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This work describes the development and characterization of tetragonal barium titanate nanoparticles (BTO NPs) and their surface functionalization with dopamine dodecylamine (DDA), a lipophilic organic ligand. The so‐obtained lipophilic NPs (BTO‐DDA) are then formulated at low loadings (< 5 wt.%) into liquid photocurable resins for vat photopolymerization (VP) and 3D printed into solid objects. The printed composites are mechanically characterized in order to assess the effect of the nanomaterial on the mechanical properties of the 3D printed polymer, revealing no significant variations in the mechanical properties (tensile or flexural) of the nanocomposites compared to the original polymer matrix. In light of these results, the printed nanocomposites are studied in terms of their capacity to generate a separation of charge by the piezoelectric effect, typical of the BTO crystal structure. This study reveals that BTO‐loaded nanocomposites display outstanding piezoelectric coefficients as high as 50 pC/N when BTO‐DDA is formulated at 3.0 wt.%, only slightly less than one‐third of the piezoelectric coefficient previously reported for bulk BTO, while preserving the mechanical properties of the polymer matrix. [ABSTRACT FROM AUTHOR]

In this study, olive pit agro-waste from the olive oil industry is valorized by incorporating it as an additive in a polyethylene terephthalate glycol (PETG) matrix to develop bio-based composite materials for large format additive manufacturing (LFAM). The olive pits were first ground into olive pit powder (OPP) and then functionalized by polymerizing poly(butylene adipate-co-terephthalate) PBAT on their surface, resulting in a hydrophobic, modified olive pit powder (MOPP) with enhanced compatibility with the PETG matrix. OPP and MOPP composites were compounded and 3D-printed via Fused Granular Fabrication (FGF) using 5, 10, and 15 wt.% concentrations. The PBAT coating increased the degradation temperature and specific heat capacity of the material, contributing to a lower melt viscosity during printing, as confirmed by MFR, MDSC, and TGA analyses. Tensile testing revealed that MOPP composites generally exhibited superior mechanical properties compared to OPP composites, likely due to the improved compatibility between PBAT on the MOPP surface and the PETG matrix. SEM analysis further validated these findings, showing a highly irregular and porous fracture surface in OPP composites, while MOPP composites displayed a smooth surface with well-integrated MOPP in the PETG matrix. [ABSTRACT FROM AUTHOR]

Microcrystalline cellulose (MCC) is an emerging material with outstanding properties in many scientific and industrial fields, in particular as an additive in composite materials. Its surface modification allows for the fine-tuning of its properties and the exploitation of these materials in a plethora of applications. In this paper, we present the covalent linkage of a luminescent Ir-complex onto the surface of MCC, representing the first incorporation of an organometallic luminescent probe in this biomaterial. This goal has been achieved with an easy and sustainable procedure, which employs a Bronsted-acid ionic liquid as a catalyst for the esterification reaction of -OH cellulose surface groups. The obtained luminescent cellulose microcrystals display high and stable emissions with the incorporation of only a small amount of iridium (III). Incorporation of MCC-Ir in dry and wet matrices, such as films and gels, has been also demonstrated, showing the maintenance of the luminescent properties even in possible final manufacturers. [ABSTRACT FROM AUTHOR]

Since the advent of polymer-based 3D printing technology, the scientific community has directed great effort towards the development of new polymeric formulations that would allow applying this technique to various fields of application, ranging from materials science to tissue engineering. However, most of the available materials are nevertheless oil-based and cost-ineffective. This work presents a novel bio-based resin for stereolithographic DLP 3D printing formulated by mixing a photocurable polyester obtained from renewable resources (poly(1,3-propanediyl-co-glyceryl) itaconate-co-vanillate, PPGIV) with methacrylated citrate and itaconate crosslinkers (bis(HEMA) itaconate, BHI, and tris(HEMA) citrate, THC) and appropriate photopolymerization initiators, terminators and dyes. As a proof-of-concept, a photocurable ink is formulated with phosphorescent Ir(III) cyclometalated complexes and its potential applications have been demonstrated for both rigid and flexible structures. [ABSTRACT FROM AUTHOR]

• Spectral characterization of the electro-mechanical properties of piezoelectric polymeric nanocomposites under compression. • System for the quantitative measurements of the piezoelectric coefficient with high-sensitivity in the low force regime. • Synthesis of piezoelectric BaTiO3 nanoparticles with enhanced affinity with organic solvents via surface functionalization. • Soft piezoelectric nanocomposites based on PDMS and functionalized BaTiO3 nanoparticles. [Display omitted] We present a modular system for the quantitative characterization of the piezoelectric coefficient of piezoelectric polymers and soft polymeric nanocomposites in the compression mode. Our approach is based on an apparatus providing spectral information on the electro-mechanical response in a selected range of frequencies of compressive loads (10–1200 Hz), with high sensitivity (down to 0.5 pC/N) and automated data acquisition modalities, enabling repeatability and reproducibility of the electro-mechanical characterization in the low-force regime (0.1 N 1.5 N). The system is modular and can be developed to cover the 2 mHz-1.2 kHz frequency range in charge mode and the 2 μHz-1200 Hz in voltage mode. We calibrated and validated the apparatus functionality using a commercial PVDF piezoelectric polymer. The suitability of the system for the quantitative measurements of the piezoelectricity of soft polymeric nanocomposites was then assessed by performing measurements of a novel piezoelectric nanocomposite material. This consisted of a polydimethylsiloxane (PDMS) matrix with embedded BaTiO 3 nanoparticles, engineered with functional surface coatings to favor their homogeneous dispersion into the polymer. The proposed system demonstrated to be an effective solution for the systematic characterization of the electro-mechanical conversion properties of soft piezoelectric materials in view of soft robotics and energy harvesting applications. [ABSTRACT FROM AUTHOR]

Glioblastoma multiforme (GBM) is the most aggressive primary tumor of the central nervous system and the diagnosis is often dismal. GBM pharmacological treatment is strongly limited by its intracranial location beyond the blood–brain barrier (BBB). While Temozolomide (TMZ) exhibits the best clinical performance, still less than 20% crosses the BBB, therefore requiring administration of very high doses with resulting unnecessary systemic side effects. Here, we aimed at designing new negative temperature-responsive gel formulations able to locally release TMZ beyond the BBB. The biocompatibility of a chitosan-β-glycerophosphate-based thermogel (THG)-containing mesoporous SiO2 nanoparticles (THG@SiO2) or polycaprolactone microparticles (THG@PCL) was ascertained in vitro and in vivo by cell counting and histological examination. Next, we loaded TMZ into such matrices (THG@SiO2-TMZ and THG@PCL-TMZ) and tested their therapeutic potential both in vitro and in vivo, in a glioblastoma resection and recurrence mouse model based on orthotopic growth of human cancer cells. The two newly designed anticancer formulations, consisting in TMZ-silica (SiO2@TMZ) dispersed in the thermogel matrix (THG@SiO2-TMZ) and TMZ, spray-dried on PLC and incorporated into the thermogel (THG@PCL-TMZ), induced cell death in vitro. When applied intracranially to a resected U87-MG-Red-FLuc human GBM model, THG@SiO2-TMZ and THG@PCL-TMZ caused a significant reduction in the growth of tumor recurrences, when compared to untreated controls. THG@SiO2-TMZ and THG@PCL-TMZ are therefore new promising gel-based local therapy candidates for the treatment of GBM. [ABSTRACT FROM AUTHOR]

Photothermal therapy has always been a very attractive anti-cancer strategy, drawing a lot of attention thanks to its excellent performance as a non-invasive and pretty safe technique. Lately, nanostructures have become the main characters of the play of cancer therapy due to their ability to absorb near-infrared radiation and efficient light-to-heat conversion. Here we present the synthesis of polyethylene glycol (PEG)-stabilized hybrid ultrasmall (<20 nm) gold–silver nanotriangles (AuAgNTrs) and their application in photothermal therapy. The obtained AuAgNTrs were deeply investigated using high-resolution transmission electron microscopy (HR-TEM). The cell viability assay was performed on U-87 glioblastoma multiforme cell model. Excellent photothermal performance of AuAgNTrs upon irradiation with NIR laser was demonstrated in suspension and in vitro, with >80% cell viability decrease already after 10 min laser irradiation with a laser power P = 3W/cm2 that was proved to be harmless to the control cells. Moreover, a previous cell viability test had shown that the nanoparticles themselves were reasonably biocompatible: without irradiation cell viability remained high. Herein, we show that our hybrid AuAgNTrs exhibit very exciting potential as nanostructures for hyperthermia cancer therapy, mostly due to their easy synthesis protocol, excellent cell compatibility and promising photothermal features. [ABSTRACT FROM AUTHOR]

Gold nanorods (GNRs) showed to be a suitable contrast agent in photoacoustics (PA), and are able to provide a tunable absorption contrast against background tissue, while a detectable PA signal can be generated from highly localized and targeted areas. A crucial issue for these imaging techniques is represented by the discrimination between exogenous and endogenous contrast and the assessment of the real PA signal magnitude. The application of image resolution/unmixing methods was implemented and optimized to recover the relative magnitude spectra and distribution maps of image constituents of the biological sample based on multivariate analysis (multivariate curve resolution—alternating least squares, MCR-ALS) in the presence of GNRs with tunable absorption properties. The proposed data analysis methodology is demonstrated on real PA images from experimental animal models and ex-vivo preparations. [ABSTRACT FROM AUTHOR]

Correction for 'Phosphorescent bio-based resin for digital light processing (DLP) 3D-printing' by Mirko Maturi et al., Green Chem., 2020, 22, 6212–6224, DOI: 10.1039/D0GC01983F. [ABSTRACT FROM AUTHOR]

Residual nonvisible bladder cancer after proper treatment caused by technological and therapeutic limitations is responsible for tumor relapse and progression. This study aimed to demonstrate the feasibility of a solution for simultaneous detection and treatment of bladder cancer lesions smaller than one millimeter. The α5β1 integrin was identified as a specific marker in 81% of human high-grade nonmuscle invasive bladder cancers and used as a target for the delivery of targeted gold nanorods (GNRs). In a preclinical model of orthotopic bladder cancer expressing the α5β1 integrin, the photoacoustic imaging of targeted GNRs visualized lesions smaller than one millimeter, and their irradiation with continuous laser was used to induce GNR-assisted hyperthermia. Necrosis of the tumor mass, improved survival, and computational modeling were applied to demonstrate the efficacy and safety of this solution. Our study highlights the potential of the GNR-assisted theranostic strategy as a complementary solution in clinical practice to reduce the risk of nonvisible residual bladder cancer after current treatment. Further validation through clinical studies will support the findings of the present study. [ABSTRACT FROM AUTHOR]

We report in the present study on the catalytic properties of the Deinococcus radiodurans DNA polymerase III α subunit (αDr). The αDr enzyme was overexpressed in Escherichia coli, both in soluble form and as inclusion bodies. When purified from soluble protein extracts, αDr was found to be tightly associated with E. coli RNA polymerase, from which αDr could not be dissociated. On the contrary, when refolded from inclusion bodies, αDr was devoid of E. coli RNA polymerase and was purified to homogeneity. When assayed with different DNA substrates, αDr featured slower DNA extension rates when compared with the corresponding enzyme from E. coli (E. coli DNA Pol III, αEc), unless under high ionic strength conditions or in the presence of manganese. Further assays were performed using a ssDNA and a dsDNA, whose recombination yields a DNA substrate. Surprisingly, αDr was found to be incapable of recombination-dependent DNA polymerase activity, whereas αEc was competent in this action. However, in the presence of the RecA recombinase, αDr was able to efficiently extend the DNA substrate produced by recombination. Upon comparing the rates of RecA-dependent and RecA-independent DNA polymerase activities, we detected a significant activation of αDr by the recombinase. Conversely, the activity of αEc was found maximal under non-recombination conditions. Overall, our observations indicate a sharp contrast between the catalytic actions of αDr and αEc, with αDr more performing under recombination conditions, and αEc preferring DNA substrates whose extension does not require recombination events. [ABSTRACT FROM AUTHOR]

This work shows the synthesis of a drug delivery system made of casein nanoparticles able to host hydrophobic molecules and be functionalized with aptamers targeting the epidermal growth factor receptor. In vitro cell viability and uptake analyses, performed on triple-negative breast cancer cells, confirmed the safety profile and the target selectivity. [ABSTRACT FROM AUTHOR]

Hybrid hydrogels made of chemically modified pectin, gelatin and xanthan gum have been formulated and processed through a double crosslinking step, aimed at wound healing applications. The formulation of hybrid hydrogels finds its cornerstone in the possibility to create a supportive environment for cell adhesion and proliferation, ensuring the transport of nutrients via porous structures, together with mechanical properties closely comparable to the native tissue. The hydrogels present a good swelling behavior, resistance to dissolution and fragmentation in simulated biological environment (PBS 1× and DMEM) for up to 20 days and the porous structure, as pictured via scanning electron microscopy, has been foreseen to help cell migration and the exchange of biomolecules. Rheological characterization showed desired mechanical features, while the biocompatibility has been assessed via live/dead assay on murine fibroblasts. Finally, the hybrid hydrogels have also been proved suitable for mechanical extrusion, demonstrating the possibility of cell encapsulation in the future perspective of 3D bioprinting applications. [ABSTRACT FROM AUTHOR]

• 3D model of mouse bladder was constructed to simulate treatment outcome of GNR-PTT. • GNRs were introduced via intratumoural injection and intravesical instillation. • GNR-PTT treatment outcome is affected by the GNR distribution inside the tumour. • Intravesical instillation is advantageous over intratumoural injection during GNR-PTT. Gold nanorod-assisted photothermal therapy (GNR-PTT) is a cancer treatment whereby GNRs incorporated into the tumour act as photo-absorbers to elevate the thermal destruction effect. In the case of bladder, there are few possible routes to target the tumour with GNRs, namely peri /intra-tumoural injection and intravesical instillation of GNRs. These two approaches lead to different GNR distribution inside the tumour and can affect the treatment outcome. The present study investigates the effects of heterogeneous GNR distribution in a typical setup of GNR-PTT. Three cases were considered. Case 1 considered the GNRs at the tumour centre, while Case 2 represents a hypothetical scenario where GNRs are distributed at the tumour periphery; these two cases represent intratumoural accumulation with different degree of GNR spread inside the tumour. Case 3 is achieved when GNRs target the exposed tumoural surface that is invading the bladder wall, when they are delivered by intravesical instillation. Results indicate that for a laser power of 0.6 W and GNR volume fraction of 0.01%, Case 2 and 3 were successful in achieving complete tumour eradication after 330 and 470 s of laser irradiation, respectively. Case 1 failed to form complete tumour damage when the GNRs are concentrated at the tumour centre but managed to produce complete tumour damage if the spread of GNRs is wider. Results from Case 2 also demonstrated a different heating profile from Case 1, suggesting that thermal ablation during GNR-PTT is dependant on the GNRs distribution inside the tumour. Case 3 shows similar results to Case 2 whereby gradual but uniform heating is observed. Cases 2 and 3 show that uniformly heating the tumour can reduce damage to the surrounding tissues. Different GNR distribution associated with the different methods of introducing GNRs to the bladder during GNR-PTT affect the treatment outcome of bladder cancer in mice. Insufficient spreading during intratumoural injection of GNRs can render the treatment ineffective, while administered via intravesical instillation. GNR distribution achieved through intravesical instillation present some advantages over intratumoural injection and is worthy of further exploration. [ABSTRACT FROM AUTHOR]

A selective functionalization of dopamine amino group with the photoluminescent 7-nitroben-zofurazan was achieved through a one-pot protection-functionalization-deprotection sequence. The resulting fluorescent catecholic ligand was used as a capping agent for iron oxide nanoparticles thus obtaining photoluminescent magnetic nanoparticles (PL-MNPs). The PL-MNPs were then embedded into PLGA-b-PEG polymeric nanocarriers which quenched the emission of the capping agent. Full recovery of fluorescence was observed after disassembling the polymeric layer of the nanoparticle, thus supporting the use of PL-MNPs as a multifunctional system for targeted drug delivery. [ABSTRACT FROM AUTHOR]