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Multicomponent nanomaterials consisting of dense scintillating particles functionalized by or embedding optically active conjugated photosensitizers (PSs) for cytotoxic reactive oxygen species (ROS) have been proposed in the last decade as coadjuvant agents for radiotherapy of cancer. They have been designed to make scintillation-activated sensitizers for ROS production in an aqueous environment under exposure to ionizing radiations. However, a detailed understanding of the global energy partitioning process occurring during the scintillation is still missing, in particular regarding the role of the non-radiative energy transfer between the nanoscintillator and the conjugated moieties which is usually considered crucial for the activation of PSs and therefore pivotal to enhance the therapeutic effect. We investigate this mechanism in a series of PS-functionalized scintillating nanotubes where the non-radiative energy transfer yield has been tuned by control of the intermolecular distance between the nanotube and the conjugated system. The obtained results indicate that non-radiative energy transfer has a negligible effect on the ROS sensitization efficiency, thus opening the way to the development of different architectures for breakthrough radiotherapy coadjutants to be tested in clinics.

Retrieving the starting monomer from polymers synthesized by reversible deactivation radical polymerization has recently emerged as an efficient way to increase the recyclability of such materials and potentially enable their industrial implementation. To date, most methods have primarily focused on utilizing high temperatures (typically from 120 °C to 180 °C) to trigger an efficient depolymerization reaction. In this work, we show that, in the presence of Eosin Y under light irradiation, a much faster depolymerization of polymers made by reversible addition-fragmentation chain-transfer (RAFT) polymerization can be triggered even at a lower temperatures (i.e. 100 °C). For instance, green light, in conjunction with ppm amounts of Eosin Y, resulted in depolymerization acceleration of poly(methyl methacrylate) from 16% (thermal depolymerization at 100°C) to 37% within 1 hour, and a final 80% of depolymerization after 8 hours, as confirmed by both 1H-NMR and SEC analysis. The enhanced depolymerization rate was attributed to the activation of the macroCTA from Eosin Y, thus resulting in a faster macroradical generation. Notably, this method was found to be compatible with different wavelengths (e.g. blue, red and white irradiation), solvents, and RAFT agents, thus highlighting the potential of light to significantly improve current depolymerization approaches., Polymer Chemistry, 14 (3), ISSN:1759-9962, ISSN:1759-9954

A significant part of psychic suffering is connected to the contemporary sociocultural crisis. The impressive transformations that have taken place in recent decades have led to a different and more complex organisation of needs and of the social and emotional life. On the psychic level, a diminished capacity for symbolic representation and a profound disorientation in processes of subjectivation have been observed. Couple crises frequently reveal the fragility of the link in its constituent aspects where individuals appear to have difficulty in forming intersubjective contracts. The function of the couple psychotherapist becomes essential in rooting the relationship within a more meaningful and profound psychic dimension.

Natural and anthropogenic gas radionuclides such as radon, xenon, hydrogen and krypton isotopes must be monitored to be managed as pathogenic agents, radioactive diagnostic agents or nuclear activity indicators. State-of-the-art detectors based on liquid scintillators suffer from laborious preparation and limited solubility for gases, which affect the accuracy of the measurements. The actual challenge is to find solid scintillating materials simultaneously capable of concentrating radioactive gases and efficiently producing visible light revealed with high sensitivity. The high porosity, combined with the use of scintillating building blocks in metal–organic frameworks (MOFs), offers the possibility to satisfy these requisites. We demonstrate the capability of a hafnium-based MOF incorporating dicarboxy-9,10-diphenylanthracene as a scintillating conjugated ligand to detect gas radionuclides. Metal–organic frameworks show fast scintillation, a fluorescence yield of ∼40%, and accessible porosity suitable for hosting noble gas atoms and ions. Adsorption and detection of 85Kr, 222Rn and 3H radionuclides are explored through a newly developed device that is based on a time coincidence technique. Metal–organic framework crystalline powder demonstrated an improved sensitivity, showing a linear response down to a radioactivity value below 1 kBq m−3 for 85Kr, which outperforms commercial devices. These results support the possible use of scintillating porous MOFs to fabricate sensitive detectors of natural and anthropogenic radionuclides.

Given an irrational vector $\alpha$ in $\mathbb{R}^{d}$, a continuous function $f(x)$ on the torus $\mathbb{T}^{d}$ and suitable weights $\Phi(N,n)$ such that $\sum_{n=-\infty}^{+\infty}\Phi(N,n)=1$, we estimate the speed of convergence to the integral $\int_{\mathbb{T}^{d}}f(y)dy$ of the weighted sum $\sum_{n=-\infty}^{+\infty}\Phi(N,n) f(x+n\alpha)$ as $N\rightarrow +\infty$. Whereas for the arithmetic means $N^{-1}\sum_{n=1}^{N}f(x+n\alpha)$ the speed of convergence is never faster than $cN^{-1}$, for other means such speed can be accelerated. We estimate the speed of convergence in two theorems with different flavor. The first result is a metric one, and it provides an estimate of the speed of convergence in terms of the Fourier transform of the weights $\Phi(N,n)$ and the smoothness of the function $f(x)$ which holds for almost every $\alpha$. The second result is a deterministic one, and the speed of convergence is estimated also in terms of the Diophantine properties of the given irrational vector $\alpha\in\mathbb R^d$., Comment: 28 pages

In this work we consider smooth unbounded worm domains $\mathcal Z_\lambda$ in $\mathbb C^2$ and show that the Bergman projection, densely defined on the Sobolev spaces $H^{s,p}(\mathcal Z_\lambda)$, $p\in(1,\infty)$, $s\ge0$, does not extend to a bounded operator $P_\lambda:H^{s,p}(\mathcal Z_\lambda)\to H^{s,p}(\mathcal Z_\lambda)$ when $s>0$ or $p\neq2$. The same irregularity was known in the case of the non-smooth unbounded worm. This improved result shows that the irregularity of the projection is not a consequence of the irregularity of the boundary but instead of the infinite windings of the worm domain., Comment: Revised version. To appear on the Mediterranean Journal of Mathematics

This paper addresses the challenge of the robotized insertion of ring-shaped elastic objects into parts' outer grooves, which is a key operation in several industrial processes. We propose a novel flexible strategy to insert ring-shaped elastic objects of different sizes and stiffnesses, exploiting a generic robot and a simple - yet effective - fixture. Despite the overall complexity of the procedure is entirely poured on the mentioned fixture, its simplicity of realization and implementation allows to equip the robot with a generic gripper, without the use of any additional sensor. The effectiveness of the proposed strategy is assessed via experimental tests.

Cefonicid is a common second-generation cephalosporin, and the 7-amino-3-[sulphomethyl-1-H-tetrazol-5-yl-thiomethyl]-3-cephem-4-carboxylate monosodium salt is a key synthetic intermediate in its preparation. Despite the considerable international demand for this antibiotic, its preparation is hampered by low synthetic yield, long reaction time, and time-consuming industrial filtration over charcoal after the purification step. In the context of the industrial production of pharmaceutical intermediates, in which the balance between streamlining and enhancing productivity is necessary in order to compete in the global active pharmaceutical ingredients (API) market, we have investigated an efficient and practical procedure for the synthesis of a key cefonicid intermediate that features a telescopic route whose synthetic steps are all performed at room temperature; from the displacement of the acetoxy group with boron trifluoride to crystallization without treatment with charcoal. In other words, a simpler, scalable, cost-effective and energy-saving protocol is herein reported as a means of moving towards commercial manufacturing. The optimization of the process parameters and the industrial-scale impact assessment should pave the way for industrialization.

Radiation (RT) remains the most frequently used treatment against cancer. The main limitation of RT is its lack of specificity for cancer tissues and the limited maximum radiation dose that can be safely delivered without damaging the surrounding healthy tissues. A step forward in the development of better RT is achieved by coupling it with other treatments, such as photodynamic therapy (PDT). PDT is an anti-cancer therapy that relies on the light activation of non-toxic molecules—called photosensitizers—to generate ROS such as singlet oxygen. By conjugating photosensitizers to dense nanoscintillators in hybrid architectures, the PDT could be activated during RT, leading to cell death through an additional pathway with respect to the one activated by RT alone. Therefore, combining RT and PDT can lead to a synergistic enhancement of the overall efficacy of RT. However, the involvement of hybrids in combination with ionizing radiation is not trivial: the comprehension of the relationship among RT, scintillation emission of the nanoscintillator, and therapeutic effects of the locally excited photosensitizers is desirable to optimize the design of the hybrid nanoparticles for improved effects in radio-oncology. Here, we discuss the working principles of the PDT-activated RT methods, pointing out the guidelines for the development of effective coadjutants to be tested in clinics.

Continuous-flow chemistry has become a mainstream process and a notable trend among emerging technologies for drug synthesis. It is routinely used in academic and industrial laboratories to generate a wide variety of molecules and building blocks. The advantages it provides, in terms of safety, speed, cost efficiency and small-equipment footprint compared to analog batch processes, have been known for some time. What has become even more important in recent years is its compliance with the quality objectives that are required by drug-development protocols that integrate inline analysis and purification tools. There can be no doubt that worldwide government agencies have strongly encouraged the study and implementation of this innovative, sustainable and environmentally friendly technology. In this brief review, we list and evaluate the development and applications of continuous-flow processes for antibiotic synthesis. This work spans the period of 2012–2022 and highlights the main cases in which either active ingredients or their intermediates were produced under continuous flow. We hope that this manuscript will provide an overview of the field and a starting point for a deeper understanding of the impact of flow chemistry on the broad panorama of antibiotic synthesis.

Shortening and rotational deformity of the lower limb (SRD) is a major complication of hip fracture surgery. It causes not only hip joint dysfunction but also functional impairments due to abnormal gait parameters, decreased gait velocity, and poor balance. Despite a number of previous studies, the effect of SRD on the postsurgical recovery of these patients is still not clear.To compare the functional abilities and balance before and after rehabilitation for people with and without SRD after hip fracture surgery and to assess whether SRD affects rehabilitation.Prospective observational study.Inpatients of a rehabilitation unit.A total of 102 people with hip fracture (62 without SRD and 40 with SRD at the time of admission to the unit).Berg Balance Scale (BBS) and Functional Independence Measure (FIM) motor score, administered before and after rehabilitation.Motor rehabilitation.Before rehabilitation, patients with SRD had lower motor-FIM (p = .002) and BBS (p = .001) scores than those without SRD. After rehabilitation, both groups showed similar improvements in motor-FIM, BBS, range of motion, muscle strength, and pain scores (p .001, for all), but patients with SRD still had lower motor-FIM and BBS scores (p = .014 and .003, respectively) and lower effectiveness in motor-FIM and BBS (p = .039 and p = .034, respectively) than those without SRD.SRD is associated with lower levels of balance and functional abilities before and after rehabilitation and it adversely affects rehabilitation for patients with hip fractures.

International audience; Natural radioactive gases and anthropogenic radionuclides such as radon, xenon, hydrogen and krypton isotopes, need to be carefully monitored to be properly managed as pathogenic agents, radioactive diagnostic agents or indicators of nuclear activity. State-of-the-art gas detectors based on liquid scintillators suffer from many drawbacks such as lengthy sample preparation procedures and limited solubility of gaseous radionuclides, which produces a detrimental effect on measurement sensitivity. A potential breakthrough solution to this problem is the use of solid porous scintillators that act as gas concentrators and therefore could increase detection sensitivity. Highly porous scintillating metal-organic frameworks (MOFs) stand out as relevant materials for the realization of these devices. We demonstrate the capability of porous hafnium-based MOF nanocrystals exploiting dicarboxy-9,10-diphenylanthracene (DPA) as a scintillating conjugated linker to detect gas radionuclides. The nanocrystals show fast scintillation properties in the nanosecond domain, a fluorescence quantum yield of ~40% and an accessible porosity suitable to host noble gas atoms and ions. The MOFs have been tested for the adsorption and detection of the radionuclides 85Kr, 222Rn and 3H in a customized newly developed device based on a time coincidence technique. For all of them, MOF nanocrystals demonstrate an improved sensitivity with respect to a reference detector, showing an excellent linear response down to an activity value lower than 1 kBq·m-3 that outperforms that of commercial devices. The results obtained strongly support the possible use of scintillating porous MOF nanocrystals as the building block of ultrasensitive sensors for the detection of natural and anthropogenic radioactive gases.

Owing to its unique ability to efficiently convert low-energy photons into high-energy photons, triplet-triplet annihilation (TTA) based photon upconversion is a promising strategy for harvesting the low-energy tail of the solar spectrum for photovoltaic technologies. However, breaking through the upconversion quantum efficiency is not easy due to the few examples of existing annihilators that maximize the efficiency of singlet generation by TTA. Here, we present a new bichromophoric annihilator (PCP) that is paired with a metallic porphyrin as a sensitizer in low viscosity solution, and the system shows a record red-to-green external upconversion yield of 42%. This value can be achieved thanks to the photophysical properties of PCP that allow achieving a unitary triplet-to-singlet conversion efficiency and to its structural features that enable high fluorescence yields even at high concentrations.

Luminescent solar concentrators (LSCs) have recently emerged as valuable candidates for the realization of aesthetically pleasing solar windows for near-zero-energy consumption buildings. The growing demand by the building-integrated photovoltaic sector is urging the development of sustainable production methods that minimize the use of polluting organic solvents and hazardous materials, while still enabling industrial-grade LSCs. Here, we introduce a new class of benzothieno-benzothiophene (BTBT) derivatives as highly efficient reabsorption-free emitters for transparent LSCs featuring high stability and a solvent-free chemical access with sustainability factor as low as 21, 10 to 50 times lower than conventional LSC emitters. By embedding our BTBT emitters in optical-grade polymeric waveguides, we produced large-area (40 cm × 40 cm) LSCs with optical power efficiency as high as 3% (corresponding to an optical quantum efficiency of 54%). These results represent an important advancement toward sustainable solar glazing systems for green architecture.The growing demand for building-integrated photovoltaic technologies for near-zero-energy buildings is motivating the scientific community to develop devices that meet the functional, energetic, and aesthetic needs for sustainable architecture. Luminescent solar concentrators (LSCs) are emerging as valuable solutions to realize aesthetically pleasing semitransparent photovoltaic windows capable of converting urban buildings into energy generators. In this work, we report on efficient, transparent LSCs based on a novel class of reabsorption-free derivatives synthesized through a solvent-free route that massively improves the sustainability factor with respect to the state of the art. Optical-grade polymeric LSCs are produced via industrial methods with an optical power efficiency as high as 3% despite their transparency in the visible region. These results represent an important step forward for sustainable solar glazing systems for environmentally friendly architecture. Efficient and aesthetically pleasing solar technologies, such as LSC photovoltaic windows, are becoming essential for the widespread of zero-energy buildings. The more the LSC technology gains appeal, the higher the need becomes for efficient and sustainable materials and production routes. Through a new mechanochemical route, we produce efficient, reabsorption-free LSC emitters with a massively increased sustainability factor. The integration of such derivatives into industrial-grade LSCs leads to an optical efficiency of 3% for large-area devices.

International audience; Radioactive gas monitoring is an important topic for homeland security, medical research and metrology. Our research aims at developing a new ultrasensitive detection system based on timecoincidence techniques exploiting porous scintillators, which enhance the interaction probability of emitted ionizing radiations and concentrate the radioactive material by absorption of gases. Considering their fast scintillation [1] and compositional tunability [2], here highly-porous fluorescent hafnium based metal-organic frameworks nanocrystals are included in a polystyrene aerogel matrix to obtain a hierarchical pore size distribution particularly favorable for gas absorption and realizing a prototype scintillating detector tested for sensing the 85Kr, 222Rn, and 3H radioactive gas species.

The present contribution will be an overview of porous materials as radiation frequency converters, by integration of acceptor and donor into a single framework, for light upgrading and downgrading. Two active components will be co-assembled in varied molar fractions to reach the optimal balance. A few strategies of bond formation will be compared to form mix-ligand MOFs and PAFs. In some instances, even three components, each with its own function, can be comprised in the structures. The chromophore density and the distance between donors and acceptors can be fine-modulated, for benchmark efficiency. Morphology and size of the nanocrystals was also a parameter kept under control and excitation diffusion was modelled. Additionally, dynamics in porous materials will be addressed in detail by spectroscopic techniques: fast molecular reorientation and, specifically, dipole reorientation is a challenging task as explored in conjunction with gas diffusion. CO2 and Xe learn during diffusion steps, the shape and orientation of the channels, as detected by anisotropic line-shape analysis of 13C and hyperpolarized 129Xe NMR resonances. These spectroscopic observations, together with DFT and molecular dynamics simulations, help understand gas sorption and measure diffusion times by jump frequency of the gas species from site to site in the material, through orientation imprinting. Overall, a structure-property comparison among porous systems, from metal-organic to covalent and molecular porous materials, will be traced as regards the potentials to realize the desired performances. 1) Nature Photonics 2021 https://doi.org/10.1038/s41566-021-00769-z 2) Adv. Mater. 2019, 31, 1903309 3) Chem. Sci., 2019, 10, 730

The photon upconversion based on triplet–triplet annihilation (TTA) is a mechanism that converts the absorbed low-energy electromagnetic radiation into higher energy photons also at extremely low excitation intensities, but its use in actual technologies is still hindered by the limited availability of efficient annihilator moieties. We present here the results obtained by the synthesis and application of two new fluorinated chromophores based on phenazine and acridine structures, respectively. Both compounds show upconverted emission demonstrating their ability as TTA annihilator. More interesting, the acridine-based chromophore shows an excellent TTA yield that overcomes the one of some of best model systems. By correlating the experimental data and the quantum mechanical modeling of the investigated compound, we propose an alternative efficient pathway for the generation of the upconverted emissive states involving the peculiar high-energy triplet levels of the dye, thus suggesting a new development strategy for TTA annihilators based on the fine tuning of their high-energy excited states properties.Graphical abstract

In this paper we consider the question of sampling for spaces of entire functions of exponential type in several variables. The novelty resides in the growth condition we impose on the entire functions, that is, that their restriction to a hypersurface is square integrable with respect to a natural measure. The hypersurface we consider is the boundary bU of the Siegel upper half-space U and it is fundamental that bU can be identified with the Heisenberg group Hn. We consider entire functions in Cn+1 of exponential type with respect to the hypersurface bU whose restriction to bU are square integrable with respect to the Haar measure on Hn. For these functions we prove a version of the Whittaker–Kotelnikov–Shannon Theorem. Instrumental in our work are spaces of entire functions in Cn+1 of exponential type with respect to the hypersurface bU whose restrictions to bU belong to some homogeneous Sobolev space on Hn. For these spaces, using the group Fourier transform on Hn, we prove a Paley–Wiener type theorem and a Plancherel–Pólya type inequality.

Porous materials provide a versatile and robust platform for the development of optical materials with unique photonic and scintillating properties. The rigid and directional connectivity of the frameworks allows for the effective inclusion of a high density of organic cromophores avoiding aggregation issues, while the precise spatial arrangement governs the intermolecular interactions between emitting moieties. Highly porous emitting framework (PEF) nanoparticles comprising diphenylanthracene moieties were generated by Yamamoto-type Ullmann coupling reaction[1]. The nanoparticles display a surface area of 680 m2 g-1 and excellent emission properties with a photoluminescence quantum yield ~ 0.70 and decay time of 3.9 ns. The effective inclusion of a porphyrin sensitizer through the accessible porosity generates self-standing sensitized triplet-triplet annihilation (sTTA) upconverters with upconversion quantum yield as high as 0.15, a record value for solid-state materials. We propose nanocrystalline MOFs based on zirconium oxy-hydroxy clusters as fast scintillators. The MOFs nanocrystals with diphenylanthracene ligands display photoluminescence quantum yield up to 0.64 ± 0.09 and high radioluminescence and scintillation under high-energy excitations. The encapsulation of nanocrystals with 50 nm size generates innovative composite fast scintillators with high light yield and fast time response and an ultrafast scintillation rise time of ~ 50 ps[2]. The co-assembly of two conjugated luminescent ligands with complementary absorption and emission properties in Zr-MOFs shows effective non-radiative energy transfer, allowing for fast exciton diffusion and fast emission with large Stokes shift (~ 6000 cm-1) which inhibites re-absorption processes. Notably, the MOF inclusion in a continuous polymeric matrix provides enhanced scintillating properties compared with the homo-ligand nanocrystals[3]. [1] Advanced Materials, 2019, 31, 1903309. [2] Nature Photonics, 2021,15, 393-400. [3] Nature Communications, ASAP.

The photon upconversion based on sensitized triplet-triplet annihilation (sTTA-UC) is a spin-flip mechanism exploited to recover the energy stored on dark triplet states in conjugated systems. In this process, a high-energy fluorescent singlet is created through the collision and fusion of two low-energy triplets belonging to different diffusing molecules. Its high yield in solution under low excitation intensity and noncoherent light highlighted the huge potential of sTTA-UC to provide a breakthrough in solar technologies. However, its diffusion-limited nature restrains its efficiency in the solid state. To overcome this issue, we propose a single-molecule system that is able to host simultaneously more than one triplet, thus enabling a diffusion-free intramolecular TTA. We obtain the first direct demonstration of intramolecular triplet fusion by tailored photoluminescence spectroscopy experiments, thus opening the way to realize a new family of single-molecule upconverters with huge potential in solar and lighting technologies by accessing the natural triplets' energy reservoir.

The conversion of low-energy photons into radiation of higher energy is useful for bioimaging, 3D displays and other applications. In particular, upconversion of the infrared portion of the solar spectrum, which is typically not absorbed by the light-harvesting materials used in solar technologies, allows additional photons to be harnessed and boosts the efficiency of photovoltaic and photocatalytic devices. Therefore, low power photon upconversion of non-coherent light based on sensitized triplet-triplet annihilation (sTTA) has been recently recognized as a potential viable approach towards enhancing the efficiency of sunlight-powered devices through sub-bandgap photon harvesting. The sTTA permits the conversion of light into radiation of higher energy involving a sequence of photophysical processes between two moieties, respectively a light harvester/triplet sensitizer and an annihilator/emitter. High up-conversion yields under solar irradiance can be observed in low viscosity solutions of dyes, but in solid materials, which are better suited for integration in devices, the process is usually less efficient. The ability to control triplet excitons in the solid state is therefore crucial to obtain high performance solid upconverters. In this chapter, we will discuss the results obtained in several systems, such as dye-doped polymers/nanoparticles, amorphous/crystalline supramolecular structures and many others, highlighting the materials design guidelines to obtain efficient upconverters at the solid state that can match the strict requirements of solar technologies.

Abstract The Chinese Panorpa species without anal horn are normally assigned to the Panorpa davidi group. Here, we taxonomically revise the P. davidi group, which currently includes 17 known species and four new species: P. gaokaii sp. nov., P. huayuani sp. nov., P. uncinata sp. nov. and P. yaoluopingensis sp. nov. Panorpa shanyangensis Chou & Wang, 1981 and P. sexspinosa zhongnanensis Chou & Ran, 1981 are treated as junior synonyms of P. sexspinosa Cheng, 1949. We describe for the first time the male of P. stigmosa Zhou, 2006, and the females of P. curva Carpenter, 1938, P. davidi Navás, 1908, P. difficilis Carpenter, 1938, P. fructa Cheng, 1949, and P. jinchuana Hua, Sun & Li, 2001. A key to species of the group is provided. Phylogenetic analyses of maximum parsimony and maximum likelihood based on 79 morphological characters show that the newly defined P. davidi group is a well-supported monophyletic group and is sister to the genus Cerapanorpa Gao, Ma & Hua, 2016.

Little is known about the outcome predictors in peripheral neuropathy (PN). This prospective observational study aimed to identify possible factors predicting the functional abilities in older patients with PN undergoing motor rehabilitation. Data were collected in 80 PN patients, aged over 65 years, performing a standard inpatient motor rehabilitation program. The total Functional Independence Measure (FIM) score after rehabilitation, as well as efficiency and effectiveness in total-FIM, were the outcome measures. Backward multiple regression analyses identified the predictors of functional status. At the end of rehabilitation, total-FIM score was 102.66 ± 10.75, efficiency in total-FIM 0.64 ± 0.29 and effectiveness in total-FIM 48.81 ± 15.35%. Katz index at admission was a predictor of the final total-FIM score (beta 0.46, p

The sensitization of scintillation in polymeric composites based on fluorescent nanocomplexes. The archive contains 5 text files (including this annotation.txt) and one pdf file (ESI of the paper): 1. Annotation.txt (this file) 2. Nanomat_Scint_Sensitization_figure 2_Absorption_PL_TRPL _ energy transfer yield rate_Au8 superstructures and rhodamine 6G.TXT 3. Nanomat_Scint_Sensitization_figure 3_ RL spectra of the composite series as function of the emitter Rh6G concentration.txt 4. README Nanomat_scint.txt- where 2,3 files are described 5. nanomaterials-ESI.zip In this paper, the sensitization of scintillation was investigated in crosslinked polymeric composite materials loaded with luminescent gold clusters aggregates acting as sensitizers, and with rhodamine 6G as emitting dye. The findings enabled to give an expression of the sensitization efficacy as a function of the characteristic parameters of the employed luminescent systems and offer a guideline for the realization of composite materials with maximized sensitization effect. The name of the individual files is a short description of the content that has been explained with details in README.txt. All files are collected in one directory. The file 'README Nanomat_scint.txt' contains short description of the individual files.

In the last 15 years, the attention dedicated to organic conjugated systems experienced outstanding growth because of the renewed interest in mechanisms involving triplet states such as singlet fission, thermally activated delayed fluorescence, and intersystem crossing enhanced phosphorescence. Photon upconversion via sensitized triplet–triplet annihilation ( sTTA) enables the conversion of low-energy photons into high-energy ones, and it has been proposed in multicomponent systems as an efficient managing strategy of non-coherent photons. This mechanism exploits the annihilation of two optically dark triplet states of emitter moieties to produce high-energy photons. The annihilating triplets are sensitized through Dexter energy transfer by a light-harvester, typically a conjugated molecule or a nanocrystal, so sTTA upconversion is usually performed in bi-component systems. The high yield observed at low excitation intensities stimulated thriving research in the field, leading to the development of a large family of fully organic and hybrid sTTA multicomponent upconverters. Here, we compare the evolution of these two families of systems with respect to the sTTA upconversion main figures of merit, highlighting the strengths and weaknesses of both approaches, according to the results reported in the literature. The data presented are also discussed in the perspective of future developments in the field, pointing out the challenges that are still to be faced for the technological use of the sTTA upconversion process.

In this work we study what we call Siegel--dissipative vector of commuting operators $(A_1,\ldots, A_{d+1})$ on a Hilbert space $\mathcal H$ and we obtain a von Neumann type inequality which involves the Drury--Arveson space $DA$ on the Siegel upper half-space $\mathcal U$. The operator $A_{d+1}$ is allowed to be unbounded and it is the infinitesimal generator of a contraction semigroup $\{e^{-i\tau A_{d+1}}\}_{\tau, Comment: 17 pages. Typos were fixed and the references updated

Rotors, motors and switches in the solid state find a favorable playground in porous materials, such as Metal Organic Frameworks (MOFs) and Porous Aromatic Frameworks (PAFs), thanks to their large free volume, which allows for fast dynamics. We fabricated MOFs and PAFs with reorientable linkers and benchmark mobility also at very low temperature, to reduce the energy demand for motion-activation and light stimulus-response.[1] A fast molecular rotor in a Zn-MOF endowed with continuous, unidirectional hyperfast rotation with energy barrier of 6.2 cal/mol and high frequency persistent for several turns is achieved (Figure 1). Ligh responsive porous switchable frameworks took advantage of quantitative photoisomerization in the solid state and porosity of the framework to modulate the gas adsorption in response to light.[2] MOF nanocrystals comprising high-Z linking nodes interacting with the ionizing radiation, arranged in an orderly fashion at a nanometric distance from ligand emitters showed ultrafast sensitization of the ligand fluorescence, thus supporting the development of new engineered scintillators.[3] References [1] A. Comotti, P. Sozzani et al. Nat. Chem. 12 (2020) 845; [2] A. Comotti, B. Feringa, et al. Nature Chem. 12 (2020) 595; [3] A. Comotti, A. Vedda, A. Monguzzi, et al. Nature Photonics (2021), https://doi.org/10.1038/s41566-021-00769-z. Financial support from the Italian Ministry of University and Research (MIUR) through the grant ‘Dipartimenti di Eccellenza-2017 Materials For Energy’ is acknowledged. This research was funded by the PRIN-2015CTEBBA-003.

The search for new sophisticated functions integrated in porous solids prompted us to engineer switches and motors in metal-organic and covalent architectures for the construction of working nanodevices. 3D Porous Aromatic Frameworks were built with photo-active monomer units, and could be switched on command between two permanent states, entailing structure breathing and gas sorption switching. A fast molecular rotor in the solid state whose rotation speed approaches that of unhindered rotations in organic moieties even at very low temperatures (10 GHz below 2 K) was realized generating continuous, unidirectional hyperfast rotation with an energy barrier of 6.2 cal/mol. The energy transfer effect with radiation up-grading was also realized in Porous Emitting Frameworks (PEFs): porphyrin (red absorber) and diphenyl-antracene (blue emitter) were integrated in a 3D network showing very effective convertion of low energy light into photons of higher energy. With a similar concept, motors were inserted into metal-organic frameworks (MOFS), wherein two linkers with complementary absorption-emission properties were integrated in the same materials. The linkers were put in action by the visible light up-grading to UV-radiation, for fuelling the motors. MOF nanocrystals comprising high-Z linking nodes interacting with the ionizing radiation, arranged in an orderly fashion at a nanometric distance from ligand emitters showed ultrafast sensitization of the ligand fluorescence, thus supporting the development of new engineered scintillators. A. Comotti, B. L. Feringa et al Nature Chem. 2020, 12, 595; A. Comotti, P. Sozzani et al Nature Chem. 2020, 12, 845; P. Sozzani, A. Comotti, A. Monguzzi et al Adv. Mater. 2019, 31, 1903309; A. Comotti, B. L. Feringa et al J. Am. Chem. Soc. 2020, 142, 9048; A. Comotti, A. Monguzzi et al Nature Photonics 2021, doi 10.1038/s41566-021-00769-z.

The robotic manipulation of deformable linear objects (DLOs) such as cables is currently a challenge. In this work, we propose a set of skills based on data from tactile sensors mounted on the end effector fingertips to allow the robot to optimally grasp a DLO and follow its contour. These skills are applied to perform a wiring operation.

The interest in collaborative robotics applications keeps increasing with the advancing of the years. Such growth is due to the robot's flexibility in the production line and to the interactions that may happen with the human partner. However, human-robot collaboration is far from being adopted in practice, especially for complex industrial applications such as assembly tasks. This work formalises an architecture that models human and robot workflows and synchronises their activities, spots errors during the human task execution, and notifies the operator that something unexpected happened. The system has then been tested in an industrial collaborative assembly operation.

In this work we explore the theme of $L^p$-boundedness of Bergman projections of domains that can be covered, in the sense of ramified coverings, by "nice" domains (e.g. strictly pseudoconvex domains with real analytic boundary). In particular, we focus on two-dimensional normal ramified coverings whose covering group is a finite unitary reflection group. In an infinite family of examples we are able to prove $L^p$-boundedness of the Bergman projection for every $p\in(1,\infty)$., 24 pages

Sensitized triplet-triplet annihilation-based photon upconversion is a photo-physical process that affords anti-Stokes-shifted emission after annihilation of two metastable triplet excitons of an emitter dye and the formation of a fluorescent singlet state. While this process readily occurs in solutions under conditions where the mobility of the dye molecules is high, particular architectures are required to facilitate efficient energy transfers in solid polymers. One possibility is to incorporate liquid upconverting domains into solid polymer matrices. Another possibility is to reduce the intermolecular distance between the dyes below the Dexter radius, allowing exciton migration via triplet hopping. We introduce herein nanostructured materials that combine both of these features. These glassy nanostructured polymer systems contain liquid upconverting nanodroplets that are stabilized with a block copolymer surfactant and are fabricated under ambient conditions in a facile one-step protocol. The dyes concentrate in the nanostructured liquid domains, and this enables hopping-mediated ET and TTA between the dyes and leads to an upconversion efficiency of similar to 20%.

We report on design and fabrication of Ni 2+ -doped glass-ceramics from a low-alkali optical glass in Li 2 O-Na 2 O-Ga 2 O 3 -SiO 2 -GeO 2 system by melting technique and subsequent thermally controlled nano-crystallization. The analysis of differential scanning calorimetry, X-ray diffraction, transmission electron microscopy, absorption and fluorescence spectroscopy reveals, for the first time, the real possibility of optimizing the integrated intensity of Ni 2+ near-infrared emission through controlled pre-treatments at temperatures of nanophase nucleation, with the enhancement up to a factor of four with respect to gallium germanosilicate glass-ceramics obtained without pre-treatments. Importantly, the effects on the light emission are shown to be related to the influence of pre-treatment on size and size distribution of the gallium oxide nanocrystals which result from subsequent crystallization at higher temperature.

Primary sclerosing cholangitis (PSC) is a progressive bile duct disease associated with inflammatory bowel disease (PSC-IBD).To investigate whether patients with PSC-IBD benefit from a gluten-free and amylase trypsin inhibitor (ATI)-free diet (GFD).We performed a prospective clinical pilot study administering an eight-week GFD. The primary outcomes were colonic inflammation assessed by proctosigmoidoscopy, and liver stiffness (surrogate for fibrosis, inflammation and cholestasis) measured by transient elastography before and after GFD. Amongst the secondary (exploratory) outcomes were colonic mucosal and serum cytokine/chemokine changes, the intestinal microbiome and transcriptome dynamics, and shifts in serum markers of hepatic fibrogenesis.Fifteen patients with PSC-IBD completed the study. The study did not meet its primary outcome: the endoscopic score and liver stiffness remained unchanged. However, the expression of pro-inflammatory mucosal cytokines and chemokines such as IL6, IL8, CCL2, and TNFα was significantly down-regulated. Two critical markers of liver fibrosis and matrix remodelling, thrombospondin-2 and -4, decreased significantly. The microbiota composition changed slightly, including a decrease in the pathogen Romboutsia ilealis. The intestinal transcriptome indicated a gut barrier improvement. Pruritus, fatigue, overall well-being, faecal calprotectin levels, and serum alkaline phosphatase did not change significantly.This study did not demonstrate a clinical improvement with short-term GFD in patients with PSC-IBD. However, a gluten/ATI-free diet may improve biomarkers of intestinal inflammation and barrier function in these patients with associated with changes in the enteric microbiota. Further investigation of the therapeutic potential of gluten-free diets in PSC-IBD is warranted.

We provide a multidimensional weighted Euler--MacLaurin summation formula on polytopes and a multidimensional generalization of a result due to L. J. Mordell on the series expansion in Bernoulli polynomials. These results are consequences of a more general series expansion; namely, if $\chi _{\tau\mathcal{P}}$ denotes the characteristic function of a dilated integer convex polytope $\mathcal{P}$ and $q$ is a function with suitable regularity, we prove that the periodization of $q\chi_{\tau\mathcal{P}}$ admits an expansion in terms of multivariate Bernoulli polynomials. These multivariate polynomials are related to the Lerch Zeta function. In order to prove our results we need to carefully study the asymptotic expansion of $\widehat{q\chi_{\tau\mathcal{P}}}$, the Fourier transform of $q\chi _{\tau\mathcal{P}}$., Comment: 38 pages, 1 table

Meropenem is currently the most common carbapenem in clinical applications. Industrially, the final synthetic step is characterized by a heterogeneous catalytic hydrogenation in batch mode with hydrogen and Pd/C. The required high-quality standard is very difficult to meet and specific conditions are required to remove both protecting groups [i.e., p-nitrobenzyl (pNB) and p-nitrobenzyloxycarbonyl (pNZ)] simultaneously. The three-phase gas–liquid–solid system makes this step difficult and unsafe. The introduction of new technologies for small-molecule synthesis in recent years has opened up new landscapes in process chemistry. In this context, we have investigated meropenem hydrogenolysis using microwave (MW)-assisted flow chemistry for use as a new technology with industrial prospects. The reaction parameters (catalyst amount, T, P, residence time, flow rate) in the move from the batch process to semi-continuous flow were investigated under mild conditions to determine their influence on the reaction rate. The optimization of the residence time (840 s) and the number of cycles (4) allowed us to develop a novel protocol that halves the reaction time compared to batch production (14 min vs. 30 min) while maintaining the same product quality. The increase in productivity using this semi-continuous flow technique compensates for the slightly lower yield (70% vs. 74%) obtained in batch mode.

As a model radio-photodynamic therapy (RPDT) agent, we developed a multicomponent nanomaterial by anchoring conjugated chromophores on the surface of scintillating chrysotile nanotubes. Its ultimate composition makes the system a scintillation-activated photosensitizer for the singlet oxygen production. This nanomaterial shows a remarkable ability to enhance the production of singlet oxygen in an aqueous environment, under X-ray irradiation, boosting its production by almost 1 order of magnitude. Its efficiency as a coadjutant for radiotherapy has been tested in vitro, showing a striking efficacy in enhancing both the prompt cytotoxicity of the ionizing radiation and the long-term cytotoxicity given by radiation-activated apoptosis. Notably, the beneficial activity of the RPDT agent is prominent at low levels of delivered doses comparable to the one employed in clinical treatments. This opens the possibility of effectively reducing the therapy exposure and consequently undesired collateral effects due to prolonged exposure of patients to high-energy radiation.

Scintillators, materials that produce light pulses upon interaction with ionizing radiation, are widely employed in radiation detectors. In advanced medical-imaging technologies, fast scintillators enabling a time resolution of tens of picoseconds are required to achieve high-resolution imaging at the millimetre length scale. Here we demonstrate that composite materials based on fluorescent metal–organic framework (MOF) nanocrystals can work as fast scintillators. We present a prototype scintillator fabricated by embedding MOF nanocrystals in a polymer. The MOF comprises zirconium oxo-hydroxy clusters, high-Z linking nodes interacting with the ionizing radiation, arranged in an orderly fashion at a nanometric distance from 9,10-diphenylanthracene ligand emitters. Their incorporation in the framework enables fast sensitization of the ligand fluorescence, thus avoiding issues typically arising from the intimate mixing of complementary elements. This proof-of-concept prototype device shows an ultrafast scintillation rise time of ~50 ps, thus supporting the development of new scintillators based on engineered fluorescent MOF nanocrystals. Composites of fluorescent metal–organic framework nanocrystals in a polymer are exploited to create fast scintillators with a rise time of about 50 ps.

The photon upconversion based on sensitized triplet-triplet annihilation (sTTA-UC) is a spin-flip mechanism exploited to recover the energy of dark triplet states in conjugated systems. In this process a high-energy fluorescent singlet is created through the collision and fusion of two low-energy triplets belonging to different diffusing molecules. Its excellent yield in solution under low excitation intensity and non-coherent light highlighted the huge potential of sTTA-UC to provide a breakthrough in solar technologies. However, its diffusion-limited bi-molecular nature limits its efficiency in the solid state. To overcome this issue, we designed a molecular systems able to host simultaneously more than one triplet, thus enabling a diffusion-free intramolecular TTA. We obtain the first direct demonstration of intramolecular triplet fusion by tailored photoluminescence spectroscopy experiments, thus opening the way to realize a new family of single molecule upconverters with huge potential in solar and lightening technologies by accessing the natural triplets energy reservoir.

Cefonicid is a second-generation cephalosporin sold under the brand name Sintocef™. It is an injectable drug obtained via a freeze-drying process and is also available for oral preparations. The high-quality standard required is very challenging to satisfy, and current production protocols are characterized by steps that are lengthy and cumbersome, making the product unattractive for the international market. Industrial R&D is constantly working on the process optimization for API synthesis, with the aim of increasing productivity and decreasing production costs and waste. We herein report a new and efficient method for the synthesis of the cefonicid benzathine salt that provides a good yield and high product stability. The double-nucleophilic and lipophilic nature of N′,N″-dibenzylethylene diacetate enables the deformylation of the OH-protected group on the mandelic moiety and also enables product crystallization to occur. We demonstrate that the formyl group in the peculiar position has high reactivity, promoting an amidation reaction that deprotects a hydroxy group and generates a new C-N bond in the reaction by-product. Several amines and OH-protected groups have been studied, but none were able to replicate the excellent results of benzathine diacetate.

A high efficiency emission with a massive Stokes shift is obtained by fluorescent conjugated acene building blocks arranged in nanocrystals. The two ligands of equal molecular length and connectivity, yet complementary electronic properties, are co-assembled by zirconium oxy-hydroxy clusters, generating highly crystalline hetero-MOF nanoparticles The fast diffusion of singlet molecular excitons in the framework, coupled with the fine matching of ligands absorption and emission properties, enables to achieve an ultrafast activation of the low energy emission by diffusion-mediated non-radiative energy transfer in the 100 ps time scale, by using a low amount of co-ligands. This allow to obtain MOF nanocrystals with a fluorescence quantum efficiency of ̴ 70% and an actual Stokes shift as large as 750 meV. This large Stokes shift suppresses the reabsorption of fast emission issues in bulk devices, pivotal for a plethora of applications in photonics and photon managing spacing from solar technologies, imaging, and detection of high energy radiation. These features allowed to realize a prototypal fast nanocomposite scintillator that shows an enhanced performance with respect to the homo-ligand nanocrystals, achieving benchmark. values which compete with those of some inorganic and organic commercial systems.