High Photon Upconversion Efficiency with Hybrid Triplet Sensitizers by Ultrafast Hole-Routing in Electronic-Doped Nanocrystals

Low-power photon upconversion (UC) based on sensitized triplet–triplet annihilation (sTTA) is considered as the most promising upward wavelength-shifting technique to enhance the light-harvesting capability of solar devices. Colloidal nanocrystals (NCs) with conjugated organic ligands have been recently proposed to extend the limited light-harvesting capability of molecular absorbers. Key to their functioning is efficient energy transfer (ET) from the NC to the triplet state of the ligands that sensitize free annihilator moieties responsible for the upconverted luminescence. The ET efficiency is typically limited by parasitic processes, above all nonradiative hole-transfer to the ligand highest occupied molecular orbital (HOMO). Here, a new exciton-manipulation approach is demonstrated that enables loss-free ET by electronically doping CdSe NCs with gold impurities that introduce a hole-accepting intragap state above the HOMO energy of 9-anthracene acid ligands. Upon photoexcitation, the NC photoholes are rapidly routed to the Au-level, producing a long-lived bound exciton in perfect resonance with the ligand triplet. This hinders hole-transfer leading to ≈100% efficient ET that translates into an upconversion quantum yield as high as ≈12% (≈24% in the normalized definition), which is the highest performance for NC-based upconverters based on sTTA to date and approaches the record efficiency of optimized organic systems.     

Fatigue response up to 109 cycles of a structural epoxy adhesive

In the present paper, the very‐high‐cycle fatigue (VHCF) response of a structural adhesive used for automotive applications, Betaforce 4600G modified with microspheres, has been experimentally assessed. Ultrasonic fully reversed tension–compression tests up to 10⁹ cycles have been carried out with the testing machine developed by the authors on adhesives without macroscopic defects and on adhesives with artificial defects, inserted during the butt‐joint preparation. Fracture surfaces have been observed with the optical microscope and the P‐S‐N curves estimated. Experimental results have shown that defect location significantly affects the VHCF strength and fracture surfaces exhibit a peculiar morphology with three distinct characteristic regions.     

The evolving model of communication in sociotechnical systems

Reflection on the natural/artificial, real/imaginary, subjective/objective dicotomies is increasingly the subject of debate on systems of communication, which make more and more widespread use of expert and/or intelligent advanced technologies. This paper analyses different forms of communication operating in a socio-technical system. The analysis is concerned with changes in creativity and participation of the human being in the decision and production processes within various contexts of social life. It is thus important to verify the possibility of an interpolation between vital world, social system, and information technologies in order to understand a possible interrelation between therational and therelational components in the presentsocio-technical system.     

BiFeO3 films doped in the A or B sites: effects on the structural and morphological properties

Metal-Organic Chemical Vapor Deposition (MOCVD) has been applied to the fabrication of BiFeO3 films undoped and doped with Ba or Ti on SrTiO3 (100) and YSZ (100) substrates. The films have been deposited using a multi-metal source, consisting of the Bi(phenyl)3, Fe(tmhd)3 and Ba(hfa)2 tetraglyme or Ti(tmhd)2(O-iPr)2 (phenyl = -C6H5, H-tmhd = 2,2,6,6-tetramethyl-3,5-heptandione; O-iPr = iso-propoxide; H-hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = CH3O(CH2CH2O)4CH3) precursor mixture. The structural and morphological characterization of films has been carried out using X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). Chemical compositional studies have been performed by energy dispersive X-ray (EDX) analysis. Structural and morphological characterizations point to the formation of homogeneous and flat surfaces for both undoped and doped BiFeO3 films.     

Cover Image,Volume 97, Issue 2

The cover image, by Shanise Lisie Mello El Halal et al., is based on the Research Paper Morphological, mechanical, barrier and properties of films based on acetylated starch and cellulose from barley, DOI: 10.1002/jsfa.7773 .

     

A New Human Platelet Lysate for Mesenchymal Stem Cell Production Compliant with Good Manufacturing Practice Conditions Preserves the Chemical Characteristics and Biological Activity of Lyo-Secretome Isolated by Ultrafiltration

Recently, we proposed a Good Manufacturing Practice (GMP)-compliant production process for freeze-dried mesenchymal stem cell (MSC)-secretome (lyo-secretome): after serum starvation, the cell supernatant was collected, and the secretome was concentrated by ultrafiltration and freeze-dried, obtaining a standardized ready-to-use and stable powder. In this work, we modified the type of human platelet lysate (HPL) used as an MSC culture supplement during the lyo-secretome production process: the aim was to verify whether this change had an impact on product quality and also whether this new procedure could be validated according to GMP, proving the process robustness. MSCs were cultured with two HPLs: the standard previously validated one (HPL-E) and the new one (HPL-S). From the same pool of platelets, two batches of HPL were obtained: HPL-E (by repeated freezing and thawing cycles) and HPL-S (by adding Ca-gluconate to form a clot and its subsequent mechanical wringing). Bone marrow MSCs from three donors were separately cultured with the two HPLs until the third passage and then employed to produce lyo-secretome. The following indicators were selected to evaluate the process performance: (i) the lyo-secretome quantitative composition (in lipids and proteins), (ii) the EVs size distribution, and (iii) anti-elastase and (iv) immunomodulant activity as potency tests. The new HPL supplementation for MSCs culture induced only a few minimal changes in protein/lipid content and EVs size distribution; despite this, it did not significantly influence biological activity. The donor intrinsic MSCs variability in secretome secretion instead strongly affected the quality of the finished product and could be mitigated by concentrating the final product to reach a determined protein (and lipid) concentration. In conclusion, the modification of the type of HPL in the MSCs culture during lyo-secretome production induces only minimal changes in the composition but not in the potency, and therefore, the new procedure can be validated according to GMP.     

Effect of Environmental Exposure on the Fracture Properties of an Epoxy Adhesive

An experimental study was carried out about the effect of warm moisture on the fracture energy of an adhesive system formed by steel adherends joined by an epoxy adhesive. The specimens were double cantilever beams, manufactured with the open-face technique. The halves of the specimens (single beams covered by the “primary” adhesive layer) were degraded in a climatic cell at 50°C and 100% RH, for time periods in the range of 1–5 weeks. At the end of each desired period, the half-specimens were dried, to account for irreversible effects only, and the bonds were completed with the second halves.

Static fracture tests were carried out on an Instron 100 kN machine, monitoring crack propagation with a charge-coupled device microscope. The data were processed by means of the Simple Beam Theory to calculate the strain energy release rate and the R-curves were obtained. Similar trends were found for initial and steady critical strain energy release rates: compared to unexposed specimens, great part of the reduction (about ?50%, ?40%, respectively) occurred in the first week, stabilized values (about ?80%, ?60%) were observed after 3 weeks. The load-displacement curves decreased likewise. The fracture, mostly interfacial, followed a stepped crack path between the adherends.     

Eu-doped titania nanofibers: processing, thermal behaviour and luminescent properties

Undoped and Europium-doped titania nanofibers have been fabricated by electrospinning technique, using a single multielement Titanium/Europium source. In this communication we present the synthesis, structural and spectroscopic characterisation of Eu-doped TiO2 nanofibers starting from polyvinylpyrrolidone, titanium tetraisopropoxide (Ti(OiPr)4) and Eu(hfa)3 x diglyme (Hhfa = 1,1,1,5,5,5-hexafluoroacetyacetone, diglyme = CH3O(CH2CH2O)2CH3). The chosen system allowed to investigate a wide compositional range, i.e., from 3 to 10% mol of Eu3+. Microstructure was studied by means of scanning electron microscopy (SEM), thermal behaviour followed by thermogravimetric and differential thermal analysis (TG-DTA). Phase analysis was performed by means of X-ray diffraction (XRD) and high temperature X-ray diffraction analysis (HT-XRD) up to 1100 degrees C. Luminescence properties were investigated by means of luminescence spectroscopy, using a laser excitation source at 395 nm. All electrospun materials consisted of randomly oriented nanofibers of fairly uniform diameter. The average fiber size was 80-100 nm and 40 nm for, respectively, Eu-doped and undoped TiO2 calcinated at 500 degrees C. The presence of Europium shifted toward higher values either the crystallization temperature of anatase and the anatase to rutile phase transition, the latter being accompanied by the formation of the Eu2Ti2O7 phase. The doped samples showed a strong luminescence of Eu3+ ions. The emission spectra were dominated by the 5D0 --> 7F2 emission, suggesting a notable distortion around the Eu3+ ions. The broadening of the bands pointed to the presence of a relevant inhomogeneous disorder around the Eu3+ sites. The Eu3+ doped TiO2 nanofibers showed a higher emission intensity with respect to the PVP/TiO2 ones.     

Characterization of polyurethane resins by FTIR,TGA, and XRD

Fourier Transformed Infrared Spectroscopy, Thermogravimetric Analysis, and X‐ray Diffractometry have been used to investigate the rigid, semi rigid, and soft polyurethane (PU) forms, which were developed by the Group of Analytic Chemistry and Technology of Polymers ‐ USP ‐ São Carlos. The –NCO/–OH ratios were 0.6, 0.5, and 0.3% for rigid, semi rigid, and soft PUs, respectively, showing that different ratios cause differences in thermal behaviors and crystalline structures of the synthesized PU resins. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dynamic Nature of Noncoding RNA Regulation of Adaptive Immune Response

Immune response plays a fundamental role in protecting the organism from infections; however, dysregulation often occurs and can be detrimental for the organism, leading to a variety of immune-mediated diseases. Recently our understanding of the molecular and cellular networks regulating the immune response, and, in particular, adaptive immunity, has improved dramatically. For many years, much of the focus has been on the study of protein regulators; nevertheless, recent evidence points to a fundamental role for specific classes of noncoding RNAs (ncRNAs) in regulating development, activation and homeostasis of the immune system. Although microRNAs (miRNAs) are the most comprehensive and well-studied, a number of reports suggest the exciting possibility that long ncRNAs (lncRNAs) could mediate host response and immune function. Finally, evidence is also accumulating that suggests a role for miRNAs and other small ncRNAs in autocrine, paracrine and exocrine signaling events, thus highlighting an elaborate network of regulatory interactions mediated by different classes of ncRNAs during immune response. This review will explore the multifaceted roles of ncRNAs in the adaptive immune response. In particular, we will focus on the well-established role of miRNAs and on the emerging role of lncRNAs and circulating ncRNAs, which all make indispensable contributions to the understanding of the multilayered modulation of the adaptive immune response.