Differential Solvent DEEP-STD NMR and MD Simulations Enable the Determinants of the Molecular Recognition of Heparin Oligosaccharides by Antithrombin to Be Disentangled.

The interaction of heparin with antithrombin (AT) involves a specific sequence corresponding to the pentasaccharide GlcNAc/NS6S-GlcA-GlcNS3S6S-IdoA2S-GlcNS6S (AGA*IA). Recent studies have revealed that two AGA*IA-containing hexasaccharides, which differ in the sulfation degree of the iduronic acid unit, exhibit similar binding to AT, albeit with different affinities. However, the lack of experimental data concerning the molecular contacts between these ligands and the amino acids within the protein-binding site prevents a detailed description of the complexes. Differential epitope mapping (DEEP)-STD NMR, in combination with MD simulations, enables the experimental observation and comparison of two heparin pentasaccharides interacting with AT, revealing slightly different bound orientations and distinct affinities of both glycans for AT. We demonstrate the effectiveness of the differential solvent DEEP-STD NMR approach in determining the presence of polar residues in the recognition sites of glycosaminoglycan-binding proteins.

Speeding-up the Determination of Protein-Ligand Affinities by STD NMR: The Reduced Data Set STD NMR Approach (rd-STD NMR).

STD NMR spectroscopy is a powerful ligand-observed NMR tool for screening and characterizing the interactions of small molecules and low molecular weight fragments with a given macromolecule, identifying the main intermolecular contacts in the bound state. It is also a powerful analytical technique for the accurate determination of protein-ligand dissociation constants (KD) of medium-to-weak affinity, of interest in the pharmaceutical industry. However, accurate KD determination and epitope mapping requires a long series of experiments at increasing saturation times to carry out a full analysis using the so-called STD NMR build-up curve approach and apply the "initial slopes approximation". Here, we have developed a new protocol to bypass this important limitation, which allows us to obtain initial slopes by using just two saturation times and, hence, to very quickly determine precise protein-ligand dissociation constants by STD NMR.

Fluorinated Man9 as a High Mannose Mimetic to Unravel Its Recognition by DC-SIGN Using NMR.

Lectins are capable of reading out the structural information contained in carbohydrates through specific recognition processes. Determining the binding epitope of the sugar is fundamental to understanding this recognition event. Nuclear magnetic resonance (NMR) is a powerful tool to obtain this structural information in solution; however, when the sugar involved is a complex oligosaccharide, such as high mannose, the signal overlap found in the NMR spectra precludes an accurate analysis of the interaction. The introduction of tags into these complex oligosaccharides could overcome these problems and facilitate NMR studies. Here, we show the preparation of the Man9 of high mannose with some fluorine tags and the study of the interaction with its receptor, dendritic cell-specific intercellular adhesion molecule-3-grabbing nonintegrin (DC-SIGN). This fluorinated ligand has allowed us to apply heteronuclear two-dimensional (2D) 1H,19F STD-TOCSYreF NMR experiments, using the initial slope approach, which has facilitated the analysis of the Man9/DC-SIGN interaction, unequivocally providing the binding epitope.

[Concordance between the Work Capability Index and the Years of Surviving Disability Estimated using the PoRT-9LSQ methodology]. / Concordancia entre el Índice de Capacidad Laboral y los Años de Discapacidad Sobrevenida Estimados mediante metodología PoRT-9LSQ.

OBJECTIVE: To analyze the association between lifestyles and health risk factors that can lead to prematurely leaving work, with the expected Years Lived with Disability (AYLD) in a working population, and to calculate the correlation between the Work Ability Index (WAI) and the Work Ability Score (WAS), and then both of these with the AYLD and its economic cost. METHODS: A cross-sectional study in a sample of workers who underwent a health examination. The information was collected using the ICL and WAS questionnaires, applying the PoRT-9LSQ methodology. Linear regression and analysis of variance (ANOVA) were used to analyze the association between the risk factors and AYLD. The correlation between WAI and WAS was analyzed using the intraclass correlation coefficient (ICC), and then between each of these the AYLD and its economic cost using adjusted linear regression.  Results: A total of 590 workers were included. Factors that most influenced the average AYLD were a sedentary lifestyle, poor diet, and overweight/obesity, with statistically significant differences according to sex, shift, and occupation (p<0.05). An ICC of 93.0%  was found between ICL and WAS, a good/excellent rating. The adjusted linear regression between ICL and ADSE was 7.982-0.136xICL (p<0.05), and was similar for WAS.  Conclusions: The WAI is useful for predicting AYLD in the working population. This can facilitate decisionmaking by health personnel to identify vulnerable people, encouraging changes in lifestyle and self-care.

OBJETIVO: Analizar la asociación entre los estilos de vida y factores de riesgo para la salud que pueden suponer un abandono prematuro del trabajo, con los años de discapacidad sobrevenida estimados (ADSE) en población laboral, y calcular la correlación entre el Índice de Capacidad Laboral (ICL) y el Work Ability Score (WAS), y ambos con los ADSE y su coste económico. Métodos: Estudio transversal en una muestra de trabajadores a los que se realizó un examen de salud. La información se recogió mediante los cuestionarios ICL y WAS, y la metodología PoRT-9LSQ. Se realizó un análisis de la asociación entre los factores de riesgo analizados y los ADSE mediante regresión lineal y análisis de la varianza (ANOVA). Se analizó la correlación entre ICL y WAS usando el coeficiente de correlación intraclase (CCI), y con los ADSE y su coste económico mediante regresión lineal ajustada.  Resultados: Se incluyeron 590 trabajadores. Los factores que más influyeron en la media de ADSE fueron el sedentarismo, la mala alimentación y el sobrepeso/obesidad, con diferencias estadísticamente significativas según sexo, turno y ocupación (p<0,05). El CCI entre ICL y WAS fue del 93,0% para una valoración excelente/buena. La regresión lineal ajustada entre ICL y los ADSE fue de 7,982-0,136xICL (p<0,05), siendo similar para el WAS.  Conclusiones: El ICL se ha mostrado útil para la predictibilidad de los ADSE en población laboral, lo que facilitará la toma de decisiones del personal sanitario para identificar personas vulnerables favoreciendo cambios en los estilos de vida y el autocuidado.

Concordancia entre el Índice de Capacidad Laboral y los Años de Discapacidad Sobrevenida Estimados mediante metodología PoRT-9LSQ / Concordance between the Work Capability Index and the Years of Surviving Disability Estimated using the PoRT-9LSQ methodology

Objetivo: Analizar la asociación entre los estilos de vida y factores de riesgo para la salud que pueden suponer un abandono prematuro del trabajo, con los años de discapacidad sobrevenida estimados (ADSE) en población laboral, y calcular la correlación entre el Índice de Capacidad Laboral (ICL) y el Work Ability Score (WAS), y ambos con los ADSE y su coste económico.Métodos: Estudio transversal en una muestra de trabajadores a los que se realizó un exa-men de salud. La información se recogió mediante los cuestionarios ICL y WAS, y la meto-dología PoRT-9LSQ. Se realizó un análisis de la asociación entre los factores de riesgo ana-lizados y los ADSE mediante regresión lineal y análisis de la varianza (ANOVA). Se analizó la correlación entre ICL y WAS usando el coeficiente de correlación intraclase (CCI), y con los ADSE y su coste económico mediante regresión lineal ajustada. Resultados: Se incluyeron 590 trabajadores. Los factores que más influyeron en la media de ADSE fueron el sedentarismo, la mala alimentación y el sobrepeso/obesidad, con dife-rencias estadísticamente significativas según sexo, turno y ocupación (p<0,05). El CCI entre ICL y WAS fue del 93,0% para una valoración excelente/buena. La regresión lineal ajustada entre ICL y los ADSE fue de 7,982-0,136xICL (p<0,05), siendo similar para el WAS. Conclusiones: El ICL se ha mostrado útil para la predictibilidad de los ADSE en población la-boral, lo que facilitará la toma de decisiones del personal sanitario para identificar personas vulnerables favoreciendo cambios en los estilos de vida y el autocuidado (AU)

Objetivo: Analizar la asociación entre los estilos de vida y factores de riesgo para la salud que pueden suponer un abandono prematuro del trabajo, con los años de discapacidad sobrevenida estimados (ADSE) en población laboral, y calcular la correlación entre el Índice de Capacidad Laboral (ICL) y el Work Ability Score (WAS), y ambos con los ADSE y su coste económico.Métodos: Estudio transversal en una muestra de trabajadores a los que se realizó un exa-men de salud. La información se recogió mediante los cuestionarios ICL y WAS, y la meto-dología PoRT-9LSQ. Se realizó un análisis de la asociación entre los factores de riesgo ana-lizados y los ADSE mediante regresión lineal y análisis de la varianza (ANOVA). Se analizó la correlación entre ICL y WAS usando el coeficiente de correlación intraclase (CCI), y con los ADSE y su coste económico mediante regresión lineal ajustada. Resultados: Se incluyeron 590 trabajadores. Los factores que más influyeron en la media de ADSE fueron el sedentarismo, la mala alimentación y el sobrepeso/obesidad, con dife-rencias estadísticamente significativas según sexo, turno y ocupación (p<0,05). El CCI entre ICL y WAS fue del 93,0% para una valoración excelente/buena. La regresión lineal ajustada entre ICL y los ADSE fue de 7,982-0,136xICL (p<0,05), siendo similar para el WAS. Conclusiones: El ICL se ha mostrado útil para la predictibilidad de los ADSE en población la-boral, lo que facilitará la toma de decisiones del personal sanitario para identificar personas vulnerables favoreciendo cambios en los estilos de vida y el autocuidado Conclusions: The WAI is useful for predicting AYLD in the working population. This can facilitate decisionmaking by health personnel to identify vulnerable people, encouraging changes in lifestyle and self-care (AU)

3D-patterned inverse-designed mid-infrared metaoptics.

Modern imaging systems can be enhanced in efficiency, compactness, and application through the introduction of multilayer nanopatterned structures for manipulation of light based on its fundamental properties. High transmission multispectral imaging is elusive due to the commonplace use of filter arrays which discard most of the incident light. Further, given the challenges of miniaturizing optical systems, most cameras do not leverage the wealth of information in polarization and spatial degrees of freedom. Optical metamaterials can respond to these electromagnetic properties but have been explored primarily in single-layer geometries, limiting their performance and multifunctional capacity. Here we use advanced two-photon lithography to realize multilayer scattering structures that achieve highly nontrivial optical transformations intended to process light just before it reaches a focal plane array. Computationally optimized multispectral and polarimetric sorting devices are fabricated with submicron feature sizes and experimentally validated in the mid-infrared. A final structure shown in simulation redirects light based on its angular momentum. These devices demonstrate that with precise 3-dimensional nanopatterning, one can directly modify the scattering properties of a sensor array to create advanced imaging systems.

Uptake of Pb and the Formation of Mixed (Ba,Pb)SO4 Monolayers on Barite During Cyclic Exposure to Lead-Containing Sulfuric Acid.

Barite (BaSO4) is a common additive in lead-acid batteries, where it acts as a nucleating agent to promote the reversible formation and dissolution of PbSO4 during battery cycling. However, little is known about the molecular-scale mechanisms that control the nucleation and cyclic evolution of PbSO4 over a battery's lifetime. In this study, we explore the responses of a barite (001) surface to cycles of high and low lead concentrations in 100 mM sulfuric acid solution using in situ atomic force microscopy and high-resolution X-ray reflectivity. We find that PbSO4 epitaxial films readily nucleate on the barite surface, even from solutions that are undersaturated relative to bulk PbSO4. Despite this, barite (001) proves to be an ineffective nucleator of bulk PbSO4, as multilayer growth is suppressed even in highly supersaturated solutions. Instead, we find evidence that Pb2+ ions can directly exchange with Ba2+ to create mixed (Ba,Pb)SO4 surfaces. These chemically mixed surfaces do not host PbSO4 monolayers as readily as pristine barite, and the original reactivity is not regained until a fresh surface is re-established by aggressive etching. Our results can be partly explained by traditional models of thin-film growth, which predict a Stranski-Krastanov (S-K) growth mode, where monolayer films are stabilized by a reduction in surface energy, but multilayer growth is inhibited by epitaxial strain. Complementary density functional theory calculations confirm the basic energetic terms of the model but also show evidence for thickness-dependent energetics that are more complex than would be predicted from traditional models. The experimental results are better understood by extending the model to consider the formation of mixed surfaces and films, which have reduced strain and interfacial energies relative to pure films while also being stabilized by entropy of mixing. These insights into nonstoichiometric heteroepitaxy will enable better predictions of how barite affects PbSO4 nucleation in battery environments.

Baculovirus-mediated expression of a Helicobacter pylori protein-based multiepitope hybrid gene induces a potent B cell response in mice.

Helicobacter pylori is a gram-negative bacterium that is present in over half of the world's population. The colonization of the stomach́s gastric mucosa by H. pylori is related to the onset of chronic gastritis, peptic ulcer, and cancer. The estimated deaths from gastric cancer caused by this bacterial infection are in the 15,000-150,000 range. Current treatment for controlling the colonization of H. pylori includes the administration of two to four antibiotics and a gastric ATPase proton pump inhibitor. Nevertheless, the bacterium has shown increased resistance to antibiotics. Despite an extensive list of attempts to develop a vaccine, no approved vaccine against H. pylori is available. Recombinant viruses are a novel alternative for the control of primary pathogenic agents. In this work, we employed a baculovirus that carries a Thp1 transgene coding for nine H. pylori epitopes, some from the literature, and others were selected in silico from the sequence of H. pylori proteins (carbonic anhydrase, urease B subunit, gamma-glutamyl transpeptidase, Lpp20, Cag7, and CagL). We verified the expression of this hybrid multiepitopic protein in HeLa cells. Mice were inoculated with the recombinant baculovirus Bac-Thp1 using various administration routes: intranasal, intragastric, intramuscular, and a combination of intranasal and intragastric. We identified a strong adjuvant-independent IgG-antibody response in the serum of recombinant baculovirus-Thp1 inoculated mice, which was specific for a strain of H. pylori isolated from a human patient. The bacterium-specific IgG-antibodies were present in sera 125 days after the first vaccine administration. Also, H. pylori-specific IgA-antibodies were found in feces at 82 days after the first inoculation. A baculovirus-based vaccine for H. pylori is promising for controlling this pathogen in humans.

Patenting trends by Mexican pharmaceutical companies.

Aim: the activity of patent claims by Mexican pharmaceutical companies is unknown. Objective: analyse the trend in patents of Mexican pharmaceutical companies. Method: a search for patents was carried out in the patent database of the Mexican Institute of Industrial Property, using the list of Mexican pharmaceutical companies belonging to the Mexican Association of Pharmaceutical Research Industries, and the codes A61K, A61P and C07 of the International Patent Classification. Results: the leading companies in patent applications were Liomont, Senosiain and RIMSA; however, Mexican pharmaceutical companies claim very few patents, only 266 patent applications in the period 2000-2020, with a technological factor with a value of zero, and a commercial factor of little value. Conclusion: Mexican pharmaceutical companies lack a robust patent system, without growth, and with a low percentage of patents with high commercial value.

Tuning the Diradical Character of Indolocarbazoles: Impact of Structural Isomerism and Substitution Position.

In this study, a set of 10 positional indolocarbazole (ICz) isomers substituted with dicyanomethylene groups connected via para or meta positions are computationally investigated with the aim of exploring the efficiency of structural isomerism and substitution position in controlling their optical and electronic properties. Unrestricted density functional theory (DFT), a spin-flip time-dependent DFT approach, and the multireference CASSCF/NEVPT2 method have been applied to correlate the diradical character with the energetic trends (i.e., singlet-triplet energy gaps). In addition, the nucleus-independent chemical shift together with ACID plots and Raman intensity calculations were used to strengthen the relationship between the diradical character and (anti)aromaticity. Our study reveals that the substitution pattern and structural isomerism represent a very effective way to tune the diradical properties in ICz-based systems with meta-substituted systems with a V-shaped structure displaying the largest diradical character. Thus, this work contributes to the elucidation of the challenging chemical reactivity and physical properties of diradicaloid systems, guiding experimental chemists to produce new molecules with desirable properties.

Humidified rapid-insufflation ventilatory exchange is a means of oxygenation during rigid bronchoscopy: A case series.

Humidified rapid-insufflation ventilatory exchange (HRIVE) is an option for maintenance of oxygenation. This technique allows for oxygenation while the patient is apnoeic due to continuous positive airway pressure and gas exchange through flow-dependent dead space flushing. There is no study about the usage of HRIVE during rigid bronchoscopy. This retrospective study looked at rigid bronchoscopy cases utilizing HRIVE. Data points assessing adequacy of oxygenation and ventilation were recorded at time points: oxygen saturation (SpO2), partial pressure of oxygen (PaO2) and partial pressure of carbon dioxide (PaCO2). Our nine cases had an average baseline SpO2 of 99.26%, 95.56% at 10 min into HRIVE and 95.27% at the end of HRIVE. The average baseline PaO2 was 309.01 mmHg, 124.99 mmHg at 10 min into HRIVE and 128.17 mmHg at the end of HRIVE. The average baseline PaCO2 was 43.26 mmHg, 68.76 mmHg at 10 min into HRIVE and 75.52 mmHg at the end of HRIVE. The average pre-HRIVE end-tidal CO2 (ETCO2) was 38.56 mmHg and the average post-HRIVE ETCO2 was 61.22 mmHg. The average baseline pH was 7.36, 7.22 at 10 min into HRIVE and 7.19 at the end of HRIVE. In this small cohort study, HRIVE was able to maintain adequate oxygenation via the rigid bronchoscope in a select group of patients. Hypercapnia and respiratory acidosis did result after 10 min, which may predispose certain patient populations to complications. HRIVE potentially offers an additional option of oxygenation via the rigid bronchoscope.

Self-assembling, supramolecular chemistry and pharmacology of amphotericin B: Poly-aggregates, oligomers and monomers.

Antifungal drugs such as amphotericin B (AmB) interact with lipids and phospholipids located on fungal cell membranes to disrupt them and create pores, leading to cell apoptosis and therefore efficacy. At the same time, the interaction can also take place with cell components from mammalian cells, leading to toxicity. AmB was selected as a model antifungal drug due to the complexity of its supramolecular chemical structure which can self-assemble in three different aggregation states in aqueous media: monomer, oligomer (also known as dimer) and poly-aggregate. The interplay between AmB self-assembly and its efficacy or toxicity against fungal or mammalian cells is not yet fully understood. To the best of our knowledge, this is the first report that investigates the role of excipients in the supramolecular chemistry of AmB and the impact on its biological activity and toxicity. The monomeric state was obtained by complexation with cyclodextrins resulting in the most toxic state, which was attributed to the greater production of highly reactive oxygen species upon disruption of mammalian cell membranes, a less specific mechanism of action compared to the binding to the ergosterol located in fungal cell membranes. The interaction between AmB and sodium deoxycholate resulted in the oligomeric and poly-aggregated forms which bound more selectively to the ergosterol of fungal cell membranes. NMR combined with XRD studies elucidated the interaction between drug and excipient to achieve the AmB aggregation states, and ultimately, their diffusivity across membranes. A linear correlation between particle size and the efficacy/toxicity ratio was established allowing to modulate the biological effect of the drug and hence, to improve pharmacological regimens. However, particle size is not the only factor modulating the biological response but also the equilibrium of each state which dictates the fraction of free monomeric form available. Tuning the aggregation state of AmB formulations is a promising strategy to trigger a more selective response against fungal cells and to reduce the toxicity in mammalian cells.

Effect of Nafion content and hydration level on the electrochemical area of a Pt nanocatalyst in the triple-phase boundary.

Despite the great scientific effort, there are still some aspects of a polymeric membrane-based fuel cell (PEMFC) operation that are difficult to access experimentally. This is the case of the so-called triple-phase boundary (TPB), where the ionomer (commonly Nafion) interacts with the supported nanocatalyst (commonly Pt) and is key to the catalytic activity of the system. In this work, we use molecular dynamics simulations and electrochemical experiments on a Nafion/Pt/C system. We perform a systematic analysis, at an atomistic level, to evaluate the effect of several fundamental factors and their intercorrelation on the electrochemically active area (ECSA) of the catalysts. Our results reveal that at high Nafion contents, the catalyst utilization is affected due to the strong interaction between the sulfonic groups of the ionomer and the surface of the Pt nanoparticles (NPs). On the other hand, when the hydration level of the membrane decreases, the sulfonic groups have a greater occupation on the NP surface, covering the active area with hydrophobic Nafion chains and therefore increasing the inactive area. Voltammograms can corroborate our calculations. Overall, this investigation allows us to rationalize how the catalyst utilization is affected, which is an important step in establishing the relationship between the environment and the effectiveness and durability of the PEMFC system.

Quantification of BERT Diagnosis Generalizability Across Medical Specialties Using Semantic Dataset Distance.

Deep learning models in healthcare may fail to generalize on data from unseen corpora. Additionally, no quantitative metric exists to tell how existing models will perform on new data. Previous studies demonstrated that NLP models of medical notes generalize variably between institutions, but ignored other levels of healthcare organization. We measured SciBERT diagnosis sentiment classifier generalizability between medical specialties using EHR sentences from MIMIC-III. Models trained on one specialty performed better on internal test sets than mixed or external test sets (mean AUCs 0.92, 0.87, and 0.83, respectively; p = 0.016). When models are trained on more specialties, they have better test performances (p < 1e-4). Model performance on new corpora is directly correlated to the similarity between train and test sentence content (p < 1e-4). Future studies should assess additional axes of generalization to ensure deep learning models fulfil their intended purpose across institutions, specialties, and practices.

Molecular Recognition of Natural and Non-Natural Substrates by Cellodextrin Phosphorylase from Ruminiclostridium Thermocellum Investigated by NMR Spectroscopy.

ß-1→4-Glucan polysaccharides like cellulose, derivatives and analogues, are attracting attention due to their unique physicochemical properties, as ideal candidates for many different applications in biotechnology. Access to these polysaccharides with a high level of purity at scale is still challenging, and eco-friendly alternatives by using enzymes in vitro are highly desirable. One prominent candidate enzyme is cellodextrin phosphorylase (CDP) from Ruminiclostridium thermocellum, which is able to yield cellulose oligomers from short cellodextrins and α-d-glucose 1-phosphate (Glc-1-P) as substrates. Remarkably, its broad specificity towards donors and acceptors allows the generation of highly diverse cellulose-based structures to produce novel materials. However, to fully exploit this CDP broad specificity, a detailed understanding of the molecular recognition of substrates by this enzyme in solution is needed. Herein, we provide a detailed investigation of the molecular recognition of ligands by CDP in solution by saturation transfer difference (STD) NMR spectroscopy, tr-NOESY and protein-ligand docking. Our results, discussed in the context of previous reaction kinetics data in the literature, allow a better understanding of the structural basis of the broad binding specificity of this biotechnologically relevant enzyme.

Dual-Salt Electrolytes to Effectively Reduce Impedance Rise of High-Nickel Lithium-Ion Batteries.

Simply mixing several lithium salts in one electrolyte to obtain blended salt electrolytes has been demonstrated as a promising strategy to formulate advanced electrolytes for lithium metal batteries (LMBs) and lithium-ion batteries (LIBs). In this study, we report the use of dual-salt electrolytes containing lithium hexafluorophosphate (LiPF6) and lithium difluorophosphate (LiDFP) in ethylene carbonate/ethyl methyl carbonate (EC/EMC) mixture and tested them in layered high-nickel LIB cells. LiNi0.94Co0.06O2 was synthesized through a coprecipitation method and was used as a representative high-nickel cathode for the U.S. DOE realizing next-generation cathode (RNGC) deep dive program. The ionic conductivity of dual-salt electrolytes can be maintained by controlling the amount of LiDFP. Techniques including 1H Nuclear Magnetic Resonance (NMR), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-mass spectrometry (ICP-MS), and differential voltage analysis (DVA) were used to understand the improved performance. The multifaceted benefits of using the dual-salt electrolytes include (1) reduced transesterification, (2) formation of a stable cathode electrolyte interface, and (3) mitigation of cathode degradation at high voltages, especially stabilization of oxide particles during the H2 ↔ H3 transformation.

Imaging from the visible to the longwave infrared wavelengths via an inverse-designed flat lens.

It is generally assumed that correcting chromatic aberrations in imaging requires multiple optical elements. Here, we show that by allowing the phase in the image plane to be a free parameter, it is possible to correct chromatic variation of focal length over an extremely large bandwidth, from the visible (Vis) to the longwave infrared (LWIR) wavelengths using a single diffractive surface, i.e., a flat lens. Specifically, we designed, fabricated and characterized a flat, multi-level diffractive lens (MDL) with a thickness of ≤ 10µm, diameter of ∼1mm, and focal length of 18mm, which was constant over the operating bandwidth of λ=0.45µm (blue) to 15µm (LWIR). We experimentally characterized the point-spread functions, aberrations and imaging performance of cameras comprised of this MDL and appropriate image sensors for λ=0.45µm to 11µm. We further show using simulations that such extreme achromatic MDLs can be achieved even at high numerical apertures (NA=0.81). By drastically increasing the operating bandwidth and eliminating several refractive lenses, our approach enables thinner, lighter and simpler imaging systems.

Spin diffusion transfer difference (SDTD) NMR: An advanced method for the characterisation of water structuration within particle networks.

HYPOTHESIS: The classical STD NMR protocol to monitor solvent interactions in gels is strongly dependent on gelator and solvent concentrations and does not report on the degree of structuration of the solvent at the particle/solvent interface. We hypothesised that, for suspensions of large gelator particles, solvent structuration could be characterised by STD NMR when taking into account the particle-to-solvent 1H-1H spin diffusion transfer using the 1D diffusion equation. EXPERIMENTS: We have carried out a systematic study on effect of gelator and solvent concentrations, and gelator surface charge, affecting the behaviour of the classical STD NMR build-up curves. To do so, we have characterised solvent interactions in dispersions of starch and cellulose-like particles prepared in deuterated water and alcohol/D2O mixtures. FINDINGS: The Spin Diffusion Transfer Difference (SDTD) NMR protocol is independent of the gelator and solvent concentrations, hence allowing the estimation of the degree of solvent structuration within different particle networks. In addition, the simulation of SDTD build-up curves using the general one-dimensional diffusion equation allows the determination of minimum distances (r) and spin diffusion rates (D) at the particle/solvent interface. This novel NMR protocol can be readily extended to characterise the solvent(s) organisation in any type of colloidal systems constituted by large particles.

Edible Chitosan/Propolis Coatings and Their Effect on Ripening, Development of Aspergillus flavus, and Sensory Quality in Fig Fruit, during Controlled Storage.

Biodegradable alternatives for the control of Aspergillus flavus in fig fruit were tested with the application of coatings based on chitosan (CS) and propolis (P). To potentiate the fungicidal effect, nanoparticles of these two (CSNPs and PNPs) were also considered. The objectives of this research were to evaluate the effect of different formulations on: (a) the ripening process of the fig, (b) the incidence of A. flavus and the production of aflatoxins, and (c) the acceptance of the treated fruit by a panel. The nanostructured coatings did not influence the ripening process of the fruit during the 12 days of storage, however, the antioxidant activity increased by approximately 30% with the coating CS + PNPs + P. The figs treated with CS + CSNPs + PNPs + P, inhibited the growth of the fungus by about 20% to 30% under laboratory and semi-commercial conditions. For all treatments, the aflatoxin production was lower than 20 ppb compared to the control with values of c.a. 250 ppb. The sensory quality was acceptable among the panel. The edible coatings can be a non-toxic alternative for post-harvest preservation and the consumption of fig fruit. The next step will be its inclusion and evaluation at a commercial level in packing houses.

Dynamic Covalent Properties of a Novel Indolo[3,2-b]carbazole Diradical.

This work describes the synthesis and properties of a dicyanomethylene-substituted indolo[3,2-b]carbazole diradical ICz-CN. This quinoidal system dimerises almost completely to (ICz-CN)2 , which contains two long C(sp3 )-C(sp3 ) σ-bonds between the dicyanomethylene units. The minor open-shell ICz-CN component in the solid-state mixture was identified by EPR spectroscopy. Cyclic voltammetry and UV-visible spectroelectrochemical data, as well as comparison with reference monomer ICz-Br reveal that the nature of the one-electron oxidation of (ICz-CN)2 at ambient temperature and ICz-CN at elevated temperature is very similar in all these compounds due to the prevailing localization of their HOMO on the ICz backbone. The peculiar cathodic behaviour reflects the co-existence of (ICz-CN)2 and ICz-CN. The involvement of the dicyanomethylene groups stabilizes the close-lying LUMO and LUMO+1 of (ICz-CN)2 and especially ICz-CN compared to ICz-Br, resulting in a distinctive cathodic response at low overpotentials. Differently from neutral ICz-CN, its radical anion and dianion are remarkably stable under ambient conditions. The UV/Vis(-NIR) electronic transitions in parent (ICz-CN)2 and ICz-CN and their different redox forms have been assigned convincingly with the aid of TD-DFT calculations. The σ-bond in neutral (ICz-CN)2 is cleaved in solution and in the solid-state upon soft external stimuli (temperature, pressure), showing a strong chromism from light yellow to blue-green. Notably, in the solid state, the monomeric diradical species is predominantly formed under high hydrostatic pressure (>1 GPa).