 811), a Ni-rich Li ion battery cathode material, using elemental analysis, X-ray and neutron diffraction, magnetometry, and polarized neutron scattering measurements. We find that the samples, labeled S1 and S2, have the composition Li1-xNi0.9+x-yMnyCo0.1O2, with x = 0.025(2), y = 0.120(2) for S1 and x = 0.002(2), y = 0.094(2) for S2, corresponding to different concentrations of magnetic ions and excess Ni2+ in the Li+ layers. Both samples show a peak in the zero-field-cooled (ZFC) dc susceptibility at 8.0(2) K, but the temperature at which the ZFC and FC (field-cooled) curves deviate is substantially different: 64(2) K for S1 and 122(2) K for S2. The ac susceptibility measurements show that the transition for S1 shifts with frequency whereas no such shift is observed for S2 within the resolution of our measurements. Our results demonstrate the sample dependence of magnetic properties in Li NMC 811, consistent with previous reports on the parent material LiNiO2. We further establish that a combination of experimental techniques is necessary to accurately determine the chemical composition of next-generation battery materials with multiple cations.
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For many years, the dogma has been that insulin resistance precedes the development of hyperinsulinemia. However, recent data suggest a reverse order and place hyperinsulinemia mechanistically upstream of insulin resistance. Genetic background, consumption of the "modern" Western diet and over-nutrition may increase insulin secretion, decrease insulin pulses and/or reduce hepatic insulin clearance, thereby causing hyperinsulinemia. Hyperinsulinemia disturbs the balance of the insulin-GH-IGF axis and shifts the insulin : GH ratio towards insulin and away from GH. This insulin-GH shift promotes energy storage and lipid synthesis and hinders lipid breakdown, resulting in obesity due to higher fat accumulation and lower energy expenditure. Hyperinsulinemia is an important etiological factor in the development of metabolic syndrome, type 2 diabetes, cardiovascular disease, cancer and premature mortality. It has been further hypothesized that nutritionally driven insulin exposure controls the rate of mammalian aging. Interventions that normalize/reduce plasma insulin concentrations might play a key role in the prevention and treatment of age-related decline, obesity, type 2 diabetes, cardiovascular disease and cancer. Caloric restriction, increasing hepatic insulin clearance and maximizing insulin sensitivity are at present the three main strategies available for managing hyperinsulinemia. This may slow down age-related physiological decline and prevent age-related diseases. Drugs that reduce insulin (hyper) secretion, normalize pulsatile insulin secretion and/or increase hepatic insulin clearance may also have the potential to prevent or delay the progression of hyperinsulinemia-mediated diseases. Future research should focus on new strategies to minimize hyperinsulinemia at an early stage, aiming at successfully preventing and treating hyperinsulinemia-mediated diseases.
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Envejecimiento/patología , Enfermedades Cardiovasculares/patología , Diabetes Mellitus Tipo 2/patología , Hiperinsulinismo/complicaciones , Resistencia a la Insulina , Neoplasias/patología , Obesidad/patología , Enfermedades Cardiovasculares/etiología , Diabetes Mellitus Tipo 2/etiología , Humanos , Neoplasias/etiologíaRESUMEN
Bond-dependent magnetic interactions can generate exotic phases such as Kitaev spin-liquid states. Experimentally determining the values of bond-dependent interactions is a challenging but crucial problem. Here, I show that each symmetry-allowed nearest-neighbor interaction on triangular and honeycomb lattices has a distinct signature in paramagnetic neutron-diffraction data, and that such data contain sufficient information to determine the spin Hamiltonian unambiguously via unconstrained fits. Moreover, I show that bond-dependent interactions can often be extracted from powder-averaged data. These results facilitate experimental determination of spin Hamiltonians for materials that do not show conventional magnetic ordering.
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We present a comprehensive neutron scattering study of the breathing pyrochlore magnet LiGaCr_{4}S_{8}. We observe an unconventional magnetic excitation spectrum with a separation of high- and low-energy spin dynamics in the correlated paramagnetic regime above a spin-freezing transition at 12(2) K. By fitting to magnetic diffuse-scattering data, we parametrize the spin Hamiltonian. We find that interactions are ferromagnetic within the large and small tetrahedra of the breathing pyrochlore lattice, but antiferromagnetic further-neighbor interactions are also essential to explain our data, in qualitative agreement with density-functional-theory predictions [Ghosh et al., npj Quantum Mater. 4, 63 (2019)2397-464810.1038/s41535-019-0202-z]. We explain the origin of geometrical frustration in LiGaCr_{4}S_{8} in terms of net antiferromagnetic coupling between emergent tetrahedral spin clusters that occupy a face-centered-cubic lattice. Our results provide insight into the emergence of frustration in the presence of strong further-neighbor couplings, and a blueprint for the determination of magnetic interactions in classical spin liquids.
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Understanding the effect of chemical composition on the strength of magnetic interactions is key to the design of magnets with high operating temperatures. The magnetic divalent first-row transition metal (TM) thiocyanates are a class of chemically simple layered molecular frameworks. Here, we report two new members of the family, manganese(II) thiocyanate, Mn(NCS)2, and iron(II) thiocyanate, Fe(NCS)2. Using magnetic susceptibility measurements on these materials and on cobalt(II) thiocyanate and nickel(II) thiocyanate, Co(NCS)2 and Ni(NCS)2, respectively, we identify significantly stronger net antiferromagnetic interactions between the earlier TM ions-a decrease in the Weiss constant, θ, from 29 K for Ni(NCS)2 to -115 K for Mn(NCS)2-a consequence of more diffuse 3d orbitals, increased orbital overlap, and increasing numbers of unpaired t2g electrons. We elucidate the magnetic structures of these materials: Mn(NCS)2, Fe(NCS)2, and Co(NCS)2 order into the same antiferromagnetic commensurate ground state, while Ni(NCS)2 adopts a ground state structure consisting of ferromagnetically ordered layers stacked antiferromagnetically. We show that significantly stronger exchange interactions can be realized in these thiocyanate frameworks by using earlier TMs.
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The zebrafish (Danio rerio) is a small teleost fish that is becoming increasingly popular in laboratories worldwide and several attributes have also placed the zebrafish under the spotlight of (eco)toxicological studies. Since the 1990s, international organizations such as ISO and OECD have published guidelines for the use of zebrafish in ecotoxicological assessment of environmental toxicants such as the Fish Embryo Acute Toxicity (FET) test, OECD n° 236 guideline. This protocol uses 3,4-dichloroaniline (DCA), an aniline pesticide whose toxicity to fish species at early life stages is well known, as a positive control. Despite its use, little is known about its molecular mechanisms, especially in the context of the FET test. Therefore, this study aimed to investigate such changes in zebrafish larvae exposed to DCA (4 mg/L) for 96 hours using gel-free proteomics. Twenty-four proteins detected in both groups were identified as significantly affected by DCA exposure, and, when considering group-specific entities, 48 proteins were exclusive to DCA (group-specific proteins) while 248 were only detected in the control group. Proteins modulated by DCA treatment were found to be involved in metabolic processes, especially lipids and hormone metabolism (eg, Apoa1 and Apoa1b and vitelogenins), as well as proteins important for developmental processes and organogenesis (eg, Myhc4, Acta2, Sncb, and Marcksb). The results presented here may therefore provide a better understanding of the relationships between molecular changes and phenotype in zebrafish larvae treated with DCA, the reference compound of the FET test.