Visible Light-Mediated Late-Stage Thioetherification of Mercaptopurine Derivatives.

We disclose herein a novel and general radical approach to alkylthiopurines, encompassing 4 types of thiopurines, as well as their corresponding ribosides. This strategy is achieved through visible light-mediated late-stage functionalization of the sulfur atoms of mercaptopurines. The in situ-generated disulfide was proposed as the pivotal neutral intermediate for this transformation. We present herein a novel photo-mediated homolytic C-S bond formation for the preparation of alkylthiopurines and alkylthiopurine nucleosides. Despite the presence of reactive sites for the Minisci reaction, chemoselective S-alkylation remained the predominant pathway. This method allows for the late-stage introduction of a broad spectrum of alkyl groups onto the sulfur atom of unprotective mercaptopurine derivatives, encompassing 2-, 6-, and 8-mercaptopurine rings. Organoborons serve as efficient and eco-friendly alkylating reagents, providing advantages in terms of readily availability, stability, and reduced toxicity. Further derivatization of the thioetherified nucleosides, together with anti-tumor assays, led to the discovery of potent anti-tumor agents with an IC50 value reaching 6.1 µM (Comp. 31 for Jurkat).

Mesoscopic Analysis of Rounded and Hybrid Aggregates in Recycled Rubber Concrete.

Recycled rubber concrete (RRC), a sustainable building material, provides a solution to the environmental issues posed by rubber waste. This research introduces a sophisticated hybrid random aggregate model for RRC. The model is established by combining convex polygon aggregates and rounded rubber co-casting schemes with supplemental tools developed in MATLAB and Fortran for processing. Numerical analyses, based on the base force element method (BFEM) of the complementary energy principle, are performed on RRC's uniaxial tensile and compressive behaviors using the proposed aggregate models. This study identified the interfacial transition zone (ITZ) around the rubber as RRC's weakest area. Here, cracks originate and progress to the aggregate, leading to widespread cracking. Primary cracks form perpendicular to the load under tension, whereas bifurcated cracks result from compression, echoing conventional concrete's failure mechanisms. Additionally, the hybrid aggregate model outperformed the rounded aggregate model, exhibiting closer peak strengths and more accurate aggregate shapes. The method's validity is supported by experimental findings, resulting In detailed stress-strain curves and damage contour diagrams.

Analysis of Mechanical Properties and Failure Mechanism of Lightweight Aggregate Concrete Based on Meso Level.

The relationship between the macroscopic mechanical properties of lightweight aggregate concrete and its microstructure is a hot topic in the discipline of concrete materials. It is very meaningful to provide an efficient numerical analysis method to conduct a meso-level analysis. This study proposes an automatic dissection algorithm and adapts the calculation program of the base force element method to conduct a non-linear damage analysis. In the numerical simulation, three groups of 100 mm × 100 mm × 100 mm specimens were selected for the uniaxial compression experiment and uniaxial tensile experiment, respectively. The average tensile strength of the numerical simulation for the uniaxial compression test was 21.86 MPa. The stress-strain softening curve, stress contour plot, strain contour plot, and damage plot of the light aggregate concrete were also analyzed. These research results provide data for analyzing the failure mechanism of light aggregate concrete and reveal the failure mechanism of light aggregate concrete. At the same time, the reliability of the proposed algorithm is verified. Our aim is to provide a more efficient and accurate analysis of meso-damage in lightweight aggregate concrete, which benefits industries involved in production, construction, and structural engineering.

Analysis of Tensile Strength and Failure Mechanism Based on Parallel Homogenization Model for Recycled Concrete.

In this paper, a parallel homogenization model for recycled concrete was proposed. A new type of finite element method, the base force element method, based on the complementary energy principle and the parallel homogenization model, is used to conduct meso-level damage research on recycled concrete. The stress-strain softening curve and failure mechanism of the recycled concrete under uniaxial tensile load are analyzed using the nonlinear damage analysis program of the base force element method based on the parallel homogenization model. The tensile strength and destructive mechanisms of recycled concrete materials are studied using this parallel homogenization model. The calculation results are compared with the results of the experiments and meso-level random aggregate model analysis methods. The research results show that this parallel homogenization analysis method can be used to analyze the nonlinear damage analysis of recycled concrete materials. The tensile strength, stress-strain softening curve, and crack propagation process of recycled concrete materials can be obtained using the present method.

Numerical Simulation of Dynamic Mechanical Properties of Concrete under Uniaxial Compression.

Based on the base force element method (BFEM), the dynamic mechanical behavior of concrete under uniaxial compression loading at different strain rates is investigated. The concrete can be considered as a three-phase composite material composed of aggregate, cement mortar, and interfacial transition zone (ITZ) on the meso-level. A two-dimensional random aggregate model is generated by the Monte Carlo method. A multi-linear two-dimensional damage model is applied to describe the damage properties of each phase in the concrete. The strain-softening behavior, strain-rate effect, and failure patterns of the concrete are studied. The numerical results find that the peaks of compressive stress and compressive strain of concrete show the rate-sensitivity in various degrees under different strain rates. The calculated results of the dynamic enhancement factors are in a good agreement with the formula given by the Comité Euro-International du Béton (CEB) and other experimental results. The failure diagram of the specimen clearly describes the compressive failure process of the concrete specimen. This failure's characteristics are similar to the experimental results.