Solid-state sensory properties of Calix-Poly(Phenylene Ethynylene)s toward nitroaromatic explosives

This study is primarily focused in establishing the solid-state sensory abilities of several luminescent polymeric calix[4]arene-based materials toward selected nitroaromatic compounds (NACs), creating the foundations for their future application as high performance materials for detection of high explosives. The phenylene ethynylene-type polymers possessing bis-calix[4]arene scaffolds in their core were designed to take advantage of the known recognition abilities of calixarene compounds toward neutral guests, particularly in solid-state, therefore providing enhanced sensitivity and selectivity in the sensing of a given analyte. It was found that all the calix[4]arene-poly(para-phenylene ethynylene)s here reported displayed high sensitivities toward the detection of nitrobenzene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene (TNT). Particularly effective and significant was the response of the films (25-60 nm of thickness) upon exposure to TNT vapor (10 ppb): over 50% of fluorescence quenching was achieved in only 10 s. In contrast, a model polymer lacking the calixarene units showed only reduced quenching activity for the same set of analytes, clearly highlighting the relevance of the macrocyclics in promoting the signaling of the transduction event. The films exhibited high photostability (less than 0.5% loss of fluorescence intensity up to 15 min of continuous irradiation) and the fluorescence quenching sensitivity could be fully recovered after exposure of the quenched films to saturated vapors of hydrazine (the initial fluorescence intensities were usually recovered within 2-5 min of exposure to hydrazine)

Hydrogel 3D in vitro tumor models for screening cell aggregation mediated drug response

Hydrogel-based 3D in vitro models comprising tumor ECM-mimetic biomaterials exhibit superlative potential as preclinical testing platforms for drug discovery and bioperformance screening. However, during hydrogel design and testing stages, the ideal selection between cancer cell laden 3D models or spheroid embedded hydrogel platforms remains to be elucidated. Selecting a disease-mimicking cellular arrangement within ECM hydrogels is paramount for anti-cancer therapeutics performance evaluation and may lead to differential outcomes. To investigate the effects assigned to varying cellular-arrangement, we developed dense 3D spheroid microtumors and cell-laden MG-63 osteosarcoma platforms embedded in GelMA and Matrigel ECM-mimetic scaffolds. These platforms enabled cancer cells/3D microtissues maturation and lorlatinib drug performance screening. Initial 3D spheroids assembly via the liquid overlay technique, resulted in the fabrication of dense cellular aggregates with reproducible size, morphology and necrotic core formation, thus mimicking the native tumor. Upon in vitro maturation, MG-63 spheroids encapsulated in hydrogel scaffolds exhibited significantly higher invasion and drug resistance than their cell laden hydrogel counterparts. Such data reveals inherent physiological and drug response variances among randomly distributed osteosarcoma cells and 3D spheroid-laden hydrogels. Overall, this highlights the importance of evaluating different cellular aggregation states when designing ECM-mimetic hydrogels for in vitro tumor modeling and high-throughput screening of anti-cancer therapeutics.publishe

Novel laser-induced luminescence resulting from benzophenone/O-propylated p-tert-butylcalix[4]arene complexes. A diffuse reflectance study

Laser-induced room temperature luminescence of air-equilibrated benzophenone/O-propylated p-tert-butylcalix[ 4] arene solid powdered samples revealed the existence of a novel emission, in contrast with benzophenone/p-tertbutylcalix[ 4] arene complexes, where only benzophenone emits. This novel emission was identified as phosphorescence of 1-phenyl-1,2-propanedione, which is formed as the result of an hydrogen atom abstraction reaction of the triplet excited benzophenone from the propoxy substituents of the calixarene. Room temperature phosphorescence was obtained in air-equilibrated samples in all propylated hosts. The decay times of the benzophenone emission vary greatly with the degree of propylation, the shortest lifetimes being obtained in the tri- and tetrapropylated calixarenes. Triplet - triplet absorption of benzophenone was detected in all cases, and is the predominant absorption in the p-tert-butylcalix[ 4] arene case, where an endo-calix complex is formed. Benzophenone ketyl radical formation occurs with the O-propylated p-tert-butylcalix[ 4] arenes hosts, suggesting a different type of host/guest molecular arrangement. Diffuse reflectance laser. ash photolysis and gas chromatography - mass spectrometry techniques provided complementary information, the former about transient species and the latter regarding the final products formed after light absorption. Product analysis and identification clearly show that the two main degradation photoproducts following laser excitation in the propylated substrates are 1-phenyl-1,2- propanedione and 2- hydroxybenzophenone, although several other minor photodegradation products were identified. A detailed mechanistic analysis is proposed. While the solution photochemistry of benzophenone is dominated by the hydrogen abstraction reaction from suitable hydrogen donors, in these solid powdered samples, the alpha-cleavage reaction also plays an important role. This finding occurs even with one single laser pulse which lasts only a few nanoseconds, and is apparently related to the fact that scattered radiation exists, due to multiple internal reflections possibly trapping light within non-absorbing microcrystals in the sample, and is detected until at least 20 mus after the laser pulse. This could explain how photoproducts thus formed could also be excited with only one laser pulse

Lean Safety - assessment of the impact of 5S and Visual Management on safety

This study was developed in a furniture company and aimed to implement some Lean tools, such as 5S and Visual Management to reduce waste, by improving the production process. To carry out this analysis an observation plan was used, having the Spaghetti diagram as a reference as well as the value-added analysis of the operations. The implementation of 5S's allowed the improvement of the visual management and the organization through a reorganization of the layout, as well as normalization of the production process. With this, a reduction of 40% was achieved in terms of waste related to activities that did not add value to the product, such as unnecessary movements, waiting times and even movement of materials, having achieved a level of productivity of 74% and 87% in the finishing and joinery sections, respectively. In addition to improvements in the production process, the impact of the measures at the safety level (lean safety) was assessed. For this purpose, a questionnaire was prepared to assess the opinion of the employees, in which 40% considered that the implementation of the tools provided a greater motivation to develop their work activities safelyinfo:eu-repo/semantics/publishedVersio

Long-lived NIR emission in sulfur-doped zeolites due to the presence of [S3]2- clusters

Funding Information: The authors want to acknowledge the Portuguese Foundation for Science and Technology for funding through the grants SFRH/BD/145009/2019 and SFRH/BPD/120599/2016 , the individual contract 2020.00252. CEECIND and several projects PTDC/QUI-QFI/32007/2017, UIDB/04565/2020, UIDP/04565/2020, LA/P/0140/2020, LAQV-REQUIMTE (LA/P/0008/2020, UIDB/50006/2020 and UIDP/50006/2020), VICARTE (UIDP/00729/2020, UIDB/00729/2020) and C2TN (UIDB/04349/2020). MOSTMICRO-ITQB R&D Unit (UIDB/04612/2020, UIDP/04612/2020) and LS4FUTURE Associated Laboratory (LA/P/0087/2020) and by European Union's Horizon 2020 research and innovation program under grant agreement No. 810856. Funding Information: The authors want to acknowledge the Portuguese Foundation for Science and Technology for funding through the grants SFRH/BD/145009/2019 and SFRH/BPD/120599/2016, the individual contract 2020.00252. CEECIND and several projects PTDC/QUI-QFI/32007/2017, UIDB/04565/2020, UIDP/04565/2020, LA/P/0140/2020, LAQV-REQUIMTE (LA/P/0008/2020, UIDB/50006/2020 and UIDP/50006/2020), VICARTE (UIDP/00729/2020, UIDB/00729/2020) and C2TN (UIDB/04349/2020). MOSTMICRO-ITQB R&D Unit (UIDB/04612/2020, UIDP/04612/2020) and LS4FUTURE Associated Laboratory (LA/P/0087/2020) and by European Union's Horizon 2020 research and innovation program under grant agreement No. 810856. Publisher Copyright: © 2023 The Author(s)The exploration of novel long-lived near-infrared (NIR) luminescent materials has attracted significant attention due to their applications in optical communications, anticounterfeiting, and bioimaging. However, these materials usually present low photoluminescence quantum yields and low photo- and chemical stability. Novel emitters that overcome these limitations are in demand. In this study, NIR emission was achieved using widely available, sustainable, and non-toxic materials through the synthesis of sulfur-doped zeolites, with different S/Cl ratios. With a combination of computational calculations (TD-DFT) and spectroscopic data, this emission was assigned to the radiative decay of excited triplet states of [S3]2- clusters, which resulted in a remarkably high Stokes shift (1.97 eV, 440 nm) and an average decay time of 0.54 ms. These new materials present high stability, external quantum efficiency of up to 17%, and a long-lived NIR emission, placing these compounds in a unique position to be used in applications demanding NIR emitters.publishersversionpublishe

Color and Luminescence stability of selected dental materials in vitro

To study luminescence, reflectance, and color stability of dental composites and ceramics. Materials and Methods: IPS e.max, IPS Classic, Gradia, and Sinfony materials were tested, both unpolished (as-cast) and polished specimens. Coffee, tea, red wine, and distilled water (control) were used as staining drinks. Disk-shaped specimens were soaked in the staining drinks for up to 5 days. Color was measured by a colorimeter. Fluorescence was recorded using a spectrofluorometer, in the front-face geometry. Time-resolved fluorescence spectra were recorded using a laser nanosecond spectrofluorometer. Results: The exposure of the examined dental materials to staining drinks caused changes in color of the composites and ceramics, with the polished specimens exhibiting significantly lower color changes as compared to unpolished specimens. Composites exhibited lower color stability as compared to ceramic materials. Water also caused perceptible color changes in most materials. The materials tested demonstrated significantly different initial luminescence intensities. Upon exposure to staining drinks, luminescence became weaker by up to 40%, dependent on the drink and the material. Time-resolved luminescence spectra exhibited some red shift of the emission band at longer times, with the lifetimes in the range of tens of nanoseconds. Conclusions: Unpolished specimens with a more developed surface have lower color stability. Specimens stored in water develop some changes in their visual appearance. The presently proposed methods are effective in evaluating the luminescence of dental materials. Luminescence needs to be tested in addition to color, as the two characteristics are uncorrelated. It is important to further improve the color and luminescence stability of dental materials

Surface Photochemistry: 3,3′-Dialkylthia and Selenocarbocyanine Dyes Adsorbed onto Microcrystalline Cellulose

In this work, thia and selenocarbocyanines with n-alkyl chains of different length, namely with methyl, ethyl, propyl, hexyl and decyl substituents, were studied in homogeneous and heterogeneous media for comparison purposes. For both carbocyanine dyes adsorbed onto microcrystalline cellulose, a remarkable increase in the fluorescence quantum yields and lifetimes were detected, when compared with solution. Contrary to the solution behaviour, where the increase in the n-alkyl chains length increases to a certain extent the fluorescence emission ΦF and τF, on powdered solid samples a decrease of ΦF and τF was observed. The use of an integrating sphere enabled us to obtain absolute ΦF’s for all the powdered samples. The main difference for liquid homogeneous samples is that the increase of the alkyl chain strongly decreases the ΦF values, both for thiacarbocyanines and selenocarbocyanines. A lifetime distribution analysis for the fluorescence of these dyes adsorbed onto microcrystalline cellulose, evidenced location on the ordered and crystalline part of the substrate, as well as on the more disordered region where the lifetime is smaller. The increase of the n-alkyl chains length decreases the photoisomer emission for the dyes adsorbed onto microcrystalline cellulose, as detected for high fluences of the laser excitation, for most samples

Augmented reality-assisted ultrasound breast biopsy

Breast cancer is the most prevalent cancer in the world and the fifth-leading cause of cancer-related death. Treatment is effective in the early stages. Thus, a need to screen considerable portions of the population is crucial. When the screening procedure uncovers a suspect lesion, a biopsy is performed to assess its potential for malignancy. This procedure is usually performed using real-time Ultrasound (US) imaging. This work proposes a visualization system for US breast biopsy. It consists of an application running on AR glasses that interact with a computer application. The AR glasses track the position of QR codes mounted on an US probe and a biopsy needle. US images are shown in the user’s field of view with enhanced lesion visualization and needle trajectory. To validate the system, latency of the transmission of US images was evaluated. Usability assessment compared our proposed prototype with a traditional approach with different users. It showed that needle alignment was more precise, with 92.67 ± 2.32° in our prototype versus 89.99 ± 37.49° in a traditional system. The users also reached the lesion more accurately. Overall, the proposed solution presents promising results, and the use of AR glasses as a tracking and visualization device exhibited good performance.This work was funded by the projects “NORTE-01-0145-FEDER-000045” and “NORTE-01- 0145-FEDER-000059", supported by Northern Portugal Regional Operational Programme (NORTE 2020), under the Portugal 2020 Partnership Agreement, through the European Regional Development Fund (FEDER). It was also funded by national funds, through the FCT (Fundação para a Ciência e a Tecnologia) and FCT/MCTES in the scope of the project UIDB/05549/2020, UIDP/05549/2020 and LASI-LA/P/0104/2020. The authors also acknowledge FCT, Portugal and the European Social Found, European Union, for funding support through the “Programa Operacional Capital Humano” (POCH) in the scope of the PhD grants SFRH/BD/136721/2018 (Oliveira B.) and SFRH/BD/136670 (Torres H. R.)

A proactive approach to the conservation of historic and cultural Heritage: The HeritageCare methodology

Presently, no systematic policy for the preventive conservation of the built cultural heritage exists in South-West Europe. Current approaches for inspection, diagnosis, monitoring and reactive conservation are normally intermittent, unplanned, expensive and lack methodical strategy. The available financial resources are scarce and are mostly addressed to listed buildings. Besides, owners and stakeholders often reveal reluctance to invest in preventive conservation and maintenance programs. In view of these considerations, and driven by the principle “prevention is better than cure”, the HeritageCare project has developed a system for the preventive conservation and maintenance of the built heritage. The main aim of this paper is to briefly describe the methodology, including its three levels of service, and present the main results of the implementation and validation of the service level 1 on a case study belonging to the Portuguese architectural heritage.This work was carried out within the scope of the project HeritageCare (SOE1/P5/P0258), co-funded by the Interreg-Sudoe/FEDER program and included in the research activities of the ISISE Research Centre, also financed by FEDER funds through the Competitiveness Factors Operational Program – COMPETE and by national funds through FCT – Foundation for Science and Technology within the scope of the project POCI-01-0145-FEDER-007633. Authors would like to express their gratitude to the Centre for Computer Graphics, HeritageCare partner, for the development of the platform (and supporting database) and the mobile application, outputs of the project HeritageCare. Authors would like to express their gratitude to the Santa Maria de la Real Foundation, HeritageCare partner, for the placement of the monitoring system at the Ducal Palace, Guimarães, Portugal

Aminodi(hetero)arylamines in the thieno[3,2-b]pyridine series: synthesis, effects in human tumor cells growth, cell cycle analysis, apoptosis and evaluation of toxicity using non-tumor cells

Three aminodi(hetero)arylamines were prepared via a palladium-catalyzed C-N Buchwald-Hartwig coupling of methyl 3-aminothieno[3,2-b]pyridine-2-carboxylate with different bromonitrobenzenes, followed by reduction of the nitro groups of the coupling products to the corresponding amino compounds. The aminodi(hetero)arylamines thus obtained were evaluated for their growth inhibitory effect on four human tumor cell lines MCF-7 (breast adenocarcinoma), A375-C5 (melanoma), NCI-H460 (non-small cell lung cancer) and HepG2 (hepatocellular carcinoma). The toxicity to non-tumor cells was also evaluated using a porcine liver primary cell culture (PLP1), established by us. The aminodi(hetero)arylamine with the NH2 group in the ortho position and an OMe group in the para position to the NH of the di(hetero)arylamine, is the most promising compound giving the lowest GI50 values (1.30–1.63 μM) in all the tested human tumor cell lines, presenting no toxicity to PLP1 at those concentrations. The effect of this compound on the cell cycle and induction of apoptosis was analyzed in the NCI-H460 cell line. It was observed that it altered the cell cycle profile causing a decrease in the percentage of cells in the G0/G1 phase and an increase of the apoptosis levels.Foundation for the Science and Technology (FCT–Portugal) for financial support through the NMR Portuguese network (Bruker 400 Avance III-Univ Minho). FCT and FEDER (European Fund for Regional Development) for financial support through the research centers PEst-C/QUI/UI686/2011and PEst-OE/AGR/UI0690/2011, the research project PTDC/QUI-QUI/111060/2009 and the post-Doctoralgrants attributed to R.C.C. and R.T.L. (SFRH/BPD/68344/2010 and SFRH/BPD/68787/2010, respectively). IPATIMUP is an Associate Laboratory of the Portuguese Ministry of Science, Technology and Higher Education and is partially supported by FCT