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In this study we will analyze the attitude of older adults to advertisements, differentiating between advertisements that contain rhetorical figures (trope ads) and those that do not (explicit ads). We will also study their attitude toward the brand advertised according to their degree of involvement with the product. In the course of the empirical research, a total of 183 personal surveys were carried out with people aged over 65 taking as reference 2 products with different prices and durabilities. Analysis of the results indicated that in products involving little economic effort, older adults showed the same attitude toward both trope and explicit advertisements. However, with products requiring greater economic effort, older adults showed differences in their attitudes to trope ads and to explicit ads depending on their degree of involvement with the product. These differences had a strong effect on their attitudes to the brands of the products analyzed. (Contains 2 figures and 6 tables.)

We present a novel numerical approach to track the response of a quantum system to an external perturbation that is progressively switched on. The method is applied, within the framework of the density matrix renormalization group technique, to track current-carrying states of interacting fermions in one dimension and in the presence of an Aharonov-Bohm magnetic flux. This protocol allows us to access highly excited states. We also discuss the connection with the entanglement entropy of these excited states. [ABSTRACT FROM AUTHOR]

We investigate the existence of symmetry-protected topological phases in one-dimensional alkaline-earth cold fermionic atoms with general half-integer nuclear spin I at half-filling. In this respect, some orbital degrees of freedom are required. They can be introduced by considering either the metastable excited state of alkaline-earth atoms or the p-band of the optical lattice. Using complementary techniques, we show that SU(2) Haldane topological phases are stabilised from these orbital degrees of freedom. On top of these phases, we find the emergence of topological phases with enlarged SU(2I + 1) symmetry which depend only on the nuclear-spin degrees of freedom. The main physical properties of the latter phases are further studied using a matrix-product state approach. On the one hand, we find that these phases are symmetryprotected topological phases, with respect to inversion symmetry, when I = 1/2, 5/2, 9/2,..., which is directly relevant to ytterbium and strontium cold fermions. On the other hand, for the other values of I(=half-odd integer), these topological phases are stabilised only in the presence of exact SU(2I + 1) symmetry. [ABSTRACT FROM AUTHOR]

Motivated by the ongoing investigation of SrCu2(BO3)2 under pressure, we study a variant of the two-dimensional Shastry-Sutherland (SS) spin-1/2 model with two types of dimers. Combined with the frustration of the SS model, this modification induces, in a large parameter range, a dimensional reduction at low energies, with nearly decoupled effective S=1 Haldane chains forming along one of the diagonals of the lattice. We also present evidence that the intermediate plaquette solid phase of the undistorted SS model remains stable in a finite region of the phase diagram. [ABSTRACT FROM AUTHOR]

The present work evaluates the possibility of using cross-flow filtration to recover enzymatic activities from commercial enzymes used for peeling mandarin segments. Two ceramic membranes of different pore size and molecular weight cut-off were assayed. The membrane of 40 kDa molecular weight cut-off provided better separation of enzymes and carbohydrates than the membrane of 0.14 mm pore size, since the enzymes were readily retained in the retentate fraction, while carbohydrates easily passed into the permeate fraction. After separation, both fractions (enzymes and carbohydrates) could be further used. [ABSTRACT FROM AUTHOR]

Thin films of disordered hexaborides CaB6 and SrB6 deposited by pulsed-laser deposition on MgO (100) or Al2O3 (001) substrates are ferromagnetic. A typical room-temperature moment per unit area of substrate is 350 μB nm-2, with the largest values being found for CaB6 on Al2O3. Lattice defects are the likely origin of the exotic, high-temperature magnetism. The moment, which is present in films as thin as 12 nm, appears to reside in an interface layer whose polarization is approximately 0.4 Tesla. [ABSTRACT FROM AUTHOR]

Four-spin exchange interaction has been raising intriguing questions regarding the exotic phase transitions it induces in two-dimensional quantum spin systems. In this context, we investigate the effects of a cyclic four-spin exchange in the quasi-1D limit by considering a general N-leg spin ladder. We show by means of a low-energy approach that depending on its sign, this ring exchange interaction can engender either a staggered or a uniform dimerization from the conventional phases of spin ladders. The resulting quantum phase transition is found to be described by the SU(2)N conformal field theory. This result, as well as the fractional value of the central charge at the transition, is further confirmed by a large-scale numerical study performed by means of exact diagonalization and density matrix renormalization group approaches for N≤4. [ABSTRACT FROM AUTHOR]

Thin films of disordered hexaborides CaB6 and SrB6 deposited by pulsed-laser deposition on MgO (100) or Al2O3 (001) substrates are ferromagnetic. A typical room-temperature moment per unit area of substrate is 350 μB nm-2, with the largest values being found for CaB6 on Al2O3. Lattice defects are the likely origin of the exotic, high-temperature magnetism. The moment, which is present in films as thin as 12 nm, appears to reside in an interface layer whose polarization is approximately 0.4 Tesla. [ABSTRACT FROM AUTHOR]

The zero-temperature phase diagram of a p-orbital two-component fermionic system loaded into a one-dimensional optical lattice is mapped out by means of analytical and numerical techniques. It is shown that the p-band model away from half-filling hosts various competing superconducting phases for attractive and repulsive interactions. At quarter-filling, we analyze the possible formation of incompressible Mott phases and in particular for repulsive interactions, we find the occurrence of a Mott transition with the formation of fully gapped bond-ordering waves. [ABSTRACT FROM AUTHOR]

We investigate possible realizations of exotic SU(N) symmetry-protected topological (SPT) phases with alkaline-earth cold fermionic atoms loaded into one-dimensional optical lattices. A thorough study of two-orbital generalizations of the standard SU(N) Fermi-Hubbard model, directly relevant to recent experiments, is performed. Using state-of-the-art analytical and numerical techniques, we map out the zero-temperature phase diagrams at half-filling and identify several Mott-insulating phases. While some of them are rather conventional (nondegenerate, charge-density wave, or spin-Peierls-like), we also identify, for even N, two distinct types of SPT phases: an orbital Haldane phase, analogous to a spin-N/2 Haldane phase, and a topological SU(N) phase, which we fully characterize by its entanglement properties. We also propose sets of nonlocal order parameters that characterize the SU(N) topological phases found here. [ABSTRACT FROM AUTHOR]

Subnanometric PtIn clusters have been synthesized within pure silica MFI zeolites by post-synthetic incorporation of In to Pt@K-MFI. The optimized PtIn@K-MFI catalyst outcompetes state-of-the-art PtSn formulations in ethane and propane dehydrogenations, avoiding the need of large excess of Pt promoters and harsh reductive conditions., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

We report the one-pot synthesis of a chabazite (CHA)/erionite (ERI)-type zeolite intergrowth structure characterized by adjustable extents of intergrowth enrichment and Si/Al molar ratios. This method utilizes readily synthesizable 6-azaspiro[5.6]dodecan-6-ium as the exclusive organic structure-directing agent (OSDA) within a potassium-dominant environment. High-throughput simulations were used to accurately determine the templating energy and molecular shape, facilitating the selection of an optimally biselective OSDA from among thousands of prospective candidates. The coexistence of the crystal phases, forming a distinct structure comprising disk-like CHA regions bridged by ERI-rich pillars, was corroborated via rigorous powder X-ray diffraction and integrated differential-phase contrast scanning transmission electron microscopy (iDPC S/TEM) analyses. iDPC S/TEM imaging further revealed the presence of single offretite layers dispersed within the ERI phase. The ratio of crystal phases between CHA and ERI in this type of intergrowth could be varied systematically by changing both the OSDA/Si and K/Si ratios. Two intergrown zeolite samples with different Si/Al molar ratios were tested for the selective catalytic reduction (SCR) of NO x with NH 3 , showing competitive catalytic performance and hydrothermal stability compared to that of the industry-standard commercial NH 3 -SCR catalyst, Cu-SSZ-13, prevalent in automotive applications. Collectively, this work underscores the potential of our approach for the synthesis and optimization of adjustable intergrown zeolite structures, offering competitive alternatives for key industrial processes.

Zeolites, nanoporous aluminosilicates with well-defined porous structures, are versatile materials with applications in catalysis, gas separation, and ion exchange. Hydrothermal synthesis is widely used for zeolite production, offering control over composition, crystallinity, and pore size. However, the intricate interplay of synthesis parameters necessitates a comprehensive understanding of synthesis-structure relationships to optimize the synthesis process. Hitherto, public zeolite synthesis databases only contain a subset of parameters and are small in scale, comprising up to a few thousand synthesis routes. We present ZeoSyn, a dataset of 23,961 zeolite hydrothermal synthesis routes, encompassing 233 zeolite topologies and 921 organic structure-directing agents (OSDAs). Each synthesis route comprises comprehensive synthesis parameters: 1) gel composition, 2) reaction conditions, 3) OSDAs, and 4) zeolite products. Using ZeoSyn, we develop a machine learning classifier to predict the resultant zeolite given a synthesis route with >70% accuracy. We employ SHapley Additive exPlanations (SHAP) to uncover key synthesis parameters for >200 zeolite frameworks. We introduce an aggregation approach to extend SHAP to all building units. We demonstrate applications of this approach to phase-selective and intergrowth synthesis. This comprehensive analysis illuminates the synthesis parameters pivotal in driving zeolite crystallization, offering the potential to guide the synthesis of desired zeolites. The dataset is available at https://github.com/eltonpan/zeosyn_dataset., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The inclusion of particles in a polymeric substrate to achieve certain properties is a well-known practice. In the case of textile substrates, this practice may deeply affect the structure of the produced yarns, as even a filament with no textile applications can be obtained. In this manuscript, titanium dioxide (TiO 2 ) particles were incorporated into polyester (PET) chips and the influence of these fillers on the properties of yarn and fabric, and the ultraviolet protection factor (UPF) was assessed. For this purpose, rutile and anatase crystalline forms of TiO 2 , as well as the size of the particles, were evaluated. Moreover, parameters such as mechanical properties, orientation of the macromolecules and thermal behavior were analyzed to ensure that the textile grade is maintained throughout the production process. The results showed that the inclusion of micro- and nanoparticles of TiO 2 decreases the molecular weight and tenacity of PET. Also, although orientation and crystallinity varied during the textile process, the resulting heatset fabrics did not present important differences in those parameters. Finally, the attainment of textile-grade PET-TiO 2 fabrics with UPF indexes of 50+ with both rutile and anatase and micro- and nano-sized TiO 2 forms was demonstrated.

Cu-exchanged zeolites rely on mobile solvated Cu + cations for their catalytic activity, but the role of the framework composition in transport is not fully understood. Ab initio molecular dynamics simulations can provide quantitative atomistic insight but are too computationally expensive to explore large length and time scales or diverse compositions. We report a machine-learning interatomic potential that accurately reproduces ab initio results and effectively generalizes to allow multinanosecond simulations of large supercells and diverse chemical compositions. Biased and unbiased simulations of [Cu(NH 3 ) 2 ] + mobility show that aluminum pairing in eight-membered rings accelerates local hopping and demonstrate that increased NH 3 concentration enhances long-range diffusion. The probability of finding two [Cu(NH 3 ) 2 ] + complexes in the same cage, which is key for SCR-NOx reaction, increases with Cu content and Al content but does not correlate with the long-range mobility of Cu + . Supporting experimental evidence was obtained from reactivity tests of Cu-CHA catalysts with a controlled chemical composition., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The dyeing and finishing step represents a clear hotspot in the textile supply chain as the wet processing stages require significant amounts of water, energy, and chemicals. In order to tackle environmental issues, natural dyes are gaining attention from researchers as more sustainable alternatives to synthetic ones. This review discusses the topic of natural dyes, providing a description of their main features and differences compared to synthetic dyes, and encompasses a summary of recent research in the field of natural dyes with specific reference to the following areas of sustainable innovation: extraction techniques, the preparation of substrates, the mordanting process, and the dyeing process. The literature review showed that promising new technologies and techniques have been successfully employed to improve the performance and sustainability of natural dyeing processes, but several limitations such as the poor fastness properties of natural dyes, their low affinity with textiles substrates, difficulties in the reproducibility of shades, as well as other factors such as cost-effectiveness considerations, still prevent industry from adopting natural dyes on a larger scale and will require further research in order to expand their use beyond niche applications.

In this work, we have synthesized through an efficient electrostatic deposition a Pt single-atom catalyst (SAC) supported on a Ce-MOF. The basic solution employed in the impregnation process favors the deprotonation of the hydroxyl groups allocated on the clusters that can easily interact with the cationic Pt species. The resulting material, denoted as Pt/UiO-66(Ce), shows an increment of Ce 3+ content, as demonstrated by UV-vis and Ce L 3 -edge XANES spectroscopy. These Ce 3+ species and their corresponding oxygen vacancies are able to accommodate very disperse Pt single sites. Moreover, Pt L 3 -edge XANES and CO-FTIR spectroscopy confirm the cationic nature of the supported Pt δ+ (2+ < δ < 4+). For comparison purpose, we have synthesized and characterized a well-known Pt single-site catalyst supported on nanocrystalline ceria, denoted as Pt/ n CeO 2 . Since the simultaneous presence of Ce 3+ and Pt δ+ on the MOF clusters were able to activate the oxygen molecules and the CO molecule, respectively, we tested Pt/UiO-66(Ce) for the CO oxidation reaction. Interestingly, this catalyst showed ∼six-fold increment in activity in comparison with the traditional Pt/ n CeO 2 material. Finally, the characterization after catalysis reveals that the Pt nature is preserved and that the activity is maintained during 14 h at 100 °C without any evidence of deactivation., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Approaching the level of molecular recognition of enzymes with solid catalysts is a challenging goal, achieved in this work for the competing transalkylation and disproportionation of diethylbenzene catalyzed by acid zeolites. The key diaryl intermediates for the two competing reactions only differ in the number of ethyl substituents in the aromatic rings, and therefore finding a selective zeolite able to recognize this subtle difference requires an accurate balance of the stabilization of reaction intermediates and transition states inside the zeolite microporous voids. In this work we present a computational methodology that, by combining a fast high-throughput screeening of all zeolite structures able to stabilize the key intermediates with a more computationally demanding mechanistic study only on the most promising candidates, guides the selection of the zeolite structures to be synthesized. The methodology presented is validated experimentally and allows to go beyond the conventional criteria of zeolite shape-selectivity., (© 2023. The Author(s).)

Many of the patients with COVID-19 have suffered respiratory distress requiring prolonged endotracheal intubation (ETI) resulting in laryngotracheal complication with an impact on breathing, phonation, and swallowing. Our aim is to describe laryngeal injuries diagnosed after ETI in patients with COVID-19 in a multicentre study., Methods: A prospective descriptive observational study was conducted from January 2021 to December 2021, including COVID-19 patients with laryngeal complications due to ETI diagnosed in several Spanish hospitals. We analyzed the epidemiological data, previous comorbidities, mean time to ICU admission and ETI, need for tracheostomy, mean time on invasive mechanical ventilation until tracheostomy or weaning, mean time in ICU, type of residual lesions, and their treatment., Results: We obtained the collaboration of nine hospitals during the months of January 2021 to December 2021. A total of 49 patients were referred. Tracheostomy was performed in 44.9%, being late in most cases (more than 7-10 days). The mean number of days of ETI until extubation was 17.63 days, and the main post-intubation symptoms were dysphonia, dyspnea, and dysphagia, in 87.8%, 34.7%, and 42.9%, respectively. The most frequent injury was altered laryngeal mobility, present in 79.6%. Statistically, there is a greater amount of stenosis after late ETI and after delayed tracheostomy, not observing the data with the immobility alterations., Conclusion: The mean number of days of ETI was long, according to the latest guidelines, with the need for several cycles of pronation. This long ETI may have had an impact on the increase of subsequent laryngeal sequelae, such as altered laryngeal mobility or stenosis.

The accelerated aging of polyethylene terephthalate (PET) multifilament yarns containing nano or microparticles of titanium dioxide (TiO 2 ), silicon carbide (SiC), or fluorite (CaF 2 ) at a maximum percentage of 2% has been studied. For this, the yarn samples were introduced into a climatic chamber at 50 °C, 50% relative humidity, and an ultraviolet A (UVA) irradiance of 1.4 W/m 2 . They were then removed from the chamber after periods of between 21 and 170 days of exposure. Subsequently, the variation in weight average molecular weight, number molecular weight, and polydispersity was evaluated by gel permeation chromatography (GPC), the surface appearance was evaluated using scanning electron microscopy (SEM), the thermal properties were evaluated using differential scanning calorimetry (DSC), and the mechanical properties were evaluated using dynamometry. The results showed that, at the test conditions, there was degradation in all of the exposed substrates, possibly due to the excision of the chains that make up the polymeric matrix, which resulted in the variation in the mechanical and thermal properties depending on the type and size of the particle used. This study provides insight into the evolution of the properties of PET-based nano- and microcomposites and might be helpful when selecting materials for specific applications, which is of great interest from an industrial point of view.

The objective of this work was to assess the possibility of dyeing a substrate composed of non-textile industrial hemp using natural dyes from common madder ( Rubia Tinctorum L.) and calendula ( Calendula Officialis ) and tannin and alum as mordants. The substrate used for the dyeing had a 25/75 hemp/cotton composition. The hemp raw material is an agricultural by-product that was subjected to mechanical and chemical treatments in order to cottonize the fibers, blend them with cotton, and thus obtain first 40-tex open-end yarns and then a knitted fabric. The latter was subjected to different dyeing conditions by varying the dye, mordant, and method for its application, type of water, and rinsing after dyeing. Measurements of the difference (ΔE) and intensity (K/S) of color and fastness to washing and rubbing were carried out. The results showed that dyeing of a non-textile residual hemp substrate is possible, and that calendula is a good option for dyeing it with tap water, tannin-alum set in a meta-mordanting process, and rinsing after 24 h. In this way, a contribution has been made to the circular economy of the textile industry through the use of more sustainable sources and products.

A novel ab initio methodology based on high-throughput simulations has permitted designing unique biselective organic structure-directing agents (OSDAs) that allow the efficient synthesis of CHA/AEI zeolite intergrowth materials with controlled phase compositions. Distinctive local crystallographic ordering of the CHA/AEI intergrowths was revealed at the nanoscale level using integrated differential phase contrast scanning transmission electron microscopy (iDPC STEM). These novel CHA/AEI materials have been tested for the selective catalytic reduction (SCR) of NOx, presenting an outstanding catalytic performance and hydrothermal stability, even surpassing the performance of the well-established commercial CHA-type catalyst. This methodology opens the possibility for synthetizing new zeolite intergrowths with more complex structures and unique catalytic properties., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Small-cell lung cancers (SCLC) and large-cell neuroendocrine carcinomas (LCNEC) are two types of high-grade pulmonary neuroendocrine carcinomas (NECs). Diagnostic neuroendocrine markers commonly include synaptophysin, chromogranin A, CD56, and insulinoma-associated protein 1 (INSM1). In this study, the utility of secretagogin (SCGN) was examined in the context of pulmonary NEC diagnosis. The study included 71 pulmonary NEC cases (18 SCLCs, 13 combined-SCLCs, 23 LCNECs, and 17 combined-LCNECs). Immunohistochemical stains of SCGN, synaptophysin, chromogranin A, CD56, and INSM1 were performed on whole tumor sections. The stains were evaluated based on combined staining intensity and the proportion of positive tumor cells. At least mild staining intensity in at least 1% of the cells was considered positive. Bioinformatic studies showed specific SCGN expression in neuroendocrine cells and NECs. SCGN showed diffuse nuclear and cytoplasmic staining in NECs with intra-tumoral heterogeneity. The non-neuroendocrine components were negative. The sensitivity of SCGN was no better than the other established neuroendocrine markers based on all NECs combined or LCNECs/c-LCNECs only. However, the sensitivity of SCGN (71%) was higher than chromogranin A (68%) for SCLCs/c-SCLCs only. The average proportion of SCGN positive tumor cells was 8% higher than chromogranin A (22% versus 14%, P = 0.0332) in all NECs and 18% higher for SCLC and c-SCLC cases only (32% versus 13%, P = 0.0054). The above data showed that SCGN could be used as a supplemental neuroendocrine marker to diagnose SCLC., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The modulated hydrothermal (MHT) synthesis of an active and selective Hf-MOF-808 material for the N -alkylation reaction of aniline with benzyl alcohol under base-free mild reaction conditions is reported. Through kinetic experiments and isotopically labeled NMR spectroscopy studies, we have demonstrated that the reaction mechanism occurs via borrowing hydrogen (BH) pathway, in which the alcohol dehydrogenation is the limiting step. The high concentration of defective -OH groups generated on the metallic nodes through MHT synthesis enhances the alcohol activation, while the unsaturated Hf 4+ , which acts as a Lewis acid site, is able to borrow the hydrogen from the methylene position of benzyl alcohol. This fact makes this material at least 14 times more active for the N -alkylation reaction than the material obtained via solvothermal synthesis. The methodology described in this work could be applied to a wide range of aniline and benzyl alcohol derivates, showing in all cases high selectivity toward the corresponding N -benzylaniline product. Finally, Hf-MOF-808, which acts as a true heterogeneous catalyst, can be reused in at least four consecutive runs without any activity loss., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

Zeolites are inorganic materials with wide industrial applications due to their topological diversity. Tailoring confinement effects in zeolite pores, for instance by crystallizing intergrown frameworks, can improve their catalytic and transport properties, but controlling zeolite crystallization often relies on heuristics. In this work, we use computational simulations and data mining to design organic structure-directing agents (OSDAs) to favor the synthesis of intergrown zeolites. First, we propose design principles to identify OSDAs which are selective toward both end members of the disordered structure. Then, we mine a database of hundreds of thousands of zeolite-OSDA pairs and downselect OSDA candidates to synthesize known intergrowth zeolites such as CHA/AFX, MTT/TON, and BEC/ISV. The computationally designed OSDAs balance phase competition metrics and shape selectivity toward the frameworks, thus bypassing expensive dual-OSDA approaches typically used in the synthesis of intergrowths. Finally, we propose potential OSDAs to obtain hypothesized disordered frameworks such as AEI/SAV. This work may accelerate zeolite discovery through data-driven synthesis optimization and design.

Zeolites are versatile catalysts and molecular sieves with large topological diversity, but managing phase competition in zeolite synthesis is an empirical, labor-intensive task. In this work, we controlled phase selectivity in templated zeolite synthesis from first principles by combining high-throughput atomistic simulations, literature mining, human-computer interaction, synthesis, and characterization. Proposed binding metrics distilled from more than 586,000 zeolite-molecule simulations reproduced the extracted literature and rationalized framework competition in the design of organic structure-directing agents. Energetic, geometric, and electrostatic descriptors of template molecules were found to regulate synthetic accessibility windows and aluminum distributions in pure-phase zeolites. Furthermore, these parameters allowed us to realize an intergrowth zeolite through a single bi-selective template. The computation-first approach enables control of both zeolite synthesis and structure composition using a priori theoretical descriptors.

Lung adenocarcinoma is currently staged based on invasive tumor size, excluding areas of lepidic (in situ) growth. Invasive tumor size may be determined by pathologic assessment of a surgical specimen or radiographic assessment on computerized tomography (CT) scan. When invasive tumor size is the primary stage determinate, radiographic-pathologic discordance or discordant interpretation among pathologists may alter tumor stage and treatment. We reviewed 40 cases of non-mucinous pulmonary adenocarcinoma in which tumor size was the only stage-determinant. We determined the inter-observer variability when microscopically assessing architectural patterns and its effect on pathologic stage and treatment. Additionally, we correlated pathologic and radiographic assessment of invasive tumor size and its effect on tumor stage and treatment. The intraclass correlation among three pathologists was 0.9879; all three pathologists agreed on T-stage in 75% of cases. Four cases of pathologic disagreement had the potential to alter therapy. Intraclass correlation between the pathologists and invasive tumor size determined by CT scan was 0.8482. In 23 cases (57.5%) the pathologic T-stage differed (it increased >90% of the time) from clinical T-stage (determined by CT scan) based on invasive tumor size. Five of the radiographically-pathologically discrepant cases resulted in a stage change that had the potential to alter adjuvant therapy. Our findings suggest the stage differences in pathologic staging are prognostically relevant, but unlikely to impact routine selection of adjuvant therapy, and the observed variability in clinical stage tends to select against overuse of neoadjuvant therapy when invasive tumor size is the primary stage-determinant., (Copyright © 2021 Elsevier Inc. All rights reserved.)

By combining kinetics and theoretical calculations, we show here the benefits of going beyond the concept of static localized and defined active sites on solid catalysts, into a system that globally and dynamically considers the active site located in an environment that involves a scaffold structure particularly suited for a target reaction. We demonstrate that such a system is able to direct the reaction through a preferred mechanism when two of them are competing. This is illustrated here for an industrially relevant reaction, the diethylbenzene-benzene transalkylation. The zeolite catalyst (ITQ-27) optimizes location, density, and environment of acid sites to drive the reaction through the preselected and preferred diaryl-mediated mechanism, instead of the alkyl transfer pathway. This is achieved by minimizing the activation energy of the selected pathway through weak interactions, much in the way that it occurs in enzymatic catalysts. We show that ITQ-27 outperforms previously reported zeolites for the DEB-Bz transalkylation and, more specifically, industrially relevant zeolites such as faujasite, beta, and mordenite.

The behavior of single Pt atoms and small Pt clusters was investigated for high-temperature oxidations. The high stability of these molecular sites in CHA is a key to intrinsic structure-performance descriptions of elemental steps such as O 2 dissociation, and subsequent oxidation catalysis. Subtle changes in the atomic structure of Pt are responsible for drastic changes in performance driven by specific gas/metal/support interactions. Whereas single Pt atoms and Pt clusters (> ca. 1 nm) are unable to activate, scramble, and desorb two O 2 molecules at moderate T (200 °C), clusters <1 nm do so catalytically, but undergo oxidative fragmentation. Oxidation of alkanes at high T is attributed to stable single Pt atoms, and the C-H cleavage is inferred to be rate-determining and less sensitive to changes in metal nuclearity compared to its effect on O 2 scrambling. In contrast, when combustion involves CO, catalysis is dominated by metal clusters, not single Pt atoms., (© 2021 Wiley-VCH GmbH.)

The structure of UiO-66(Ce) is formed by CeO 2- x defective nanoclusters connected by terephthalate ligands. The initial presence of accessible Ce 3+ sites in the as-synthesized UiO-66(Ce) has been determined by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR)-CO analyses. Moreover, linear scan voltammetric measurements reveal a reversible Ce 4+ /Ce 3+ interconversion within the UiO-66(Ce) material, while nanocrystalline ceria shows an irreversible voltammetric response. This suggests that terephthalic acid ligands facilitate charge transfer between subnanometric metallic nodes, explaining the higher oxidase-like activity of UiO-66(Ce) compared to nanoceria for the mild oxidation of organic dyes under aerobic conditions. Based on these results, we propose the use of Ce-based metal-organic frameworks (MOFs) as efficient catalysts for the halogenation of activated arenes, as 1,3,5-trimethoxybenzene (TMB), using oxygen as a green oxidant. Kinetic studies demonstrate that UiO-66(Ce) is at least three times more active than nanoceria under the same reaction conditions. In addition, the UiO-66(Ce) catalyst shows an excellent stability and can be reused after proper washing treatments. Finally, a general mechanism for the oxidative halogenation reaction is proposed when using Ce-MOF as a catalyst, which mimics the mechanistic pathway described for metalloenzymes. The superb control in the generation of subnanometric CeO 2- x defective clusters connected by adequate organic ligands in MOFs offers exciting opportunities in the design of Ce-based redox catalysts.

The Lewis/Brønsted catalytic properties of the Metal-Organic Framework (MOF) nodes can be tuned by simply controlling the solvent employed in the synthetic procedure. In this work, we demonstrate that Hf-MOF-808 can be prepared from a material with a higher amount of Brønsted acid sites, via modulated hydrothermal synthesis, to a material with a higher proportion of unsaturated Hf Lewis acid sites, via modulated solvothermal synthesis. The Lewis/Brønsted acid properties of the resultant metallic clusters have been studied by different characterization techniques, including XAS, FTIR and NMR spectroscopies, combined with a DFT study. The different nature of the Hf-MOF-808 materials allows their application as selective catalysts in different target reactions requiring Lewis, Brønsted or Lewis-Brønsted acid pairs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Organic structure directing agents (OSDAs) play a crucial role in the synthesis of micro- and mesoporous materials especially in the case of zeolites. Despite the wide use of OSDAs, their interaction with zeolite frameworks is poorly understood, with researchers relying on synthesis heuristics or computationally expensive techniques to predict whether an organic molecule can act as an OSDA for a certain zeolite. In this paper, we undertake a data-driven approach to unearth generalized OSDA-zeolite relationships using a comprehensive database comprising of 5,663 synthesis routes for porous materials. To generate this comprehensive database, we use natural language processing and text mining techniques to extract OSDAs, zeolite phases, and gel chemistry from the scientific literature published between 1966 and 2020. Through structural featurization of the OSDAs using weighted holistic invariant molecular (WHIM) descriptors, we relate OSDAs described in the literature to different types of cage-based, small-pore zeolites. Lastly, we adapt a generative neural network capable of suggesting new molecules as potential OSDAs for a given zeolite structure and gel chemistry. We apply this model to CHA and SFW zeolites generating several alternative OSDA candidates to those currently used in practice. These molecules are further vetted with molecular mechanics simulations to show the model generates physically meaningful predictions. Our model can automatically explore the OSDA space, reducing the amount of simulation or experimentation needed to find new OSDA candidates., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The capture of CO 2 from post-combustion streams or from other mixtures, such as natural gas, is an effective way of reducing CO 2 emissions, which contribute to the greenhouse effect in the atmosphere. One of the developing technologies for this purpose is physisorption on selective solid adsorbents. The ideal adsorbents are selective toward CO 2 , have a large adsorption capacity at atmospheric pressure and are easily regenerated, resulting in high working capacity. Therefore, adsorbents combining molecular sieving properties and low heats of adsorption of CO 2 are of clear interest as they will provide high selectivities and regenerabilities in CO 2 separation process. Here we report that some aluminophosphate (AlPO) and silicoaluminophosphate (SAPO) materials with LTA, CHA and AFI structures present lower heats of adsorption of CO 2 (13-25 kJ/mol) than their structurally analogous zeolites at comparable framework charges. In some cases, their heats of adsorption are even lower than those of pure silica composition (20-25 kJ/mol). This could mean a great improvement in the regeneration process compared to the most frequently used zeolitic adsorbents for this application while maintaining most of their adsorption capacity, if materials with the right stability and pore size and topology are found., (Copyright © 2020 Pérez-Botella, Martínez-Franco, González-Camuñas, Cantín, Palomino, Moliner, Valencia and Rey.)

The methanol-to-olefins reaction catalyzed by small-pore cage-based acid zeolites and zeotypes produces a mixture of short chain olefins, whose selectivity to ethene, propene and butene varies with the cavity architecture and with the framework composition. The product distribution of aluminosilicates and silicoaluminophosphates with the CHA and AEI structures (H-SSZ-13, H-SAPO-34, H-SSZ-39 and H-SAPO-18) has been experimentally determined, and the impact of acidity and framework flexibility on the stability of the key cationic intermediates involved in the mechanism and on the diffusion of the olefin products through the 8r windows of the catalysts has been evaluated by means of periodic DFT calculations and ab initio molecular dynamics simulations. The preferential stabilization by confinement of fully methylated hydrocarbon pool intermediates favoring the paring pathway is the main factor controlling the final olefin product distribution., (© 2020 Wiley-VCH GmbH.)

The selective incorporation of isolated framework Lewis acid sites at specific crystallographic positions in high-silica zeolites was achieved by applying a rationalized post-synthetic grafting methodology. The removal of framework Ge atoms from a Ge-BEC zeolite with low concentrations of Ge in the framework (Si/Ge ∼ 150) followed by grafting allows the synthesis of Sn-BEC zeolites with Sn atoms positionally biased into the double-4-ring (D4R) crystallographic positions of the BEC framework. Spectroscopic characterization using solid-state nuclear magnetic resonance (NMR) coupled with theoretical calculations revealed that Sn atoms preferentially form open Sn sites in the D4R of Sn-BEC. This observation was supported by IR spectra of adsorbed deuterated acetonitrile (CD 3 CN), a known titrant of Sn sites in zeolites. The catalytic implications of selective incorporation of open Sn sites in Sn-BEC were probed using the Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reaction. Although the MPVO turnover rates normalized by the total number of open Sn sites were comparable on Sn-BEC and a conventional Sn-Beta catalyst synthesized in fluoride media (Sn-Beta(F)), Sn-BEC demonstrated higher per gram reaction rates because of its larger fraction of open sites compared to Sn-Beta(F). These results highlight the advantage of placing active sites in targeted locations within a zeolite structure. The methodology presented here to selectively place catalytic active sites via sacrificial heteroatoms, such as Ge, can be generalized for the design of many other tetrahedrally-coordinated metal-containing zeolites., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Zeolites are microporous crystalline materials with well-defined cavities and pores, which can be prepared under different pore topologies and chemical compositions. Their preparation is typically defined by multiple interconnected variables (e.g., reagent sources, molar ratios, aging treatments, reaction time and temperature, among others), but unfortunately their distinctive influence, particularly on the nucleation and crystallization processes, is still far from being understood. Thus, the discovery and/or optimization of specific zeolites is closely related to the exploration of the parametric space through trial-and-error methods, generally by studying the influence of each parameter individually. In the past decade, machine learning (ML) methods have rapidly evolved to address complex problems involving highly nonlinear or massively combinatorial processes that conventional approaches cannot solve. Considering the vast and interconnected multiparametric space in zeolite synthesis, coupled with our poor understanding of the mechanisms involved in their nucleation and crystallization, the use of ML is especially timely for improving zeolite synthesis. Indeed, the complex space of zeolite synthesis requires drawing inferences from incomplete and imperfect information, for which ML methods are very well-suited to replace the intuition-based approaches traditionally used to guide experimentation. In this Account, we contend that both existing and new ML approaches can provide the "missing link" needed to complete the traditional zeolite synthesis workflow used in our quest to rationalize zeolite synthesis. Within this context, we have made important efforts on developing ML tools in different critical areas, such as (1) data-mining tools to process the large amount of data generated using high-throughput platforms; (2) novel complex algorithms to predict the formation of energetically stable hypothetical zeolites and guide the synthesis of new zeolite structures; (3) new "ab initio" organic structure directing agent predictions to direct the synthesis of hypothetical or known zeolites; (4) an automated tool for nonsupervised data extraction and classification from published research articles. ML has already revolutionized many areas in materials science by enhancing our ability to map intricate behavior to process variables, especially in the absence of well-understood mechanisms. Undoubtedly, ML is a burgeoning field with many future opportunities for further breakthroughs to advance the design of molecular sieves. For this reason, this Account includes an outlook of future research directions based on current challenges and opportunities. We envision this Account will become a hallmark reference for both well-established and new researchers in the field of zeolite synthesis.