This review presents the current state of knowledge on the (3+2) cycloaddition (32CA) reactions involving heteroarene N-oxides. While aromatic amine oxides behave similarly to nitrones, their participation in cycloaddition processes is chemically distinct due to the thermodynamic stability of the aromatic ring system. The manuscript critically examines these reactions, focusing on the competition between the formation of stable fused isoxazolidines and the tendency toward rearomatization. The latter often leads to spontaneous ring opening, elimination, or complex rearrangements rather than the isolation of the primary cycloadduct.

To underscore the critical role of predictive capabilities in third-party logistics (3PL) companies for assortment planning, particularly within the rapidly evolving e-commerce sector and business to business (B2B) flows. This study employs a comprehensive literature review on the forecasting capabilities of 3PL firms, enriched by empirical research across nine logistics facilities. It leverages statistical tools and the ARIMA_PLUS algorithm to evaluate the precision and dependability of demand and supply forecasts generated by these companies. The research reveals that 3PLs possess the ability to generate accurate demand and supply forecasts utilizing advanced forecasting tools. The effectiveness of these forecasts is closely linked to the quality of data available, and the expertise of the personnel involved. Challenges arise in forecasting for smaller order volumes, which are more common in e-commerce flows. The study also highlights that technological advancements and investments in data analytics are pivotal in enhancing forecast accuracy. The investigation focuses on a select group of 3PL companies, potentially limiting the generalizability of the findings. Moreover, the study underscores the necessity for further exploration into how technological innovations impact forecasting capabilities. By emphasizing the significance of 3PL firms' predictive abilities, also for e-commerce assortment planning, this paper addresses a notable gap in existing research. Its insights are invaluable for businesses contemplating logistics outsourcing and for 3PL providers aiming to advance their forecasting proficiency. The findings stress the importance of integrating advanced forecasting models and analytics to stay competitive in the dynamic e-commerce landscape.

This paper presents the results of a search for inhibitors targeting the SARS-CoV-2 Mpro and PLpro proteases, which are crucial enzymes involved in viral replication. The development of new molecules designed as dual non-covalent inhibitors of these proteases was based on previous research that identified a lead compound: N-phenyl-2-(7-oxo-8-(phenylaminomethyl)-2,3-dihydro-[1,4]dioxino[2,3-g]quinolin-6(7H)-yl)acetamide. This compound showed high affinity for the active sites of both Mpro and PLpro in in silico modeling. Using this lead structure as a foundation, we optimized the scaffold by introducing various substituents to create a targeted compound library. We quantitatively analyzed the relationships between the contributions of these substituents and their molecular affinity for the protease active sites. This analysis helped us identify specific substituents that enhanced interactions with both biological targets and suggest a series of 17 modified derivatives, which show promise as dual inhibitors of M^pro and PL^pro. According to docking studies, all synthesized compounds demonstrated favorable interactions within the catalytic sites of both proteases. Moreover, we found that hit-ligands 7d and 7f exhibit binding scores of -9.0 kcal/mol, which are comparable to, or even higher than, those of the reference ligands WU-02 for Mpro and XR8-89 for PLpro, respectively. We successfully implemented the proposed synthetic schemes, allowing us to prepare novel compounds for subsequent in vitro evaluation.

The usefulness of various quantum chemical algorithms (semiempirical, HF, DFT) for predicting the energy and geometry of transition states of polar pseudocyclic processes was analyzed using the example of a model cycloaddition process between (Z)-C,N-diphenylnitrone and (E)-2-phenyl-1-nitroethene. These studies clearly recommend the ωB97XD functional in 6-311+G(d) basis set as the relatively most precise tool for studying the mechanisms of polar pseudocyclic processes.

In terms of Domingo terminology, complexes of carbonyl compounds with imidazolium cations should be considered as extremely strong electrophiles. Reactions of these compounds with phenol yielding bis-phenols follow a polar mechanism. Furthermore, the discussion based on the theory of reactivity indexes can be used to predict the reactivity of respective electrophiles and regio-orientation in EAS reactions, the first stage of bis-phenol synthesis, kinetically rate-limiting for the whole process.

Several waste materials are often used in the mixt-design of asphalt concrete materials to manufacture green construction materials and among them recycled asphalt pavement (RAP) is a favorite material that can be utilized as partial replacement of natural stone aggregates. Addition of such waste and recycled materials may have a negative influence on the mechanical properties and strength or performance of asphalt pavements. In particular, resistance of asphaltic overlays made by some amounts of RAP material against cracking and crack propagation can be reduced and it is necessary to investigate possible effects of RAP addition on cracking resistance of asphalt mixtures. Passage of traffic loads from the cracked overlays and asphaltic pavements can activate all basic tensile and shear mode crack deformations (i.e., pure mode I, pure mode II and pure mode III). In addition, due to the visco-elastic nature of bitumen used in the asphalt mixture, the risk of crack propagation and failure at low temperature conditions is higher than the intermediate and high temperatures. Therefore, in this research, the influence of adding RAP material on the fracture toughness of all three basic fracture modes (namely, K_Ic, K_IIc and K_IIIc) is investigated using edge-notched disc bend (ENDB) specimens. Fracture toughness tests are conducted on hot mix asphalt (HMA) mixtures containing 0, 20 and 40 % RAP material (as replacement of natural aggregates) at five low temperatures of 0, -6, -12, -18, -24 oC. Based on the results, all fracture toughness data were decreased by increasing the temperature from -24oC to zero and increasing the RAP content from 0 to 40%. Depending on the test temperature and mixture type (HMA with or without RAP content) the K_Ic and K^IIc values were varied from 0.5 to 1.1 MPa.m^0.5. This range for KIIIc value was in the lower limit of 0.35 MPa.m^0.5 and 0.75 MPa.m^0.5. Some fracture indexes such as fracture toughness ratios (K_IIc/K_Ic, K_IIIc/K_Ic, K_IIc/K_IIIc, and Kopening/Kshearing-eff) and effective fracture toughness were determined and discussed for the investigated HMA mixtures at different temperatures.

The correlation between coefficients from Dimroth equations and descriptors of global electron density transfer was explored based on the data available in the recent literature. We established that the obtained results should be very usable for the interpretation of the organic reactivity and molecular mechanisms.

Nitrones are an interesting group of organic compounds due to their spin-trapping properties. These chemical compounds are also useful building blocks via cycloaddition reactions. In this work, a comprehensive study about correlation of selected parameters come from quantum chemical and experimental studies, namely 1H chemical shifts, IR absorption bands and UV-Vis maximum absorptions as well as reactivity descriptors such as global electrophilicity and nucleophilicity with substituent constants of Hammett, Taft, Brown and Okamoto's as well as Exner for para substituent analogues of (Z)-C-phenyl-N-methylnitrones have been study. Based on presented results it should be noted that tested models of substituent constants correlate in a satisfactory way with computational data. The opposite conclusion is observed for spectral data derived from analysis performed for synthesized nitrones. The obtained results constitute a useful element for future research on reaction mechanisms involving the tested nitrones.

This paper investigates experimentally and numerically the influence of geometry and loading conditions on the fracture response of rock materials. Seven different test samples namely “Edge-Notched-Disc-Bend (ENDB), Semi-Circular-Bend (SCB), Three-Point-Bend-Inclined-Crack (TPB-IC), Single-Edge-Notched-Bending (SENB), Asymmetric-Three-Point-Bend (ATPB), Edge-Notched-Disc-Compression (ENDC) and Double-Notched-Disc-Compression (DNDC)” made of a marble rock were manufactured and tested under bending and compressive loading conditions. The results showed that the failure loads of all samples increase with the change of pure mode I to pure mode III. However, the corresponding fracture toughness values of ENDB, SCB, TPB-IC, SENB and ATPB specimens decreased, while the ENDC and DNDC samples experienced an increase in the fracture toughness. Among the studied specimens, only the ENDB, ENDC and DNDC samples presented pure mode III with KIIIc/KIc ratio ranging from 0.735 for the ENDB specimen to 2.076 for the DNDC sample. The highest mode-I fracture toughness among all the studied specimens was obtained for the SENB and TPB-IC samples, with a value of 1.54 MPa m0.5, while the lowest value was obtained for the DNDC specimen with a value of 1.21 MPa m0.5. The sign and the magnitude of T-stress considerably depended on the loading condition and geometry of the specimens. The crack trajectories of all specimens under study were also investigated.

The nitrovinyl moiety is surely one of the most reactive fragments in organic chemistry, continuously employed to explore original pathways and reach new targets. One of the most important classes of chemicals containing this fragment are nitro-functionalised analogues of 1,3-butadiene. In this paper a comprehensive review study of these compounds is performed. The manuscript includes an analysis of physicochemical properties, spectral characteristic, synthesis, biological activity, and possible transformations of nitro substituted analogues of 1,3-butadiene. The analysis was divided into several parts, depending on the number of nitro groups included in the structure of a 1,3-butadiene analogue. In addition, the work includes information about hazards and safety principles when working with nitro compounds. Based on the analysis of the literature, it can be concluded that nitro-functionalised analogues of 1,3-butadiene exhibit diversified profile of properties, and an outstanding potential as valuable reagents in organic synthesis useful to obtain heterocycles that can be applied in medicine.