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A palladium catalyst supported on silk fibroin (Pd/SF) has been tested in the Sonogashira coupling reactions of a wide range of aryl iodides and terminal alkynes. The best catalytic performance was obtained at 90 °C using only 0.25 mol % metal loading under copper‐free conditions, in the presence of a H2O/EtOH (3 : 2 v/v) solvent mixture and triethylamine as the base, affording the coupling products in good yields. The Pd/SF‐based protocol was then successfully extended to the synthesis of benzofurans through Sonogashira‐Cacchi type annulation of 2‐iodophenol with terminal alkynes. Preliminary investigations on the recyclability and the heterogeneous behaviour of the catalyst were performed: hot filtration test and leaching test evidenced the presence of a small amount of soluble active palladium species into the reaction mixture. Nevertheless, Pd/SF could be reused in recharging test and it can be recycled in four consecutive runs with no significant deactivation. [ABSTRACT FROM AUTHOR]

The aim of this paper is to demonstrate if Jan Patočka’s overcoming of Husserl’s transcendental reduction can lead halfway to the conceptual framework of Hermann Schmitz’s New Phenomenology. I will prove that notwithstanding Patočka’s introduction of the concept of apparaître en tal que tel, his use of pictorial images as well as the adoption of conceptual oppositions prevents his philosophy from being the missing link, without question, between classic phenomenology and the New Phenomenology. [ABSTRACT FROM AUTHOR]

Bombyx mori silk fibroin (SF) is a very versatile biopolymer due to its biocompatibility and exceptional mechanical properties which make possible its use as a functional material in several applications. SF can be modified with a large variety of chemical approaches which endow the material with tailored chemical–physical properties. Here, a systematic investigation of different routes is reported to graft long alkyl chains on SF based on both liquid‐ and solid‐phase, aiming to modulate its hydrophobic behavior. The liquid phase method involves direct activation of SF tyrosine residues via diazo coupling and cycloaddition reactions, generating hydrophobic materials insoluble in any common solvent. The solid phase approach consists of the chemical modification of drop‐casted SF films by esterification of hydroxyl groups of serine, threonine, and tyrosine SF residues with acyl chlorides of fatty acids. For the solid‐state functionalization, a new class of hydrophobic pendant groups is synthesized, based on triple esters of gallic acid anhydrides, that are reacted with the biopolymer to further enhance its resulting hydrophobic features. [ABSTRACT FROM AUTHOR]

Recently, we have reported the preparation of a silk fibroin‐supported Palladium catalyst (Pd/SF) and its use in the Suzuki‐Miyaura cross‐coupling of aryl iodides. Since its synthetic applicability and structural features are still far from being fully explored, a deeper investigation is reported here. Pd/SF is tested as a catalyst for the Suzuki‐Miyaura and Ullmann coupling reactions of aryl chlorides, in H2O/EtOH solvent mixture under atmospheric conditions. Starting from the analysis of the products of the Pd/SF promoted Ullmann reactions of poly‐haloarenes, we can hypothesize the existence of catalytic pockets where monoatomic palladium species can form stable complexes with SF. To shed light on this hypothesis, Pd/SF is characterized by Wide‐Angle X‐ray Scattering (WAXS) analysis, which supports the supposition of catalytic pockets. Finally, using a computational model developed by Molecular Mechanic Energy Minimization we have estimated the dimension of the catalytic pocket of Pd/SF (about 15 Å), in good agreement with the experimental results. [ABSTRACT FROM AUTHOR]

The phenomenological reason shows how the space and the thing conceived by the scientific and natural thinking are a construction upon the unitary and meaningful world of everyday experience; therefore the aim of this essaylk is to analyse, from an Husserlian point of view, the most foundational layers of "space" and "thing" beginning from the most fundamental stratum, called by Husserl "phantom", the mere res extensa, and arriving at kinaesthetic fields in which the apprehensional character of the things depends from the interplay of sequences of K's (kinaesthetic circumstances) and i's (correlative images) which blend into a unitary and meaningful system of experience. In order to better understand Husserl's notions of thing and space, the last part of this essay is concerned about a different conception of the same concepts in Heidegger. Indirect confrontation with Heidegger, namely, allows to find some critical and weak points in Husserl's analysis of thing and space. [ABSTRACT FROM AUTHOR]

The exceptional underwater adhesive properties displayed by aquatic organisms, such as mussels (Mytilus spp.) and barnacles (Cirripedia spp.) have long inspired new approaches to adhesives with a superior performance both in wet and dry environments. Herein, a bioinspired adhesive composite that combines both adhesion mechanisms of mussels and barnacles through a blend of silk, polydopamine, and Fe3+ ions in an entirely organic, nontoxic water‐based formulation is presented. This approach seeks to recapitulate the two distinct mechanisms that underpin the adhesion properties of the Mytilus and Cirripedia, with the former secreting sticky proteinaceous filaments called byssus while the latter produces a strong proteic cement to ensure anchoring. The composite shows remarkable adhesive properties both in dry and wet conditions, favorably comparing to synthetic commercial glues and other adhesives based on natural polymers, with performance comparable to the best underwater adhesives with the additional advantage of having an entirely biological composition that requires no synthetic procedures or processing. [ABSTRACT FROM AUTHOR]

To analyse the performance of iXip in the prediction of prostate cancer (PCa) and high-grade PCa. A consecutive series of men undergoing MRI/FUSION prostate biopsies were enrolled in one centre. Indications for prostate biopsy included abnormal prostate-specific antigen (PSA) levels (PSA > 4 ng/ml) and/or abnormal digital rectal examination (DRE) and/or abnormal MRI. All patients underwent the evaluation of serum PSA-IgM concentration and the iXip ratio was calculated. Accuracy iXip for the prediction of PCa was evaluated using multivariable binary regression analysis and receiver operator characteristics (ROC) curves. Overall 160 patients with a median age of 65 (62/73) years were enrolled. Overall, 42% patients were diagnosed with PCa and 75% of them had high-grade cancer (Epstein ≥ 3). Patients with PCa were older and presented higher PSA levels, higher PIRADS scores and lower prostate volumes (PVs). On ROC analysis iXip presented an area under the curve (AUC) of 0.57 in the prediction of PCa and of 0.54 for the prediction of high-grade PCa. In our experience, immune PSA complexes are not predictors of PCa. iXip analysis should not be included in the diagnostic pathway of patients at increased risk of PCa. [ABSTRACT FROM AUTHOR]

Silk fibroin supported Pd (Pd/SF) has been prepared and used as catalyst in Suzuki–Miyaura cross‐coupling reactions in water/ethanol (4:1 v/v) mixture. The reactions proceed rapidly with aryl iodides and boronic acids with different electronic properties using low metal loading (0.38 mol‐%). Pd/SF exhibits better recyclability compared to other biopolymer‐supported Pd catalysts, up to nineteen cycles without loss of activity. [ABSTRACT FROM AUTHOR]

Silk fibroin (SF) obtained from Bombyx mori cocoon is a very promising biopolymer. It can be processed from aqueous solutions to obtain many versatile scaffolds useful in optoelectronics, photonics, and biomedicine. Aqueous solutions are prepared by dissolving degummed fibroin with chaotropic agents and then purifying by dialysis. This work presents, for the first time, a solubilization protocol, involving CeCl3·7H2O as chaotropic salt in water and ethanol, that allows to regenerate SF under a fibrous form, unlike the standard Ajisawa's method, which uses CaCl2 and allows to obtain aqueous gels. All the experimental analyses performed (SEM, XPS, WAXS, ATR‐FTIR, NMR) suggest that the fiber recovered preserves most of the morphological and structural features of the pristine SF and is doped with Ce(III) ions, that interact mainly with the oxygen atoms of CO moieties and side‐chains of amino acids. Ce(III) doped SF could be the base for new luminescent materials. [ABSTRACT FROM AUTHOR]

Background: Aim of our study is to assess outcomes and safety of button bipola transurethral enucleation of the prostate (B-TUEP) in patients with lower urinary tract symptoms (LUTS) caused by benign prostatic enlargement (BPE) in a single-center cohort study. Materials and Methods: All patients with LUTS caused by BPE undergoing button B-TUEP between May 2012 and December 2013 were prospectively enrolled in our study. Data on clinical history, physical examination, urinary symptoms, erectile function, uroflowmetry, and prostate volume were collected at 0, 1, 3, 6, 12, 24, 36, 48, and 60 months. Early and long-term complications were recorded. Results: Overall 50 patients were enrolled at baseline. Nine patients were excluded during the 5 years. All patients completed the procedure without severe complications. In terms of outcomes, improvement in International Prostate Symptom Score (IPSS) were sustained for all 5 years and mean difference from baseline at 5 years was 17 points. As well, improvements in Qmax (maximum urinary flow rate) were sustained for all 5 years and mean improvement at 5 years was 16 mL/second. Erectile function was slightly improved after surgery and maintained for the following 5 years. Conclusions: Our single-center study suggests that B-TUEP may have excellent outcomes at 5 years with no recurrence. Further multicentre studies should confirm our results. [ABSTRACT FROM AUTHOR]

Abstract Purpose To evaluate persistence rate on repeated transurethral resection of the bladder (re-TURB) 6 weeks after the first TURB in patients with pT1HG disease undergoing resection of the margins and bed on Narrow Band Imaging. Materials and methods A consecutive series of patients undergoing TURB and a diagnosis of pT1 high grade disease were prospectively enrolled. On initial TURB patients underwent classic white light resection of the tumour followed by narrow band image (NBI) resection of margins and bed. After 6 weeks from the initial TURB, patients underwent a re-TURB under white light. Persistence rates on re-TURB were recorded. Results Overall 797 patients underwent TURB, out of them 126 patients with pT1 high grade disease were included in the study. The total number of lesions was 226 meaning 1.79 lesions per patient. On re-TURB 24/126 (19%) of the patients presented residual disease with a total of 28/226 (12%) lesions identified. All these patients presented a pTa residual disease. Out of them 8/21 (38%) presented bladder cancer on the resection bed and 13/21 (62%) presented bladder cancer on margins. Conclusion Narrow Band Imaging trans -urethral resection of the bladder is an oncological effective procedure in the treatment of pT1HG disease. The procedure has a 19% of persistence rate which is inferior when compared to the available evidence on white light TURB. Further multicenter studies are needed in order to validate our results. [ABSTRACT FROM AUTHOR]

the aim of this essay is to point out that Arendt's theory of judgment rests on some theoretical bias without which it cannot be exercised. These "transcendental" conditions belong to different ontological domains that include thinking, action, world, culture and so on. So understood, Arendt's theory of judgment constitutes a theoretical "bridge" that links together what other researchers view as "discontinuities" in Arendt's thought. [ABSTRACT FROM AUTHOR]

Introduction: Understaging after initial transurethral resection is common in patients with high-risk non muscle infiltrating bladder cancer (NMIBC) and can delay accurate diagnosis and definitive treatment. The rate of upstaging from T1 to T2 disease after repeated transurethral resection ranges from 0 to 28%, although the rate of upstaging may be even higher up to 49% when muscularis propria is absent in the first specimen. A restaging classic transurethral resection of bladder tumour (re-cTURBT) is the better predictor of early stage progression. According to some reports, the rate of positivity for tumor in re-cTURBT performed within eight weeks after initial cTURBT was as high as 18-77%, and in about 40% of the patients a change in tumor stage was reported. We aimed to investigate, in high risk group, the presence of residual tumor following white light classical transurethral resection of bladder tumor (WLre-cTURBT) and the different recurrence and progression rate between patients with persistent or negative (pT0) oncological disease after WLre-cTURBT. Materials and methods: A cohort of 285 patients presenting with primitive bladder cancer underwent to WLcTURBT from January 2011 to December 2015; out of them 92 (32.28%) were T1HG. In according to EAU guidelines 2011, after 4-6 weeks all HG bladder cancer patients underwent a WL recTURBT . All patients were submitted to a subsequent followup including cystoscopy every 3 months with multiple biopsies, randomly and in the previous zone of resection; urinary citology on 3 specimens and kidney/bladder ultrasound every 6 months. The average follow-up was 48 months. Results: Following WLre-cTURBT we observed a persistent disease in 18 (15.2%) patients: 14 (77.7%) with a HG-NMIBC and 4 (22.2%) with a high grade (HG) muscle invasive bladder cancer (pT2HG). After follow up of all 92 patients according to the guidelines EAU, we observed recurrence in 36/92 (39.1%) and progression in 14/92 (15.2%). Of 14 NMIBC with persistent disease, 10 patients (71.4%) showed recurrence: 4 patients (40%) were pT1HG with concomitant carcinoma in situ (CIS), 3 patients (30%) multifocal pTaHG, 2 (20%) patients CIS and one patient (10%) a muscle invasive neoplasm (pT2HG). Instead of the group of 48 patients pT0 following WL recTURBT, we observed recurrence in 26 patients (54.1%) and in two patients (4.1%) progressions, who presented after 3 months in association with CIS. The remaining 22 patients (45.9%) with initial pT1HG are still progression free. Multivariate analysis showed that the most important variable of early progression were persistent neoplasm and histopathological findings at WLre-cTURBt (p = 0.01), followed by the result of the first cystoscopy (p = 0.002) and presence of CIS (p = 0.02). Discussion: Following WLre-cTURBt in HG-NMIBC patients we identified in 15% of cases a persistent disease with a 4.3% of MIBC. In the high risk persistent bladder neoplasms group we observed recurrent and progression rate higher than in T0 bladder tumours group (Δ = + 17.3% and Δ = + 62.5%, p < 0.05). [ABSTRACT FROM AUTHOR]

Aryl chlorides, Palladium catalyst, Silk fibroin, Suzuki-Miyaura coupling, Ullmann coupling Front Cover: Silk-Fibroin-Supported Palladium Catalyst for Suzuki-Miyaura and Ullmann Coupling Reactions of Aryl Chlorides (Eur. J. Org. Keywords: Aryl chlorides; Palladium catalyst; Silk fibroin; Suzuki-Miyaura coupling; Ullmann coupling EN Aryl chlorides Palladium catalyst Silk fibroin Suzuki-Miyaura coupling Ullmann coupling 1 1 1 04/29/22 20220427 NES 220427 B The Front Cover b shows a vortex of silk threads: From I Bombyx mori i cocoons, the silk fibroin-supported Palladium catalyst is prepared and successfully applied in the Suzuki-Miyaura and Ullmann coupling reactions of aryl chlorides for the synthesis of biaryl products. [Extracted from the article]

Silk Fibroin (SF) obtained from Bombyx mori is a very attractive biopolymer that can be useful for many technological applications, from optoelectronics and photonics to biomedicine. It can be processed from aqueous solutions to obtain many scaffolds. SF dissolution is possible only with the mediation of chaotropic salts that disrupt the secondary structure of the protein. As a consequence, recovered materials have disordered structures. In a previous paper, it was shown that, by modifying the standard Ajisawa's method by using a lanthanide salt, CeCl 3 , as the chaotropic agent, it is possible to regenerate SF as a fibrous material with a very ordered structure, similar to that of the pristine fiber, and doped with Ce +3 ions. Since SF exhibits a moderate fluorescence which can be enhanced by the incorporation of organic molecules, ions and nanoparticles, the possibility of doping it with lanthanide ions could be an appealing approach for the development of new photonic systems. Here, a systematic investigation of the behavior of degummed SF in the presence of all lanthanide ions, Ln +3 , is reported. It has been found that all lanthanide chlorides are chaotropic salts for solubilizing SF. Ln +3 ions at the beginning and the end of the series (La +3 , Pr +3 , Er +3 , Tm +3 , Yb +3 , Lu +3 ) favor the reprecipitation of fibrous SF as already found for Ce +3 . In most cases, the obtained fiber preserves the morphological and structural features of the pristine SF. With the exception of SF treated with La +3 , Tm +3 , and Lu +3 , for all the fibers re-precipitated a concentration of Ln +3 between 0.2 and 0.4% at was measured, comparable to that measured for Ce +3 -doped SF., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Rizzo, Lo Presti, Giannini, Sibillano, Milella, Guidetti, Musio, Omenetto and Farinola.)