Application to nonlinear optical properties of the RSX-QIDH double-hybrid range-separated functional.

The effective calculation of static nonlinear optical properties requires a considerably high accuracy at a reasonable computational cost, to tackle challenging organic and inorganic systems acting as precursors and/or active layers of materials in (nano-)devices. That trade-off implies to obtain very accurate electronic energies in the presence of externally applied electric fields to consequently obtain static polarizabilities ( α i j ) and hyper-polarizabilities ( ß i j k and γ i j k l ). Density functional theory is known to provide an excellent compromise between accuracy and computational cost, which is however largely impeded for these properties without introducing range-separation techniques. We thus explore here the ability of a modern (double-hybrid and range-separated) Range-Separated eXchange Quadratic Integrand Double-Hybrid exchange-correlation functional to compete in accuracy with more costly and/or tuned methods, thanks to its robust and parameter-free nature.

Kinetic and hydrogen production analysis in the sequential valorization of a Populus clone by cold alkaline extraction and pyrolysis.

This work employed a two-step biorefining process, consisting of a hemicellulose-rich liquor production through ultrasound-assisted cold alkaline extraction (CAE), followed by thermochemical treatment of the resultant solid phase. The post-CAE solid phase's pyrolytic potential was assessed by application of thermogravimetric analysis (TGA) and Friedman's isoconversional method, and also from hydrogen production. The solid phases remaining after the CAE treatment were more reactive than the untreated raw material. Notably, the alkali concentration employed in the first step was the individual variable most pronounced influence on their activation energy (Ea). Thus, at a degree of conversion α = 0.50, Ea ranged from 109.7 to 254.3 kJ/mol for the solid phases, compared to 177 kJ/mol for the raw material; this value decreased with rising glucan content. At maximal degradation, the post-CAE solid phases produced up to 15.57% v/v more hydrogen than did the untreated raw material.

Assessment of the nonempirical r2SCAN-QIDH double-hybrid density functional against large and diverse datasets.

We update the Quadratic Integrand Double-Hybrid (QIDH) model [J. Chem. Phys. 141, 031101 (2014)] by incorporating the nonempirical restored-regularized Strongly Constrained and Appropriately Normed (r2SCAN) meta-generalized gradient approximation exchange-correlation functional, thus devising a robust density functional approximation free of any empirical parameter and incorporating all the constraints so far known for the exchange-correlation kernel. We assessed the new r2SCAN-QIDH expression on the GMTKN55 database and further extend its application to various types of non-covalent interactions (e.g., S66 × 8, O24 × 5). The assessment done shows that the model becomes very competitive in accuracy with respect to parent exchange-correlation functionals of any type, but without relying on any fitted parameter or numerical training.

Accessible interferometric autocorrelator for noise-like pulses based on a Fabry-Perot cavity.

In this work, we develop experimentally a Fabry-Perot fiber optic interferometer applied to the measurement of autocorrelation of complex dynamic pulses generated by a figure-eight fiber laser. The principle is based in the superposition of multiple pulses, which requires two partially reflecting flat surfaces in parallel, resulting in a simple and compact autocorrelator design. The autocorrelation trace obtained exhibits a typical double-scaled structure for noise-like pulses (NLPs), with an ultrashort coherence spur on the order of 100 fs riding upon a broad pedestal of 120 ps. Finally, we show experimentally that the developed Fabry-Perot device is able to measure accurately the autocorrelation of NLPs, as confirmed by comparing the measurement with that of a conventional autocorrelator scheme based on a Michelson interferometer, with the additional advantages of a more compact setup and a much easier alignment procedure compared to the latter.

Correlation vs. exchange competition drives the singlet-triplet excited-state inversion in non-alternant hydrocarbons.

In this work, we focus on the understanding of the driving force behind the S1-T1 excited-state energy inversion (which would thus violate Hund's rule, making the S1 state lower in energy than the T1 state) of two non-benzenoid non-alternant hydrocarbons, composed of odd-membered rings. The molecules considered here have identical chemical composition but different atomic configuration in space. The delicate interplay between structural and electronic factors that might induce inversion and its energy extension, only by a few meV, is systematically investigated here by state-of-the-art calculations. Qualitative and quantitative accurate predictions are obtained employing post-HF methods, thanks to the balanced and careful inclusion of electron correlation effects. The obtained results might guide and rationalize new searches for molecules violating Hund's rule, concomitantly demonstrating the importance of key contributions from the theoretical method of choice.

Electronic structure of rhombus-shaped nanographenes: system size evolution from closed- to open-shell ground states.

We theoretically study and characterize a set of rhombus-shaped nanographenes of increasing size, or n-rhombenes, where n = 2-6, displaying zigzag edges leading to an enhancement of the (poly)radicaloid nature and the appearance of intrinsic magnetism as a function of n. Due to that system-dependent radicaloid nature, we employ spin-flip methods able to capture the challenging physics of the problem, thus providing accurate energy differences between high- and low-spin solutions. The theoretical predictions agree with the experimentally available magnetic exchange coupling for the recently synthesized 5-rhombene, as well as with the size at which the transition from a closed-shell to an open-shell ground-state solution occurs. We also investigate if standard DFT methods are able to reproduce the trend disclosed by spin-flip methods and if the results are highly dependent on the functional choice and/or the intrinsic spin contamination.

Excitation energies of polycylic aromatic hydrocarbons by double-hybrid functionals: Assessing the PBE0-DH and PBE-QIDH models and their range-separated versions.

A family of non-empirical double-hybrid (DH) density functionals, such as Perdew-Burke-Ernzerhof (PBE)0-DH, PBE-QIDH, and their range-separated exchange (RSX) versions RSX-0DH and RSX-QIDH, all using Perdew-Burke-Ernzerhof(PBE) exchange and correlationfunctionals, is applied here to calculate the excitation energies for increasingly longer linear and cyclic acenes as part of their intense benchmarking for excited states of all types. The energies for the two lowest-lying singlet 1La and 1Lb states of linear oligoacenes as well as the triplet 3La and 3Lb states, are calculated and compared with experimental results. These functionals clearly outperform the results obtained from hybrid functionals and favorably compare with other double-hybrid expressions also tested here, such as B2-PLYP, B2GP-PLYP, ωB2-PLYP, and ωB2GP-PLYP. The study is complemented by the computation of adiabatic S0-T1 singlet-triplet energy difference for linear acenes as well as the extension of the study to strained cyclic oligomers, showing how the family of non-empirical expressions robustly leads to competitive results.

Dietary diversity and depression: cross-sectional and longitudinal analyses in Spanish adult population with metabolic syndrome. Findings from PREDIMED-Plus trial.

OBJECTIVE: To examine the cross-sectional and longitudinal (2-year follow-up) associations between dietary diversity (DD) and depressive symptoms. DESIGN: An energy-adjusted dietary diversity score (DDS) was assessed using a validated FFQ and was categorised into quartiles (Q). The variety in each food group was classified into four categories of diversity (C). Depressive symptoms were assessed with Beck Depression Inventory-II (Beck II) questionnaire and depression cases defined as physician-diagnosed or Beck II >= 18. Linear and logistic regression models were used. SETTING: Spanish older adults with metabolic syndrome (MetS). PARTICIPANTS: A total of 6625 adults aged 55-75 years from the PREDIMED-Plus study with overweight or obesity and MetS. RESULTS: Total DDS was inversely and statistically significantly associated with depression in the cross-sectional analysis conducted; OR Q4 v. Q1 = 0·76 (95 % CI (0·64, 0·90)). This was driven by high diversity compared to low diversity (C3 v. C1) of vegetables (OR = 0·75, 95 % CI (0·57, 0·93)), cereals (OR = 0·72 (95 % CI (0·56, 0·94)) and proteins (OR = 0·27, 95 % CI (0·11, 0·62)). In the longitudinal analysis, there was no significant association between the baseline DDS and changes in depressive symptoms after 2 years of follow-up, except for DD in vegetables C4 v. C1 = (ß = 0·70, 95 % CI (0·05, 1·35)). CONCLUSIONS: According to our results, DD is inversely associated with depressive symptoms, but eating more diverse does not seem to reduce the risk of future depression. Additional longitudinal studies (with longer follow-up) are needed to confirm these findings.

Stability of the polyynic form of C18, C22, C26, and C30 nanorings: a challenge tackled by range-separated double-hybrid density functionals.

We calculate the relative energy between the cumulene and polyyne structures of a set of C4k+2 (k = 4-7) rings (C18, C22, C26, and C30 prompted by the recent synthesis of the cyclo[18]carbon (or simply C18) compounds. Reference results were obtained by a costly Quantum Monte-Carlo (QMC) approach, providing thus very accurate values allowing to systematically compare the performance of a variety of wavefunction methods [(i.e., MP2, SCS-MP2, SOS-MP2, DLPNO-CCSD, and DLPNO-CCSD(T)] as well as DFT approaches, applying for the latter a diversity of density functionals covering global and range-separated hybrid and double-hybrid models. The influence of the use of a range-separation scheme for density functionals, for both hybrid and double-hybrid expressions, is discussed according to its key role. Overall, range-separated double-hybrid functionals (e.g., RSX-QIDH) behave very accurately and provide competitive results compared with DLPNO-CCSD(T), at a more reasonable computational cost.

Violation of Hund's rule in molecules: Predicting the excited-state energy inversion by TD-DFT with double-hybrid methods.

The energy difference (ΔEST) between the lowest singlet (S1) state and the triplet (T1) excited state of a set of azaphenalene compounds, which is theoretically and experimentally known to violate Hund's rule, giving rise to the inversion of the order of those states, is calculated here with a family of double-hybrid density functionals. That excited-state inversion is known to be very challenging to reproduce for time-dependent density functional theory employing common functionals, e.g., hybrid or range-separated expressions, but not for wavefunction methods due to the inclusion of higher-than-single excitations. Therefore, we explore here if the last developed family of density functional expressions (i.e., double-hybrid models) is able to provide not only the right excited-state energy order but also accurate ΔEST values, thanks to the approximate inclusion of double excitations within these models. We herein employ standard double-hybrid (B2-PLYP, PBE-QIDH, and PBE0-2), range-separated (ωB2-PLYP and RSX-QIDH), spin-scaled (SCS/SOS-B2PLYP21, SCS-PBE-QIDH, and SOS-PBE-QIDH), and range-separated spin-scaled (SCS/SOS-ωB2-PLYP, SCS-RSX-QIDH, and SOS-RSX-QIDH) expressions to systematically assess the influence of the ingredients entering into the formulation while concomitantly providing insights for their accuracy.

[Quality indicators in hip fracture care after the implementation of an orthogeriatrics team]. / Indicadores de calidad en atención a fractura de cadera tras la implementación de un equipo de ortogeriatría.

INTRODUCTION: The incidence of hip fracture will increase dramatically in the coming decades. It has been associated with high mortality and morbidity. Orthogeriatric programs have improved outcomes in fragility hip fracture worldwide. There is little evidence in Mexico on the impact of orthogeriatrics and adherence to quality indicators. OBJECTIVE: To compare adherence to quality indicators in hip fracture before and after the implementation of an orthogeriatrics team compared to the traditional model. MATERIAL AND METHODS: Quasi-experimental study conducted in León, Mexico. Adherence to quality indicators before and after an interconsultant orthogeriatrics team was compared. The indicators measured were: surgical delay, treatment for osteoporosis, early mobilization, type of implant and delirium. RESULTS: We included 83 patients. The surgical delay was reduced from 144 to 116 hours (28 hours), the percentage of patients with early surgery was increased from 7.9 to 18%, in addition the percentage of patients with treatment for osteoporosis was increased and the incidence of delirium was reduced. CONCLUSION: Adherence to indicators is low, however, it was possible to discreetly increase adherence to these indicators. Internal policies must be generated in public hospitals to improve this adherence and see its impact on long-term outcomes.

INTRODUCCIÓN: La incidencia de fractura de cadera se incrementará radicalmente en las siguientes décadas. Se ha asociado a una mortalidad y morbilidad elevada. Los programas de ortogeriatría en hospitales públicos han demostrado mejorar los resultados asistenciales. Hay poca evidencia en México sobre el impacto de la ortogeriatría y el apego a indicadores de calidad. OBJETIVO: Comparar el apego a indicadores de calidad en fractura de cadera antes y después de la implementación de un equipo de ortogeriatría comparado con el modelo tradicional. MATERIAL Y MÉTODOS: Estudio cuasiexperimental realizado en León, México. Se comparó la adherencia a indicadores de calidad antes y después de un equipo interconsultante de ortogeriatría. Los indicadores medidos fueron: demora quirúrgica, tratamiento para osteoporosis, movilización temprana, tipo de implante y delirium. RESULTADOS: Incluimos 83 pacientes. La demora quirúrgica se disminuyó de 144 a 116 horas (28 horas), se incrementó el porcentaje de pacientes con cirugía temprana de 7.9 a 18%, además se incrementó el porcentaje de pacientes con tratamiento para osteoporosis y se logró disminuir la incidencia de delirium. CONCLUSIÓN: El apego a indicadores es bajo; sin embargo, se logró incrementar discretamente el apego a estos indicadores. Se deben generar políticas internas en los hospitales públicos para mejorar esta adherencia y ver su impacto en los resultados a largo plazo.

Fecal Microbiome Composition Does Not Predict Diet-Induced TMAO Production in Healthy Adults.

Background Trimethylamine-N-oxide (TMAO) is a small molecule derived from the metabolism of dietary nutrients by gut microbes and contributes to cardiovascular disease. Plasma TMAO increases following consumption of red meat. This metabolic change is thought to be partly because of the expansion of gut microbes able to use nutrients abundant in red meat. Methods and Results We used data from a randomized crossover study to estimate the degree to which TMAO can be estimated from fecal microbial composition. Healthy participants received a series of 3 diets that differed in protein source (red meat, white meat, and non-meat), and fecal, plasma, and urine samples were collected following 4 weeks of exposure to each diet. TMAO was quantitated in plasma and urine, while shotgun metagenomic sequencing was performed on fecal DNA. While the cai gene cluster was weakly correlated with plasma TMAO (rho=0.17, P=0.0007), elastic net models of TMAO were not improved by abundances of bacterial genes known to contribute to TMAO synthesis. A global analysis of all taxonomic groups, genes, and gene families found no meaningful predictors of TMAO. We postulated that abundances of known genes related to TMAO production do not predict bacterial metabolism, and we measured choline- and carnitine-trimethylamine lyase activity during fecal culture. Trimethylamine lyase genes were only weakly correlated with the activity of the enzymes they encode. Conclusions Fecal microbiome composition does not predict systemic TMAO because, in this case, gene copy number does not predict bacterial metabolic activity. Registration URL: https://www.clinicaltrials.gov; Unique identifier: NCT01427855.

peri-Acenoacene molecules: tuning of the singlet and triplet excitation energies by modifying their radical character.

The energy difference between singlet and triplet excitons, or ΔEST, is a key parameter for novel light-emission mechanisms (i.e., TADF or thermally activated delayed fluorescence) or other photoactivated processes. We have studied a set of conjugated molecules (peri-acenoacenes and their heteroatom-doped analogues) to observe the evolution of their excited-state properties upon increasing the system size with and without substitution with a pair of N atoms. Since these molecules exhibit a (ground-state) diradicaloid character, together with marked correlation effects influencing the excited-states formed, we have applied a variety of theoretical methods (FT-DFT, TD-DFT, SF-TD-DFT, CIS, CIS(D), SCS-CC2, SA-CASSCF, and SC-NEVPT2) to bracket the accuracy of the results while concomitantly providing insights into electronic structure. The results show how this chemical strategy (N-doping) largely modifies not only the excited-state energies but also the oscillator strengths and the ΔEST values, constituting versatile platforms for fine-tuned photophysical applications.

Clinical Outcome of Kidney Transplant Patients on the Allograft Function, Loss, Effects of HLA-DQB1-DSA+, and Graft Survival.

INTRODUCTION: Matching for HLA-DQB1 molecules and anti-DQ donor-specific antibodies (DSAs) has been less studied to allocate transplants from deceased donors in developed countries. The aim of this study was to evaluate the clinical outcome of 519 kidney transplant recipients on the allograft function, loss, and survival and with emphasis on effects of HLA-DQB1-DSA+ at minimum of 10 years' follow-up. METHODS: Five hundred nineteen kidney transplant patients were allocated into 3 groups (G) by immunologic profiles, namely, G1 (SPI-SAB HLA-DQ negative [DQ-]), G2 (SPI-SAB HLA-DQ positive DSA negative [DQ+/DSA-]), and G3 (SPI-SAB HLA-DQ DSA positive [DQ+ DSA+]), and the outcomes were reported until 10 years after transplantation. RESULTS: The proportion of rejection episodes was higher in G3 (25.0% and 26.32%, respectively) than in G1 (8.63% and 6.82%, respectively) and G2 (10.0% and 0%, respectively; P = .047 and P = .014, respectively). In G3, 3 patients lost their grafts by antibody-mediated rejection. Patients who received kidneys from deceased donors (G3) showed worse graft survival rates than those from G1 donors (P = .001). Patients from G3 had a 2.18-fold higher risk of graft loss than patients from G1 (P = .028). CONCLUSION: Allograft function was worse in G3 than in G2 or G1, and graft losses were more frequent by T-cell-mediated rejection in G1, and graft losses by antibody-mediated rejection were similar in G1 and G3 due to HLA class I (A1, 11 and B 8, 52) and HLA class II by DR7 and DQ 2, 5, 9 DSA, respectively. Allograft survival decreased in patients with HLA-DQB1 DSA. The risk of graft loss was 1.75-fold that in patients who received transplants from living donors.

Low-pressure and liquid level fiber-optic sensor based on polymeric Fabry-Perot cavity.

An experimental study of the interaction between a Mylar® polymer film and a multimode fiber-optic is presented for the simultaneous fiber-optic detection of low-pressure and liquid levels. The junction between the polymer and optical fiber produces an interference spectrum with maximal visibility and free spectral range around 9 dB and 31 nm, respectively. Water pressure, which is controlled by the liquid level, stresses the polymer. As a result, the spectrum wavelength shifts to the blue region, achieving high sensitivities around 2.49 nm/kPa and 24.5 nm/m. The polymeric membrane was analyzed using a finite element model; according to the results, the polymer shows linear stress response. Furthermore, the membrane material is operated below the yielding point. Moreover, the finite analysis provides information about the stress effect over the thickness and the birefringence changes. This sensor exhibits a quadratic polynomial fitting with an adjusted R-squared of 0.9539. The proposed sensing setup offers a cost-effective alternative for liquid level and low-pressure detection.

Negative Singlet-Triplet Excitation Energy Gap in Triangle-Shaped Molecular Emitters for Efficient Triplet Harvesting.

The full harvesting of both singlet and triplet excitons can pave the way toward more efficient molecular light-emission mechanisms (i.e., TADF or thermally activated delayed fluorescence) beyond the spin statistics limit. This TADF mechanism benefits from low (but typically positive) singlet-triplet energy gaps or ΔEST. Recent research has suggested the possibility of inverting the order of the energy of lowest singlet and triplet excited states, thus opening new pathways to promote light emission without any energy barrier through triplet to singlet conversion, which is systematically investigated here by means of theoretical methods. To this end, we have selected a set of heteroatom-substituted triangle-shaped molecules (or triangulenes) for which ΔEST < 0 is predicted. We successfully rationalize the origin of that energy inversion and the reasons for which theoretical methods might produce qualitatively inconsistent predictions depending on how they treat n-tuple excitations (e.g., the large contribution of double excitations for all of the ground and excited states involved). Unfortunately, the time-dependent density functional theory method is unable to deal with the physical effects driving this behavior, which prompted us to use more sophisticated ab initio methods here such as SA-CASSCF, SC-NEVPT2, SCS-CC2, and SCS-ADC(2).