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Calcium silicate–based materials, known for their bioactive properties, are increasingly being used in endodontic therapy. Accidental extrusion of these materials into the periapical tissue is a relatively common phenomenon that can impede periapical healing. The aim of this article is to present three endodontically retreated case reports with moderate to extensive periapical lesions and to review the literature on this topic. The comprehensive search and analysis of the relevant literature included a review of 51 articles, of which nine case reports/series from 2010 to 2023 were considered. Based on the summarized data, over 80% of the retreated cases showed complete healing of the periapical lesions, while the success rate in initially treated teeth was over 90%. Healing of periapical lesions is the most common therapeutic outcome, even in cases where extrusion occurs. Despite this conclusion, extrusion of materials into periapical tissues should be avoided. Further case reports on the extrusion of calcium silicate–based materials other than MTA are recommended. When evaluating the success rate of periapical healing in such cases, it is recommended to extend the follow‐up periods to several years.

The aim of this study was to determine the amount of extruded endodontic irrigant among needle-syringe irrigation (NSI) and laser-activated irrigation (LAI) regimens. Twenty extracted maxillary central incisors were prepared utilizing GT professional rotary files (size 40, taper 0.06). Irrigation was performed with two 27 G irrigation needles (notched open ended (ON) and single side vented (SV)) each at two different irrigant volumetric flow rates (VFR)—0.05 ml/s (3 ml/min) and 0.10 ml/s (6 ml/min). LAI was performed with Er:YAG (erbium-doped yttrium aluminum garnet) using different fiber types (X-Pulse-14/400 cylindrical tip, Preciso- 14/300 flat cylindrical tip, PIPS- 14/400 quartz tapered tip). The Er:YAG laser with a wavelength of 2940 nm (Lightwalker AT, Fotona, Ljubljana, Slovenia) was used according to the following protocol: 10 mJ per pulse, 15 Hz, pulse duration 50 μs. Irrigation time was 60 s for all protocols. Precision syringe pump (PSP) maintained constant irrigant volumetric flow rate. Apically extruded irrigant was collected and net weighed for each protocol ( N  = 10). Data were analyzed by t tests and Kruskal-Wallis. All LAI regimens had statistically significant lower irrigant extrusion compared with NSI except for the SV 27 G needle used with 0.05 ml/s VFR when compared with the Preciso fiber tip ( p  = 0,230). The largest amount of extruded irrigant was with the ON 27 G needle at the 0.10 ml/s VFR, while the smallest was after LAI with PIPS fiber tip. The lower quantity of apically extruded irrigant during LAI (X-Pulse and PIPS) points out a safer endodontic irrigation method compared with conventional irrigations.

The macrocyclic cavitand MeMeCH2 is used as a template for the mechanochemical synthesis of 0.2MeMeCH2@RHO-Zn16(Cl2Im)32 (0.2MeMeCH2@ZIF-71) and RHO-ZnBIm2 (ZIF-11) zeolitic imidazolate frameworks (ZIFs). It is shown that MeMeCH2 significantly accelerates the mechanochemical synthesis, providing high porosity products (BET surface areas of 1140 m2/g and 869 m2/g, respectively). Templation of RHO-topology ZIF frameworks constructed of linkers larger than benzimidazole (HBIm) was unsuccessful. It is also shown that cavitands other than MeMeCH2—namely MeHCH2, MeiBuCH2, HPhCH2, MePhCH2, BrPhCH2, BrC5CH2—can serve as effective templates for the synthesis of x(cavitand)@RHO-ZnIm2 products. The limitations on cavitand size and shape are explored in terms of their effectiveness as templates.

Owing to its efficiency and unique reactivity, mechanochemical processing of bulk solids has developed into a powerful tool for the synthesis and transformation of various classes of materials. Nevertheless, mechanochemistry is primarily based on simple techniques, such as milling in comminution devices. Recently, mechanochemical reactivity has started being combined with other energy sources commonly used in solution-based chemistry. Milling under controlled temperature, light irradiation, sound agitation or electrical impulses in newly developed experimental setups has led to reactions not achievable by conventional mechanochemical processing. This Perspective describes these unique reactivities and the advances in equipment tailored to synthetic mechanochemistry. These techniques — thermo-mechanochemistry, sono-mechanochemistry, electro-mechanochemistry and photo-mechanochemistry — represent a notable advance in modern mechanochemistry and herald a new level of solid-state reactivity: mechanochemistry 2.0. Mechanochemistry is the science of inducing a chemical reaction through the application of mechanical force. This Perspective focuses on combining traditional mechanochemistry with different energy inputs — heat, light, sound or electrical impulses — to advance mechanochemical synthesis.

In this work, we describe a novel halogen-bonded metal-organic cocrystal involving a square-planar Cu(ii) complex and 1,4-diiodotetrafluorobenzene (14tfib) by utilizing an amine ligand whose pendant acetyl group enables halogen bonding. The cocrystal was prepared by both mechanochemical synthesis (liquid-assisted grinding) and the conventional solution-based method. Crystal structure determination by single crystal X-ray diffraction revealed that the dominant supramolecular interactions are the I···O halogen bond between 14tfib and CuCl2(aap)2 building blocks, and the N–H···Cl hydrogen bonds between CuCl2(aap)2 molecules. The combination of halogen and hydrogen bonding leads to the formation of a 2D network. Overall, this work showcases an example of the possibility for extending the complexity of metal-organic crystal structures by using halogen bonding in a way that does not affect other hydrogen bonding synthons.

The synthesis and study of porous materials is important due to their many potential uses (storage and separation of gases, catalysis, electronic devices, etc.) These materials are typically made by solvothermal methods, which are often irreproducible, environmentally unfriendly, and limited in scope of products. Recently, solid-state synthetic methods – such as mechanochemistry – have allowed synthesis of previously unknown porous materials, and improved the efficiency and reliability of existing materials’ syntheses. This work aims to understand the underlying principles behind the solid state synthesis of porous materials, in order to develop new porous materials and study their properties. First, different rigid bowl-like molecules are used as non-ionic solid templates in the solid state synthesis of Zeolitic Imidazolate Frameworks (ZIFs), metal-organic zeolite analogues built from tetrahedral metal cations and imidazolate anions. It is shown that, when used in mechanochemical synthesis alongside zinc oxide and imidazole ligands, cavitands can act as “shoe-last” templates that both accelerate and direct solid state ZIF syntheses towards RHO topology products. Next, ZIF solid state syntheses were monitored by a manometric in situ method. When basic zinc carbonate reacts with imidazole ligands, carbon dioxide is released, and its pressure and temperature can be used to monitor the amount of product formed over time. This technique is used to monitor the synthesis of zni topology zinc imidazolate, and SOD topology zinc 2-methylimidazolate. The latter product is involved in an unexpected feedback mechanism, where the nascent ZIF absorbs the produced carbon dioxide, leading to a complex carbonate byproduct. Finally, a member of guanidinium organosulfonates, a well-known class of hydrogen-bonded organic frameworks, is unequivocally demonstrated to be ultramicroporous for the first time. Desolvation of the acetone solvate of guanidinium 1,4-benzenedisulfonate is monitored through single-crystal-to-single-crystal transformations, and the resulting porous guanidinium 1,4-benzenedisulfonate is characterized and shown to absorb nitrogen, carbon dioxide, and xenon gases. Porous guanidinium 1,4-benzenedisulfonate can be transformed into its nonporous form through thermal and mechanochemical activation, and the nonporous form can be “opened up” using gas pressure.

Crystal structure prediction (CSP) is emerging as a powerful method for the computational design of metal-organic frameworks (MOFs). In this article we employ CSP to perform high-throughput exploration of the crystal energy landscape of zinc imidazolate (ZnIm2). As the most polymorphic member of the zeolitic imidazolate framework (ZIF) family, ZnIm2 has at least 24 reported structural and topological forms, and new polymorphs still being regularly discovered. With the aid of custom-trained machine-learned interatomic potentials (MLIPs) we have performed a high-throughput sampling of over 3 million randomly-generated crystal packing arrangements and identified 9609 energy minima characterized by 1484 network topologies, including 855 topologies that have not been reported before. All but one experimentally-reported structures of ZnIm2, falling within the search boundaries, were ultimately matched with the predicted structures, demonstrating the power of the CSP method in sampling experimentally-relevant ZIF structures. Finally, through a combination of topological analysis, density and porosity considerations, we have identified a set of structures representing promising targets for future experimental screening. as well as demonstrated how structures of mechanochemically-synthesized MOFs could be identified via matching experimental powder diffraction patterns with simulated patterns from the predicted structures.

Crystal structure prediction (CSP) is emerging as a powerful method for the computational design of metal-organic frameworks (MOFs). In this article we demonstrate the high-throughput exploration of the crystal energy landscape of zinc imidazolate (ZnIm2), a highly polymorphic member of the zeolitic imidazolate (ZIF) family, with at least 24 reported structural and topological forms, with new polymorphs still being regularly discovered. With the aid of custom-trained machine-learned interatomic potentials (MLIPs) we have performed a high-throughput sampling of over 3 million randomly-generated crystal packing arrangements and identified 9626 energy minima characterized by 1493 network topologies, including 864 topologies that have not been reported before. Comparisons with previously reported structures revealed 13 topological matches to the experimentally-observed structures of ZnIm2, demonstrating the power of the CSP method in sampling experimentally-relevant ZIF structures. Finally, through a combination of topological analysis, density and porosity considerations, we have identified a set of structures representing promising targets for future experimental screening. Finally, we demonstrate how CSP can be used to assist in the identification of the products of the mechanochemical synthesis.

Background and Objectives: The incidence of colorectal cancer (CRC) in developed Western countries is constantly growing. CRC represents the third most common cancer and the second leading cancer-related cause of death worldwide. Innate and adaptive immunity play a pivotal role in the tumor response, but many of these interactions are still not well understood. Granulysin (GNLY) is an effector, cytolytic molecule, present in human cytotoxic granules of different lymphocyte subpopulations, mainly in cytotoxic T cells and NK cells. Pore-forming proteins GNLY, perforin and granzymes play a key role in cell-mediated immune responses against tumors and infections. Materials and Methods: We aimed to analyze perforin and GNLY-mediated cytotoxicity in the peripheral blood of patients with CRC by flow cytometry. Simultaneously, the cells were labeled with monoclonal antibodies against perforin, GNLY and different surface antigens (CD3, CD4, CD8 and CD56). Phenotypes of lymphocyte subpopulation and expression of perforin and GNLY were analyzed using intracellular and surface immunofluorescence. Results: Total perforin and GNLY expressions in peripheral blood mononuclear cells (PBMC) were significantly lower than in the control group. Statistically significant differences were observed in the distribution of perforin and GNLY expression in different stages of tumors classified according to Dukes’, indicating that the percentage of total perforin and GNLY was significantly diminished in accordance with tumor progression. Perforin and GNLY expression were significantly reduced in NK and NKT cells, accompanied by reduced cytolytic potential in patients with CRC and a consequent reduction in their ability to eliminate tumors and infected cells. Conclusions: The determination of cytotoxic potential may provide a valuable assessment of a patient’s immune status and represent a novel therapeutic target. Patients with CRC exhibit markedly impaired perforin- and GNLY-mediated cytotoxicity that correlates with disease progression. Assessment and restoration of cytolytic potential may therefore serve as indicators of immune competence and promising therapeutic strategies to improve perioperative and oncologic outcomes.

Food is considered as important environmental factor that plays a role in development of Hashimoto's thyroiditis (HT). The goal of our study was to identify food groups, assessed by food frequency questionnaire, that differ in consumption frequency between 491 patients with HT and 433 controls. We also analysed association of food groups with the wealth of HT-related clinical traits and symptoms. We found significantly increased consumption of animal fat (OR 1.55, p  < 0.0001) and processed meat (OR 1.16, p  = 0.0012) in HT cases, whereas controls consumed significantly more frequently red meat (OR 0.80, p  < 0.0001), non-alcoholic beverages (OR 0.82, p  < 0.0001), whole grains (OR 0.82, p  < 0.0001) and plant oil (OR 0.87, p  < 0.0001). We also observed association of plant oil consumption with increased triiodothyronine levels in HT patients (β = 0.07, p  < 0.0001), and, association of olive oil consumption with decreased systolic blood pressure (β = − 0.16, p  = 0.001) in HT patients on levothyroxine (LT4) therapy. Analysis of food consumption between HT patients with and without LT4 therapy suggest that patients do not tend to modify their diet upon HT diagnosis in our population. Our study may be of relevance to nutritionists, nutritional therapists and clinicians involved in developing dietary recommendations for HT patients.