Performance of long-wave infrared band of microstructured heavily doped InAsSb on type II superlattice layer part 1: the photonic study.

This article deals with the optical study of nanostructured components which absorb light across the entire long-wave infrared (LWIR) spectral band. The components are made of type-II superlattice (T2SL) absorber and highly doped InAsSb, the latter being nanostructured to ensure multiple resonances. We studied two components: in the first one, the T2SL has a thickness of 1.6 µm, and in the second its thickness is 300 nm. The calculated absorption spectra were shown and the components revealed high absorption thanks to optical resonance and high angular acceptance. A fabrication process has been developed, and optical measurements have confirmed the reliability of the model.

Padlocking dihydrofurannulation for the control of small degree of helicity built on a fused-tetracyclic core.

Enantioselective construction of small molecules displaying a configurationally stable helical shape built on a fused-tetracyclic core is a daunting synthetic challenge even more pronounced when five-membered rings are incorporated in the structure. The resulting higher configurational lability strongly hampers their access, and therefore the development of new efficient methodologies is timely and highly desirable. In this context, we describe a padlocking approach via the enantioselective organocatalytic domino furannulation of appropriately designed achiral fused-tricyclic precursors resulting in the synthesis of configurationally locked helically chiral tetracyclic scaffolds featuring one or two five-membered rings with the simultaneous control of central and helical chiralities.

Enantioselective Synthesis of Heteroatom-Linked Non-Biaryl Atropisomers.

Atropisomers hold significant fascination, not only for their prevalence in natural compounds but also for their biological importance and wide-ranging applications as chiral materials, ligands, and organocatalysts. While biaryl and heterobiaryl atropisomers are commonly studied, the enantioselective synthesis of less abundant heteroatom-linked non-biaryl atropisomers presents a formidable challenge in modern organic synthesis. Unlike classical atropisomers, these molecules allow rotation around two bonds, resulting in low barriers to enantiomerization through concerted bond rotations. In recent years the discovery of new configurationally stable rare non-biaryl scaffolds such as aryl amines, aryl ethers and aryl sulfones as well as innovative methodologies to control their configuration have been disclosed in the literature and constitute the topic of this minireview.

Interband cascade lasers grown simultaneously on GaSb, GaAs and Si substrates.

We report on Sb-based interband cascade lasers simultaneously grown on GaSb, GaAs and Si substrates. 8 µm x 2 mm devices exhibited similar threshold currents around 40 mA at 20°C and achieved continuous-wave (CW) operation up to 65°C on GaSb, GaAs and Si substrates despite a dislocation density of ∼ 4.108 cm-2 for both mismatched substrates. In the CW regime the output power of the devices emitting at 3.3 µm exceeded 30 mW/facet at 20°C. ICLs on GaAs and Si were subsequently aged at 50°C with an injection current of 200 mA, i.e. five times the laser-threshold current. No degradation was observed after 500 h of CW operation, demonstrating the high performance of ICLs and their tolerance to dislocations.

Enantioselective Nucleophilic Vinylic Substitution (SNV) toward 3-Alkenyl-bisoxindoles Facilitated by C6' Steric Bulk of Cinchona Alkaloid.

A C6' bulky substituted quinine-catalyzed SNV reaction between 3-substituted oxindole and (E)-3-(nitromethylene)-oxindole was developed. This enantioselective C(sp3)-C(sp2) coupling furnished bisoxindole scaffolds featuring a vinyl-substituted all-carbon quaternary stereocenter with high stereoselectivities. In addition, the gram-scale synthesis and synthetic post-transformations were conducted to demonstrate the potential synthetic usefulness.

Unlocking the monolithic integration scenario: optical coupling between GaSb diode lasers epitaxially grown on patterned Si substrates and passive SiN waveguides.

Silicon (Si) photonics has recently emerged as a key enabling technology in many application fields thanks to the mature Si process technology, the large silicon wafer size, and promising Si optical properties. The monolithic integration by direct epitaxy of III-V lasers and Si photonic devices on the same Si substrate has been considered for decades as the main obstacle to the realization of dense photonics chips. Despite considerable progress in the last decade, only discrete III-V lasers grown on bare Si wafers have been reported, whatever the wavelength and laser technology. Here we demonstrate the first semiconductor laser grown on a patterned Si photonics platform with light coupled into a waveguide. A mid-IR GaSb-based diode laser was directly grown on a pre-patterned Si photonics wafer equipped with SiN waveguides clad by SiO2. Growth and device fabrication challenges, arising from the template architecture, were overcome to demonstrate more than 10 mW outpower of emitted light in continuous wave operation at room temperature. In addition, around 10% of the light was coupled into the SiN waveguides, in good agreement with theoretical calculations for this butt-coupling configuration. This work lift an important building block and it paves the way for future low-cost, large-scale, fully integrated photonic chips.

Comorbilidades asociadas a la mortalidad por COVID-19 en adultos en Lima, Perú: un estudio de cohorte retrospectiva / Comorbidities associated with COVID-19 mortality in adults in Lima, Peru: a retrospective cohort study

RESUMEN Objetivos. Evaluar las comorbilidades asociadas a la mortalidad en pacientes adultos hospitalizados por COVID-19 de diferentes grupos de edad en hospitales de Lima y Callao. Materiales y métodos. En este estudio de cohorte retrospectiva analizamos datos de pacientes adultos hospitalizados por COVID-19, notificados al Sistema Nacional de Vigilancia Epidemiológica del Ministerio de Salud de Perú de marzo a octubre del 2020. Se estimaron riesgos relativos con intervalos de confianza al 95% mediante modelos de regresión de Poisson con varianza robusta para evaluar las comorbilidades asociadas a la mortalidad por grupos de edad: jóvenes (18-29 años), adultos (30-59 años) y mayores (≥60 años). Resultados. Se incluyeron 2366 jóvenes, 23781 adultos y 25356 adultos mayores en el análisis. Los adultos mayores presentaron la mortalidad más alta (63,7%) en comparación con adultos (27,1%) y jóvenes (8,5%). Independientemente del grupo de edad, la presencia de enfermedad neurológica, enfermedad renal, enfermedad hepática y cáncer se asoció a un mayor riesgo de mortalidad. Adicionalmente, la enfermedad cardiovascular fue también un factor de riesgo en los jóvenes; la obesidad, la diabetes, la enfermedad cardiovascular, la enfermedad pulmonar crónica y la inmunodeficiencia en los adultos; y la obesidad y la enfermedad pulmonar crónica en los mayores. Conclusiones: Independientemente de los grupos de edad, los individuos con enfermedad neurológica crónica, enfermedad renal, enfermedad hepática y cáncer tendrían un alto riesgo de morir por la COVID-19.

ABSTRACT Objectives. To evaluate comorbidities associated with mortality in adult patients hospitalized due to COVID-19 in hospitals in Lima and Callao. Materials and methods. In this retrospective cohort study, we analyzed data from adult patients hospitalized due to COVID-19 reported to the National Epidemiological Surveillance System of the Peruvian Ministry of Health from March to October 2020. We estimated relative risks with 95% confidence intervals using Poisson regression models with robust variance to assess comorbidities associated with mortality by age group: young adults (18-29 years), adults (30-59 years) and older adults (≥60 years). Results. We included 2366 young adults, 23,781 adults and 25,356 older adults. Older adults had the highest mortality (63.7%) compared to adults (27.1%) and young adults (8.5%). Regardless of age group, the presence of neurological disease, renal disease, liver disease, and cancer was associated with an increased risk of mortality. Additionally, cardiovascular disease was also a risk factor in young adults; obesity, diabetes, cardiovascular disease, chronic lung disease, and immunodeficiency in adults; and obesity and chronic lung disease in the elderly. Conclusions. Regardless of age groups, individuals with chronic neurologic disease, renal disease, liver disease, and cancer were at high risk of death from COVID-19.

Enantioselective Synthesis of Atropisomers by Oxidative Aromatization with Central-to-Axial Conversion of Chirality.

Atropisomers are fascinating objects of study by themselves for chemists but also find applications in various sub-fields of applied chemistry. Obtaining them in enantiopure form is far from being a solved challenge, and the past decades has seen a surge of methodological developments in that direction. Among these strategies, oxidative aromatization with central-to-axial conversion of chirality has gained increasing popularity. It consists of the oxidation of a cyclic non-aromatic precursors into the corresponding aromatic atropisomers. This review proposes a critical analysis of this research field by delineating it and discussing its historical background and its present state of the art to draw potential future development directions.

Enantioselective Organocatalysis and Superacid Activation: Challenges and Opportunities.

Since the pioneer reports of the groups of Akiyama and Terada on Brønsted acid organocatalysis, this field never stopped growing with the development of ingenious strategies for the activation of challenging poorly reactive substrates. The development of superacidic organocatalysts is an important way to selectively functionalize reluctant electrophiles and other approaches have also emerged such as the combination of Lewis and Brønsted acids as well as the consecutive organocatalysis and superacid activation. This Concept aims to highlight these different strategies and demonstrate their complementarity.

Catalysis Driven Six-Step Synthesis of Apratoxin A Key Polyketide Fragment.

Apratoxin A is a potent anticancer natural product whose key polyketide fragment constitutes a considerable challenge for organic synthesis, with five prior syntheses requiring 12 to 20 steps for its preparation. By combining different redox-economical catalytic stereoselective transformations, the key polyketide fragment could be rapidly prepared. Followed by a site-selective protection of the diol, this strategy enables the preparation of the apratoxin A fragment in only six steps, representing the shortest route to this polyketide.

Enantiospecific Syntheses of Congested Atropisomers through Chiral Bis(aryne) Synthetic Equivalents.

The synthetic equivalents of the enantiopure binaphthyl bis(aryne) atropisomers derived from BINOL (1,1'-bi-2,2'-naphtol) featuring a stereogenic axis vicinal to the two reactive triple bonds can be generated for the first time in solution in an enantiospecific manner. Using a two-step sequence based on the bidirectional [4+2] cycloaddition of furan derivatives followed by an aromatizative deoxygenation reaction, several 9,9'-bianthracenyl-based atropisomers could be prepared enantiospecifically in high enantiomeric purity. Alternatively, bidirectional reactions with anthracene, 2-bromostyrene, and perylene as the arynophiles afforded very congested bis(benzotriptycene), bis(tetraphene) and bis(anthra[1,2,3,4-ghi]perylene) nanocarbon atropisomers in equally high enantiomeric purity. In complement, cross reactions with two different arynophiles revealed possible. The unusual atropisomer prototypes described in this study open the way to enantiopure nanographene atropisomers designed for functions.

Determination of the Rate Constant of the [4 + 2] Cycloaddition Between an Aryne Atropisomer and Furan in Solution.

Using a specially designed prototype of a nonracemic aryne atropisomer with a low barrier to enantiomerization (ca. 36 kJ·mol-1), it was possible to determine the kinetic constant of its cycloaddition with furan in solution by a combination of theoretical calculations and experimental measurements. It was found that the reaction half-life of this aryne atropisomer in solution with 100 equivalents of furan as the trapping reagent is <150 ns at temperatures above -20 °C.

Mid-infrared III-V semiconductor lasers epitaxially grown on Si substrates.

There is currently much activity toward the integration of mid-infrared semiconductor lasers on Si substrates for developing a variety of smart, compact, sensors based on Si-photonics integrated circuits. We review this rapidly-evolving research field, focusing on the epitaxial integration of antimonide lasers, the only technology covering the whole mid-to-far-infrared spectral range. We explain how a dedicated molecular-beam epitaxy strategy allows for achieving high-performance GaSb-based diode lasers, InAs/AlSb quantum cascade lasers, and InAs/GaInSb interband cascade lasers by direct growth on on-axis (001)Si substrates, whereas GaAs-on-Si or GaSb-on-Si layers grown by metal-organic vapor phase epitaxy in large capability epitaxy tools are suitable templates for antimonide laser overgrowth. We also show that etching the facets of antimonide lasers grown on Si is a viable approach in view of photonic integrated circuits. Remarkably, this review shows that while diode lasers are sensitive to residual crystal defects, the quantum cascade and interband cascade lasers grown on Si exhibit performances comparable to those of similar devices grown on their native substrates, due to their particular band structures and radiative recombination channels. Long device lifetimes have been extrapolated for interband cascade lasers. Finally, routes to be further explored are also presented.

COVID-19 among Amazonian indigenous in Peru: mortality, incidence, and clinical characteristics.

BACKGROUND: Few studies have described the clinical characteristics of patients with COVID-19 from ethnic minority groups. Our objective was to evaluate the mortality and incidence rates, clinical characteristics and factors associated with mortality in cases with COVID-19 belonging to the Amazonian indigenous ethnic group in Peru. METHODS: We performed a retrospective cohort study including all cases from COVID-19 among Peruvian people identified as Amazonian indigenous from 07 March to 31 October 2020. We calculated the standardized mortality and incidence ratios using the indirect age-adjusted method to determine the differences between Amazonian Indigenous and the general population. In addition, we used multivariable logistic regression to determine the risk factors for death. RESULTS: A total of 19 018 laboratory confirmed COVID-19 cases were analyzed. Indigenous people had 3.18 (95% CI, 3.13-3.23) times the risk of infection and 0.34 (0.31-0.37) times the mortality risk of the general Peruvian population. Males had 1.29 (1.04-1.61) times the odds of death compared with females and for each year of age, the odds of mortality increased 1.03 (1.03-1.04) times. Cases with respiratory distress had 2.47 (1.96-3.10) times more likely to die. Having an immunodeficiency was 18.7 (6.12-57.00) times more likely to die. DISCUSSION: The Amazonian indigenous population in Peru was strongly affected by COVID-19 compared with the general Peruvian population.

Hidden Heptacyclic Chiral N-Acyl Iminium Ions: A New Entry to Enantioenriched Polycyclic Azepanes and Azocanes by Superacid-Promoted Intramolecular Pictet-Spengler Reaction.

Enantioenriched complex fused-tricyclic azepanes or bridged-polycyclic azocanes were constructed via a two-step sequence involving an enantioselective organocascade followed by superacid activation of the domino adduct. The activated oxa-bridged azepane acts as a key hidden heptacyclic chiral N-acyl iminium ion triggering a chemo- and diastereoselective intramolecular mono- or di-arylation.

Enantioselective Synthesis of Acyclic Stereotriads Featuring Fluorinated Tetrasubstituted Stereocenters.

Elaboration of enantioenriched complex acyclic stereotriads represents a challenge for modern synthesis even more when fluorinated tetrasubstituted stereocenters are targeted. We have been able to develop a simple strategy in a sequence of two unprecedented steps combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution. The aldol-Tishchenko reaction directly generates a large panel of acyclic 1,3-diols possessing a fluorinated tetrasubstituted stereocenter by condensation of fluorinated ketones with aldehydes under very mild basic conditions. The anti 1,3-diols featuring three contiguous stereogenic centers are generated with excellent diastereocontrol (typically >99 : 1 dr). Depending upon the precursors both diastereomers of stereotriads are accessible through this flexible reaction. Furthermore, from the obtained racemic scaffolds, development of an organocatalyzed kinetic resolution enabled to generate the desired enantioenriched stereotriads with excellent selectivity (typically er >95 : 5).

GaSb-based laser diodes grown on MOCVD GaAs-on-Si templates.

We report GaSb-based laser diodes (LDs) grown on on-axis (001) Si substrates and emitting at 2.3 µm. Two series of LDs were studied and compared. For the first series, a GaAs-based buffer layer was first grown by metal organic chemical vapor deposition (MOCVD) before growing the laser heterostructure by molecular-beam epitaxy (MBE). For the second series, a MOCVD GaSb buffer layer was added between the MOCVD GaAs buffer layer and the MBE laser heterostructure. Both series of LDs exhibited threshold currents in the 50-100 mA range and several mW output power at room temperature. They demonstrated continuous wave operation (CW) up to 70°C (set-up limited) without thermal rollover. Broad area LDs exhibited record threshold-current densities in the 250-350 A.cm-2 range for the second series of LDs, in spite of cracks that appeared during device processing. These results show that the design and fabrication steps of the buffer-layer stacks are critical issues in the epitaxial integration of GaSb-based optoelectronic devices on Si substrates and offer room for much performance improvement.

On the Enantioselective Phosphoric-Acid-Catalyzed Hantzsch Synthesis of Polyhydroquinolines.

A reinvestigation of a chiral phosphoric-acid-catalyzed four-component Hantzsch enantioselective synthesis of polyhydroquinolines reported in 2009 is presented. In our hands, when the reaction was performed with fidelity to the original report using a chiral enantiopure phosphoric acid catalyst, no enantioselectivity was observed. Unlike in the original report, enantioselectivity results are backed by baseline separation of the enantiomers by HPLC analyses on chiral stationary phase with UV and chiroptical detection.

Periselectivity in the Aza-Diels-Alder Reaction of 1-Azadienes with α-Oxoketenes: A Combined Experimental and Theoretical Study.

Inversions in the periselectivity of formal aza-Diels-Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the diastereoselectivity was observed, too. These variations in selectivities were fully rationalized by computational modeling using density functional theory (DFT) methods.