Giant magnetic anisotropy at nanoscale: overcoming the superparamagnetic limit

It has been recently observed for palladium and gold nanoparticles, that the magnetic moment at constant applied field does not change with temperature over the range comprised between 5 and 300 K. These samples with size smaller than 2.5 nm exhibit remanence up to room temperature. The permanent magnetism for so small samples up to so high temperatures has been explained as due to blocking of local magnetic moment by giant magnetic anisotropies. In this report we show, by analysing the anisotropy of thiol capped gold films, that the orbital momentum induced at the surface conduction electrons is crucial to understand the observed giant anisotropy. The orbital motion is driven by localised charge and/or spin through spin orbit interaction, that reaches extremely high values at the surfaces. The induced orbital moment gives rise to an effective field of the order of 103 T that is responsible of the giant anisotropy.Comment: 15 pages, 2 figures, submitted to PR

Photophysical Characterization of Isoguanine in a Prebiotic-Like Environment

It is intriguing how a mixture of organic molecules survived the prebiotic UV fluxes and evolved into the actual genetic building blocks. Scientists are trying to shed light on this issue by synthesizing nucleic acid monomers and their analogues under prebiotic Era-like conditions and by exploring their excited state dynamics. To further add to this important body of knowledge, this study discloses new insights into the photophysical properties of protonated isoguanine, an isomorph of guanine, using steady-state and femtosecond broadband transient absorption spectroscopies, and quantum mechanical calculations. Protonated isoguanine decays in ultrafast time scales following 292 nm excitation, consistently with the barrierless paths connecting the bright S1 (ππ*) state with different internal conversion funnels. Complementary calculations for neutral isoguanine predict similar photophysical properties. These results demonstrate that protonated isoguanine can be considered photostable in contrast to protonated guanine, which exhibits 40-fold longer excited state lifetimesThe authors acknowledge funding from the National Science Foundation (Grant No. CHE-1800052), the Ramón y Cajal Program (Grant: RYC-2016-20489) and the Ministerio de Ciencia, Innovación y Universidades (PGC2018-094644-B-C21, PID2021- 125207NB-C31 and PRE2019-090448 projects). L. M. F. thanks the Madrid Government (Comunidad de Madrid-Spain) under the Multiannual Agreement with Universidad Autónoma de Madrid in the line Support to Young Researchers, in the context of the V PRICIT (Regional Programme of Research and Technological Innovation) (SI3/PJI/2021-00331

Correlation between magnetic and transport properties in nanocrystalline Fe thin films: A grain-boundary magnetic disorder effect

We report on transport and magnetic measurements of islanded Fe(110) thin films. The electrical resistivity exhibits an anomalous increase at low temperatures, which disappears under the action of a magnetic field. Since such an anomaly completely disappears under the action of a magnetic field, it is inferred that it originates from spin-dependent scattering. We interpret the strong changes in the spin-dependent scattering in our films to be due to a low-temperature spin freezing of the island boundary magnetic regions that impedes ferromagnetic exchange between islands. A consequence of this magnetic behavior is the random arrangement of the individual magnetization, determined by the magnetocrystalline anisotropy of each island, resulting in an increase of the resistivity below the freezing temperature.Z.S. and J.L.M. acknowledge the Comunidad de Madrid for financial support. Work was performed under the financial support of the Comunidad de Madrid and the Spanish Commission of Science and Technology.Peer reviewe

Controlled Anisotropic Deformation of Ag Nanoparticles by Si Ion Irradiation

The shape and alignment of silver nanoparticles embedded in a glass matrix is controlled using silicon ion irradiation. Symmetric silver nanoparticles are transformed into anisotropic particles whose larger axis is along the ion beam. Upon irradiation, the surface plasmon resonance of symmetric particles splits into two resonances whose separation depends on the fluence of the ion irradiation. Simulations of the optical absorbance show that the anisotropy is caused by the deformation and alignment of the nanoparticles, and that both properties are controlled with the irradiation fluence.Comment: Submitted to Phys. Rev. Lett. (October 14, 2005

The origin of efficient triplet state population in sulfur-substituted nucleobases

Elucidating the photophysical mechanisms in sulfur-substituted nucleobases (thiobases) is essential for designing prospective drugs for photo-and chemotherapeutic applications. Although it has long been established that the phototherapeutic activity of thiobases is intimately linked to efficient intersystem crossing into reactive triplet states, the molecular factors underlying this efficiency are poorly understood. Herein we combine femtosecond transient absorption experiments with quantum chemistry and nonadiabatic dynamics simulations to investigate 2-thiocytosine as a necessary step to unravel the electronic and structural elements that lead to ultrafast and near-unity triplet-state population in thiobases in general. We show that different parts of the potential energy surfaces are stabilized to different extents via thionation, quenching the intrinsic photostability of canonical DNA and RNA nucleobases. These findings satisfactorily explain why thiobases exhibit the fastest intersystem crossing lifetimes measured to date among bio-organic molecules and have near-unity triplet yields, whereas the triplet yields of canonical nucleobases are nearly zeroS.M., P.M. and L.G. thank the Austrian Science Fund (FWF) through project P25827, the COST action CM1204 (XLIC) and the Vienna Scientific Cluster (VSC) for the allocation of computational time. We also thank F. Plasser for assistance with the TheoDORE program. I.C. and L.M.-F. thank the Comunidad Autónoma de Madrid, the Ministerio de Economía y Competitividad (Spain) for an FPU (L.M.-F.) grant, the Projects FOTOCARBON-CM S2013/MIT-2841 and No. CTQ2015-63997-C2, and the ERA-Chemistry Project PIM2010EEC-00751 for financial support, as well as the Centro de Computación Científica UAM for generous allocation of computational time. M.P., N.D. and C.E.C.-H. acknowledge the CAREER program of the National Science Foundation (Grant No. CHE-1255084) for financial suppor

Tomato STEROL GLYCOSYLTRANSFERASE 1 silencing unveils a major role of steryl glycosides in plant and fruit development

Free and glycosylated sterols localize in the plant cell plasma membrane, where in combination with other lipids regulate its structure and function. The role of glycosylated sterols in regulating membrane-associated biological processes is more relevant in plants like tomato (Solanum lycopersicum), in which glycosylated sterols are the predominant sterols. A proper ratio of free sterols versus glycosylated sterols has proven to be essential for proper plant performance in several species, but almost nothing is known in tomato. To assess the role of glycosylated sterols in tomato plant and fruit development, we generated transgenic lines of tomato cultivar Micro-Tom expressing two different amiRNAs devised to silence STEROL GLYCOSYLTRANSFERASE 1, the most actively expressed of the four genes encoding sterol glycosyltransferases in this plant. STEROL GLYCOSYLTRANSFERASE 1 gene silencing caused moderate plant dwarfism and reduced fruit size. Analysis of the profile of glycosylated sterols throughout fruit development demonstrated that the maintenance of proper levels of these compounds during the early stages of fruit development is essential for normal fruit growth, since reduced levels of glycosylated sterols trigger a transcriptional downregulatory response that affects genes involved in processes that are critical for proper fruit development, such as seed filling, cell wall extension and auxin signaling

Life-Cycle Assessment and Acoustic Simulation of Drywall Building Partitions with Bio-Based Materials

[EN] The ecological transition is a process the building industry is bound to undertake. This study aimed to develop new bio-based building partition typologies and to determine if they are suitable ecological alternatives to the conventional non-renewable ones used today. This work started with the development of a bio-based epoxy composite board and a waste-based sheep wool acoustic absorbent. Six different partition typologies combining conventional and bio-based materials were analyzed. A drywall partition composed of gypsum plasterboard and mineral wool was used as the baseline. First, a cradle-to-gate life cycle assessment was performed to compare their environmental impacts. Secondly, a mathematical simulation was performed to evaluate their airborne acoustic insulation. The LCA results show a 50% decrease in the amount of CO(2)equivalent emitted when replacing plasterboard with bio-composite boards. The bio-composites lower the overall environmental impact by 40%. In the case of the acoustic absorbents, replacing the mineral wool with cellulose or sheep wool decreases the carbon emissions and the overall environmental impact of the partition from 4% and 6%, respectively. However, while the bio-based acoustic absorbents used offer good acoustic results, the bio-composites have a lower airborne acoustic insulation than conventional gypsum plasterboard.This research was funded by the Spanish Ministry of Economy, Industry, and Competitiveness (BIA2013-41537-R). The project was co-funded by the European Regional Development Fund and it is included in the R+D National Programme for Research Aimed at the Challenges of Society.Quintana-Gallardo, A.; Alba, J.; Rey Tormos, RMD.; Crespo, J.; Guillén Guillamón, IE. (2020). Life-Cycle Assessment and Acoustic Simulation of Drywall Building Partitions with Bio-Based Materials. Polymers. 12(9):1-16. https://doi.org/10.3390/polym12091965S11612

Renal dysfunction after orthotopic heart transplantation: incidence, natural history, and risk factors

[Abstract] Background. Renal dysfunction is a common complication after orthotopic heart transplantation (HT). The importance of factors other than exposure to immunosuppressive drugs is unclear. The purpose of this study was to determine the incidence and natural history of renal dysfunction following heart transplantation, and to evaluate a number of variables as risk factors for this condition. Methods. We examined the creatinine levels at 1, 6, 12, 24, and 60 months in 262 consecutive heart transplant patients who survived at least 1 year. The potential risk factors included pre- and posttransplantation diabetes mellitus, arterial hypertension, and drugs used to control arterial hypertension. Results. 17.2% of patients showed mild renal dysfunction (creatinine 1.5-2.5 mg/dL) and 1.9% moderate dysfunction (creatinine >2.5 mg/dL) at 1 month; 29.8% showed mild and 1.1% moderate dysfunction at 6 months; 33.2% showed mild and 1.9% moderate dysfunction at 1 year; 40% showed mild, 0.9% moderate and 0.4% severe dysfunction (requiring dialysis or renal transplantation) at 2 years; and 43.6% showed mild, 1.7% moderate and 0.9% severe dysfunction at 5 years. None of the conditions analyzed as possible risk factors showed a significant association with renal dysfunction except the use of diuretics. Conclusion. The incidence of renal dysfunction after orthotopic heart transplantation was 33.6% within the first year after transplant and 44% within the first five years, although more than 95% of cases were mild. The incidence increased with time after transplantation. Renal dysfunction seems likely to be multifactorial in origin, but no individual risk factors were identified