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This manuscript evaluated the performance of silanes in cementitious matrices in the partial replacement of superplasticizers by silanes. For this, pastes with a water/cement ratio of 0.186 were produced and the superplasticizer admixture based on polycarboxylate esters was partially substituted by three types of silanes-vinyltriethoxysilane silanes (VTES), n-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPTMS), and methacryloxypropyltrimethox-ysilane (MCPTMS)-in two substitutions levels (20% and 40%), and then tested in Portland cement pastes. Specific gravity, trapped air, mini-slump, and hydration kinetics (evaluated by isothermal calorimetry up to 48 h) of the pastes were determined in the fresh state. Thus, in the hardened state, the compressive and flexural strength tests (7 and 28 days), specific gravity, and absorption by immersion of the pastes were carried out. The results showed that the substitution of 20% and 40% of VTES and AEAPTMS considerably reduced the workability and increased the air content of the pastes in comparison to the reference sample. In contrast, the incorporation of 20% and 40% of MCPTMS did not significantly affect these properties. The presence of silane, for all analyzed samples, had a delaying effect on the hydration process: the maximum delay verified had a hydration peak in approximately 36 h for the 40% MCPTMS sample and the minimum delay verified had a hydration peak in approximately 11 h for the 20% VTES sample. The replacement of 20% and 40% by any of the silanes progressively reduced the flexural strength at both 7 and 28 days. In the compressive strength, as well as in the tensile strength in flexion, there was a decrease in the results when compared to the reference, except for the MCPTMS, at 7 and 28 days. In immersion absorption, all samples showed high percentages of absorption and void index when compared to the reference.

Niobium oxide (Nb 2 O 5 ) is a semiconductor that exhibits photocatalytic properties, making it potentially valuable in addressing air pollution, self-cleaning, and self-disinfection in cement-based materials (CBMs). Therefore, this study aimed to evaluate the impact of different Nb 2 O 5 concentrations on various parameters, including rheological characteristics, hydration kinetics (measured using isothermal calorimetry), compressive strength, and photocatalytic activity, specifically in the degradation of Rhodamine B (RhB) in white Portland cement pastes. The incorporation of Nb 2 O 5 increased the yield stress and viscosity of the pastes by up to 88.9% and 33.5%, respectively, primarily due to the larger specific surface area (SSA) provided by Nb 2 O 5 . However, this addition did not significantly affect the hydration kinetics or the compressive strength of the cement pastes after 3 and 28 days. Tests focusing on the degradation of RhB in the cement pastes revealed that the inclusion of 2.0 wt.% of Nb 2 O 5 was insufficient to degrade the dye when exposed to 393 nm UV light. However, an interesting observation was made concerning RhB in the presence of CBMs, as it demonstrated a degradation mechanism that was not dependent on light. This phenomenon was attributed to the production of superoxide anion radicals resulting from the interaction between the alkaline medium and hydrogen peroxide.

This article introduces simulations of theoretical material with controlled properties for the evaluation of the effect of key parameters, as volumetric fractions, elastic properties of each phase and transition zone on the effective dynamic elastic modulus. The accuracy level of classical homogenization models was checked regarding the prediction of dynamic elastic modulus. Numerical simulations were performed with the finite element method for evaluations of the natural frequencies and their correlation with E d through frequency equations. An acoustic test validated the numerical results and obtained the elastic modulus of concretes and mortars at 0.3, 0.5 and 0.7 water-cement ratios. Hirsch calibrated according to the numerical simulation (x = 0.27) exhibited a realistic behavior for concretes of w/c = 0.3 and 0.5, with a 5% error. However, when the water-to-cement ratio (w/c) was set to 0.7, Young's modulus displayed a resemblance to the Reuss model, akin to the simulated theoretical triphasic materials, considering matrix, coarse aggregate and a transition zone. Hashin-Shtrikman bounds is not perfectly applied to theoretical biphasic materials under dynamic situations.

Pancreatic cancer (PC) is one of the deadliest cancers, and it is responsible for a number of deaths almost equal to its incidence. The high mortality rate is correlated with several explanations; the main one is the late disease stage at which the majority of patients are diagnosed. Since surgical resection has been recognised as the only curative treatment, a PC diagnosis at the initial stage is believed the main tool to improve survival. Therefore, patient stratification according to familial and genetic risk and the creation of screening protocol by using minimally invasive diagnostic tools would be appropriate. Pancreatic cystic neoplasms (PCNs) are subsets of lesions which deserve special management to avoid overtreatment. The current PC screening programs are based on the annual employment of magnetic resonance imaging with cholangiopancreatography sequences (MR/MRCP) and/or endoscopic ultrasonography (EUS). For patients unfit for MRI, computed tomography (CT) could be proposed, although CT results in lower detection rates, compared to MRI, for small lesions. The actual major limit is the incapacity to detect and characterize the pancreatic intraepithelial neoplasia (PanIN) by EUS and MR/MRCP. The possibility of utilizing artificial intelligence models to evaluate higher-risk patients could favour the diagnosis of these entities, although more data are needed to support the real utility of these applications in the field of screening. For these motives, it would be appropriate to realize screening programs in research settings.

Despite geopolymers having emerged as a more sustainable alternative to Portland cement, their rheological properties still need to be thoroughly investigated, aiming at the material's applicability. Additionally, studies that evaluated the fresh state of geopolymer composites with nanomaterials are scarce. Thus, two metakaolin-based geopolymer systems were reinforced with nanomaterials with a similar geometry: carbon nanotubes (CNT) and silicon carbide whiskers (SCW). The nanomaterials incorporation was assessed by rotational rheometry (conducted up to 110 min), isothermal calorimetry, compressive strength after 7 and 28 days, and the microstructure was investigated using X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). CNT and SCW incorporation (0.20 wt.%) did not significantly affect the yield stress and viscosity of the R2-group (based on metakaolin type 2), while increasing the rheological parameters up to 56.0% for the R1-group (based on metakaolin type 1). Both additions modified the reaction kinetics. Increments of up to 40.7% were observed in the compressive strength of geopolymer pastes with the incorporation of a SCW content of 0.2 wt.%. XRD and FTIR results suggest similar structural modifications between precursors. Nevertheless, R2 showed substantial transformations while the R1 group exhibited anhydrous material that can react over time. Overall, incorporating CNT and SCW contributed to higher mechanical increments on systems with average mechanical strength (R1) compared to systems with higher potential mechanical performance (R2).

The ornamental stone industry generates large amounts of waste thus creating environmental and human health hazards. Thus, pastes with 0-30 wt.% ornamental stone waste (OSW) incorporated into ordinary Portland cement (OPC) were produced and their rheological properties, hydration kinetics, and mechanical properties were evaluated. The CO 2 equivalent emissions related to the pastes production were estimated for each composition. The results showed that the paste with 10 wt.% of OSW exhibited similar yield stress compared to the plain OPC paste, while pastes with 20 and 30 wt.% displayed reduced yield stresses up to 15%. OSW slightly enhanced the hydration kinetics compared to plain OPC, increasing the main heat flow peak and 90-h cumulative heat values. The incorporation of OSW reduced the 1-, 3-, and 28-days compressive strength of the pastes. Water absorption results agreed with the 28 days compressive strength results, indicating that OSW increased the volume of permeable voids. Finally, OSW incorporation progressively reduced the CO 2 emission per m 3 of OPC paste, reaching a 31% reduction for the highest 30 wt.% OSW content. Overall, incorporating up to 10 wt.% with OSW led to pastes with comparable fresh and hardened properties as comported to plain OPC paste.

The functionalization process usually increases the localized defects of carbon nanotubes (CNT). Thus, the ultrasonication parameters used for dispersing non-functionalized CNT should be carefully evaluated to verify if they are adequate in dispersing functionalized CNT. Although ultrasonication is widely used for non-functionalized CNT, the effect of this dispersing process of functionalized CNT has not been thoroughly investigated. Thus, this work investigated the effect of ultrasonication on functionalized CNT + superplasticizer (SP) aqueous dispersions by ultraviolet-visible (UV-Vis) spectroscopy, dynamic light scattering (DLS), and Fourier transform infrared spectroscopy (FTIR). Furthermore, Portland cement pastes with additions of 0.05% and 0.1% CNT by cement weight and ultrasonication amplitudes of 0%, 50% and 80% were evaluated through rheometry, isothermal calorimetry, compressive strength at 1, 7 and 28 days, X-ray diffraction (XRD), and thermogravimetric analysis (TGA). FTIR results from CNT + SP dispersions indicated that ultrasonication may negatively affect SP molecules and CNT graphene structure. The increase in CNT content and amplitude of ultrasonication gradually increased the static and dynamic yield stress of paste but did not significantly affect its hydration kinetics. Compressive strength results indicated that the optimum CNT content was 0.05% by cement weight, which increased the strength of composite by up to 15.8% compared with the plain paste. CNT ultrasonication neither increases the degree of hydration of cement nor the mechanical performance of composite when compared with mixes containing unsonicated CNT. Overall, ultrasonication of functionalized CNT is not efficient in improving the fresh and hardened performance of cementitious composites.

Background: Colorectal cancer (CRC) is the second most common cause of cancer-specific death in both sexes in Western countries. KRAS mutations occur in about 50% of metastatic CRCs (mCRCs). The prognostic value of specific KRAS mutations still remains unexplored and unclear., Methods: Two hundred and forty KRAS wild-type and 206 KRAS/NRAS mutant consecutive unresectable mCRC patients with PS Eastern Cooperative Oncology Group (ECOG) 0 or 1, aged < 80 years, and with a life expectancy >3 months entered into this study. DNA was extracted from paraffin-embedded formalin-fixed tumour tissues, and it was sequenced with the Oncomine Solid Tumour DNA kit (Thermo Fisher Scientific, Waltham, MA, USA). Data were analysed using the Torrent Suite Software v5.0 (Thermo Fisher Scientific). The primary outcome was the analysis of the prognostic role of different KRAS mutations in terms of overall survival (OS)., Results: There were no significant differences among the most prevalent mutations (p.G12D, p.G12V, p.G13D, p.G12A, p.G12C, and p.G12S) in terms of age (<65 vs. ≥65 years), gender (male vs. female), grading (G1/G2 vs. G3), side of primary tumour (left vs. right), pT, and pN. At the median follow-up of 25.6 months, there were 77 deaths in KRAS-mutated patients and 94 in wild-type patients. Three homogeneous prognostic groups were identified: wild-type patients (group A, median survival: 27.5 months), p.G13D/p.G12A/p.G12V/p.G12D mutants (group B, median survival: 17.3 months), and p.G12C/p.G12S mutants (group C, median survival: 5.0 months, p < 0.0001 according to Log Rank test). Upon multivariate analysis, metastatic involvement and p.G12C/p.G12S KRAS mutation group C (vs. other mutations) emerged as independent prognostic variables for survival., Conclusions: We show that mutant KRAS is a negative prognostic factor and that p.G12C/p.G12S variants present the worst clinical courses. This information suggests a clear difference among KRAS mutations, and it will be useful to test potentiated and/or innovative therapeutic strategies in p.G12C/p.G12S metastatic CRC patients.

In the present work, we attempted to develop new metal coordination complexes of the natural flavonoid 5-hydroxyflavone with Sm(III), Eu(III), Gd(III), Tb(III). The resultant hydroxo complexes have been characterized by a variety of spectroscopic techniques, including fluorescence, FT-IR, UV-Vis, EPR and mass spectral studies. The general chemical formula of the complexes is [Ln(C 15 H₉O₃)₃(OH)₂(H₂O) x ]· n H₂O, where Ln is the lanthanide cation and x = 0 for Sm(III), x = 1 for Eu(III), Gd(III), Tb(III) and n = 0 for Sm(III), Gd(III), Tb(III), n = 1 for Eu(III), respectively. The proposed structures of the complexes were optimized by DFT calculations. Theoretical calculations and experimental determinations sustain the proposed structures of the hydroxo complexes, with two molecules of 5-hydroxyflavone acting as monoanionic bidentate chelate ligands. The interaction of the complexes with calf thymus DNA has been explored by fluorescence titration and UV-Vis absorption binding studies, and revealed that the synthesized complexes interact with DNA with binding constants (K b ) ~ 10⁴. Human serum albumin (HSA) and transferrin (Tf) binding studies have also been performed by fluorescence titration techniques (fluorescence quenching studies, synchronous fluorescence spectra). The apparent association constants (K a ) and thermodynamic parameters have been calculated from the fluorescence quenching experiment at 299 K, 308 K, and 318 K. The quenching curves indicate that the complexes bind to HSA with smaller affinity than the ligand, but to Tf with higher binding affinities than the ligand.