36 results on '"rational synthesis"'
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2. The Complexity of LTL Rational Synthesis.
- Author
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Kupferman, Orna and Shenwald, Noam
- Subjects
LOGIC - Abstract
In rational synthesis, we automatically construct a reactive system that satisfies its specification in all rational environments, namely environments that have objectives and act to fulfill them. We complete the study of the complexity of LTL rational synthesis, when the objectives are given by formulas in Linear Temporal Logic. Our contribution is threefold. First, we tighten the known upper bounds for settings that were left open in earlier work. Second, our complexity analysis is parametric, and we describe tight upper and lower bounds in each of the problem parameters: the game graph, the objectives of the system components, and the objectives of the environment components. Third, we generalize the definition of rational synthesis by adding hostile players to the setting and by combining the cooperative and non-cooperative approaches studied in earlier work. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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- View/download PDF
3. Impact in rational synthesis Co-ZIF templates for derived the structural Co@NC catalysis for high efficient hydrogen and oxygen evolution reactions.
- Author
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Wu, Qing, Gu, Junfei, Wang, Jichao, Liu, Ning, and Chaemchuen, Somboon
- Subjects
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HYDROGEN evolution reactions , *OXYGEN evolution reactions , *CATALYSIS , *ELECTROCATALYSTS , *DESIGN templates , *DOPING agents (Chemistry) - Abstract
Developing highly active and stable non-noble metal bifunctional electrocatalysts are urgently demanded in overall water splitting. Herein, tunable precursor ratio synthesis of cobalt-based ZIFs as a template derived active cobalt embedded N-doped carbon (Co@NC) catalyst. The rational synthesis of ZIF templates significantly impacts the complex nanostructure and properties of the catalyst (Co@NC). Consequently, the different nanostructures on Co@NC exhibit significance for the electrocatalyst of hydrogen and oxygen evolution reactions. The optimized Co@NC-20 provides excellent electrocatalytic activity with the lowest overpotential of 172 and 301 mV for HER and OER, respectively, at the current density of 10 mA cm−2. The bifunctional Co@NC-20 reveals a potential for overall water splitting as low as 1.68 V of 10 mA cm−2. After continuously working for 24h, the exceptional stability activity maintains 75% of the catalytic performance on Co@NC-20. The beneficial character in the synergistic effects between high-active Co species with well-protection of the metal core by carbon shell promotes their excellent performance. This study provides an essential reference for the rational design of ZIF templates for electrocatalysts with more complex structures in the future. [Display omitted] • Rational fabrication Co-ZIF template for sacrificial into Co@NC. • Ratio precursors (M:L) impact in structure/morphologies Co-ZIF template. • High efficient Co@NC electrocatalysts of OER/HER for water splitting reaction. • High active Co/N species for superior bifunctional electrocatalytic performance. • The carbon shell's well-protected core active site indicates good long-time stability features. [ABSTRACT FROM AUTHOR]
- Published
- 2023
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4. Design, Synthesis, and Utility of Defined Molecular Scaffolds
- Author
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Daisuke Sato, Zhiyuan Wu, Hikaru Fujita, and Jonathan S. Lindsey
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aqueous ,functional molecule ,graph ,hub ,peptide ,rational synthesis ,Organic chemistry ,QD241-441 - Abstract
A growing theme in chemistry is the joining of multiple organic molecular building blocks to create functional molecules. Diverse derivatizable structures—here termed “scaffolds” comprised of “hubs”—provide the foundation for systematic covalent organization of a rich variety of building blocks. This review encompasses 30 tri- or tetra-armed molecular hubs (e.g., triazine, lysine, arenes, dyes) that are used directly or in combination to give linear, cyclic, or branched scaffolds. Each scaffold is categorized by graph theory into one of 31 trees to express the molecular connectivity and overall architecture. Rational chemistry with exacting numbers of derivatizable sites is emphasized. The incorporation of water-solubilization motifs, robust or self-immolative linkers, enzymatically cleavable groups and functional appendages affords immense (and often late-stage) diversification of the scaffolds. Altogether, 107 target molecules are reviewed along with 19 syntheses to illustrate the distinctive chemistries for creating and derivatizing scaffolds. The review covers the history of the field up through 2020, briefly touching on statistically derivatized carriers employed in immunology as counterpoints to the rationally assembled and derivatized scaffolds here, although most citations are from the past two decades. The scaffolds are used widely in fields ranging from pure chemistry to artificial photosynthesis and biomedical sciences.
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- 2021
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5. Physiological modeling of the metaverse of the Mycobacterium tuberculosis β-CA inhibition mechanism.
- Author
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Giovannuzzi S, Shyamal SS, Bhowmik R, Ray R, Manaithiya A, Carta F, Parrkila S, Aspatwar A, and Supuran CT
- Subjects
- Humans, Carbonic Anhydrase Inhibitors chemistry, Carbonic Anhydrase Inhibitors pharmacology, Carbonic Anhydrase Inhibitors therapeutic use, Quantitative Structure-Activity Relationship, Molecular Docking Simulation, Bacterial Proteins metabolism, Bacterial Proteins antagonists & inhibitors, Bacterial Proteins chemistry, Antitubercular Agents pharmacology, Antitubercular Agents chemistry, Antitubercular Agents therapeutic use, Antitubercular Agents pharmacokinetics, Models, Biological, Mycobacterium tuberculosis drug effects, Carbonic Anhydrases metabolism, Carbonic Anhydrases chemistry
- Abstract
Tuberculosis (TB) is an infectious disease that primarily affects the lungs of humans and accounts for Mycobacterium tuberculosis (Mtb) bacteria as the etiologic agent. In this study, we introduce a computational framework designed to identify the important chemical features crucial for the effective inhibition of Mtb β-CAs. Through applying a mechanistic model, we elucidated the essential features pivotal for robust inhibition. Using this model, we engineered molecules that exhibit potent inhibitory activity and introduce relevant novel chemistry. The designed molecules were prioritized for synthesis based on their predicted pKi values via the QSAR (Quantitative Structure-Activity Relationship) model. All the rationally designed and synthesized compounds were evaluated in vitro against different carbonic anhydrase isoforms expressed from the pathogen Mtb; moreover, the off-target and widely human-expressed CA I and II were also evaluated. Among the reported derivatives, 2, 4, and 5 demonstrated the most valuable in vitro activity, resulting in promising candidates for the treatment of TB infection. All the synthesized molecules exhibited favorable pharmacokinetic and toxicological profiles based on in silico predictions. Docking analysis confirmed that the zinc-binding groups bind effectively into the catalytic triad of the Mtb β-Cas, supporting the in vitro outcomes with these binding interactions. Furthermore, molecules with good prediction accuracies according to previously established mechanistic and QSAR models were utilized to delve deeper into the realm of systems biology to understand their mechanism in combating tuberculotic pathogenesis. The results pointed to the key involvement of the compounds in modulating immune responses via NF-κβ1, SRC kinase, and TNF-α to modulate granuloma formation and clearance via T cells. This dual action, in which the pathogen's enzyme is inhibited while modulating the human immune machinery, represents a paradigm shift toward more effective and comprehensive treatment approaches for combating tuberculosis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)
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- 2024
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6. Strategy Logic with Imperfect Information.
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BERTHON, RAPHAËL, MAUBERT, BASTIEN, MURANO, ANIELLO, RUBIN, SASHA, and VARDI, MOSHE Y.
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NASH equilibrium ,MULTIPLAYER games ,LOGIC ,MACHINE theory ,INFORMATION storage & retrieval systems ,HIERARCHICAL Bayes model - Abstract
We introduce an extension of Strategy Logic for the imperfect-information setting, called SL
ii and study its model-checking problem. As this logic naturally captures multi-player games with imperfect information, this problem is undecidable; but we introduce a syntactical class of “hierarchical instances” for which, intuitively, as one goes down the syntactic tree of the formula, strategy quantifications are concerned with finer observations of the model, and we prove that model-checking SLii restricted to hierarchical instances is decidable. This result, because it allows for complex patterns of existential and universal quantification on strategies, greatly generalises the decidability of distributed synthesis for systems with hierarchical information. It allows us to easily derive new decidability results concerning strategic problems under imperfect information such as the existence of Nash equilibria or rational synthesis. To establish this result, we go through an intermediary, “low-level” logic much more adapted to automata techniques. QCTL∗ is an extension of CTL∗ with second-order quantification over atomic propositions that has been used to study strategic logics with perfect information. We extend it to the imperfect information setting by parameterising second-order quantifiers with observations. The simple syntax of the resulting logic, QCTL∗ii , allows us to provide a conceptually neat reduction of SLii to QCTL∗ii that separates concerns, allowing one to forget about strategies and players and focus solely on second-order quantification. While the model-checking problem of QCTL∗ii is, in general, undecidable, we identify a syntactic fragment of hierarchical formulas and prove, using an automata-theoretic approach, that it is decidable. [ABSTRACT FROM AUTHOR]- Published
- 2021
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7. Rational one-step synthesis of cobalt clusters embedded-graphitic carbon nitrides for the efficient photocatalytic CO2 reduction under ambient conditions.
- Author
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Nguyen, Duc-Trung, Nguyen, Chinh-Chien, and Do, Trong-On
- Subjects
- *
FULLERENES , *PHOTOREDUCTION , *NITRIDES , *CARBON dioxide , *COBALT , *METAL clusters , *AMINO group , *NITRIDING - Abstract
• The rational synthesis of homogeneously surface embedded cobalt clusters: g-C 3 N 4 system. • The cobalt clusters are successfully stabilized via NH 2 -bpy moieties. • Resulted photocatalyst was effective for the CO 2 reduction under sunlight irradiation. • Achieved very high rate of conversion (CO 2 to CO) and apparent quantum yield (3.2% at 420 nm). • A new one-step strategy to prepare metal clusters embedded photocatalysts. Metal clusters catalyst embedded in semiconductors is the key factor for an efficient photocatalyst toward photocatalytic CO 2 reduction. However, developing a simple method to synthesize such photocatalyst with these features has remained challenging. Herein, a rational one-step synthesis of cobalt clusters embedded in g-C 3 N 4 layers is developed for an enhanced photocatalytic CO 2 reduction. The tiny cobalt clusters are embedded into the g-C 3 N 4 structure and stabilized through the interaction with NH 2 -bpy moieties. Besides, the ligands of cobalt complex can copolymerize with urea during the synthesis owing to the presence of amino groups, thus providing a direct electron transfer between carbon nitride and cobalt clusters, which act as the light harvester and active reduction site, respectively. Consequently, a volcano relationship between the CO generation rate and the cobalt clusters incorporated into the carbon nitride matrix was found. Under optimized conditions, representative C 3 N 4 -0.5CoO x exhibits the very high CO generation rate of 2.6 μmol.h−1. Its apparent quantum yield of 3.2% at 420 nm and 1.0% at 460 nm, which is one of the highest values reported so far. The finding offers new opportunities for designing metal clusters catalysts toward photocatalytic CO 2 reduction based on the judicious use of the metal complex. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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8. Generating carbon nanotube caps of almost all chiralities, using six molecular segment types.
- Author
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Amsharov, Konstantin, Knauf, Andreas, and Tomada, Jörg
- Subjects
- *
CHIRALITY , *CARBON nanotubes , *CARBON - Abstract
We show that molecular precursors, combining six given segment types, can produce all carbon nanotubes of chiralities larger than (9,0). [ABSTRACT FROM AUTHOR]
- Published
- 2020
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- View/download PDF
9. Synthesis and crystallographic, spectroscopic and computational characterization of 3,3′,4,4′‐substituted biphenyls: effects of OR substituents on the intra‐ring torsion angle.
- Author
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Vadra, Nahir, Suarez, Sebastian A., Slep, Leonardo D., Manzano, Veronica E., Halac, Emilia B., Baggio, Ricardo F., and Cukiernik, Fabio D.
- Subjects
- *
DIHEDRAL angles , *MOLECULAR conformation , *BIPHENYL compounds , *RAMAN scattering , *QUANTUM mechanics , *SINGLE crystals - Abstract
Presented here are the synthesis, characterization and study (using single crystal X‐ray diffraction, Raman scattering, quantum mechanics calculations) of the structures of a series of biphenyls substituted in positions 3, 3′, 4 and 4′ with a variety of R (R = methyl, acetyl, hexyl) groups connected to the biphenyl core through oxygen atoms. The molecular conformation, particularly the torsion angle between aromatic rings has been extensively studied both in the solid as well as in the liquid state. The results show that the compounds appearing as rigorously planar in the solid present instead a twisted conformation in the melt. The solid versus melt issue strongly suggests that the reasons for planarity are to be found in the packing restraints. A 'rule of thumb' is suggested for the design of biphenyls with different molecular conformations, based on the selection of the OR substituent. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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10. A perspective on morphology controlled synthesis of powder by tuning chemical diffusion and reaction.
- Author
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Han, Yongsheng, Yang, Tao, and Chen, Yongxiu
- Subjects
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CHEMICAL reactions , *DENDRITIC crystals , *CHEMICAL stability , *CHEMICAL engineering , *SILVER nanoparticles , *DYNAMIC stability - Abstract
Morphology-controlled synthesis of particles by controlling chemical diffusion and reaction was reviewed in this paper, together with a perspective in building up a general model for the structure design and rational synthesis of materials. • A new approach for the rational synthesis of materials is developed. • By tuning diffusion and reaction, diverse shapes of silver particles are synthesized. • Dendritic structures are rationally synthesized by the new method. • The rationality relies on a control on chemical distributions around growing crystals. • Different concentration gradient leads to the diversity of morphologies. This paper is a review of the progress and perspective of an approach for morphology controlled synthesis of particles by tuning chemical diffusion and reaction. Rational synthesis of materials with designed structures is a long term dream of scientists and engineers. The challenges of this dream lie in the poor understanding on the formation mechanism of diverse structures and the insufficient ability to program structure evolutions. From a view of chemical engineering, a shape-controlled synthesis of particles by regulating chemical diffusion and reaction was developed, which was experimentally confirmed by synthesizing diverse morphologies of silver particles at different diffusion and reaction and synthesizing similar dendritic structures of various materials at diffusion limitation. Diffusion and reaction determines the chemical distribution in the growth front of particles, which drives the anisotropic growth of particles, forming diverse morphologies. Ongoing study focuses on the dynamic stability of structure evolution, to establish a general model for structure design and rational synthesis by considering both the local environment and the nature of materials under the concept of mesoscience. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
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11. Synthesis with Rational Environments
- Author
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Kupferman, Orna, Perelli, Giuseppe, Vardi, Moshe Y., Goebel, Randy, Series editor, Tanaka, Yuzuru, Series editor, Wahlster, Wolfgang, Series editor, and Bulling, Nils, editor
- Published
- 2015
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12. Catalysis by nanoscale gold (Au/MOx): A. Rational methods for preparation of small metallic gold particles.
- Author
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Gogate, Makarand R.
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REVERSED micelles , *CATALYSIS , *GOLD , *NANOPARTICLES , *SMALL molecules , *METAL nanoparticles - Abstract
The independent discoveries by Haruta and Hutchings in 1987 that suitably prepared, nanoscale Au particles (1-5 nm in size) are exceptionally active for CO oxidation and activation of other small molecules, under very mild conditions (even < O oC) has changed our traditional perception that gold surfaces are chemically inert towards most molecules and not catalytically very active. After 33 years since those pioneering discoveries, it is now firmly established that nanoscale Au (in the "quantum" size range of 1-5 nm), finely dispersed on suitable "reducible" supports, such as TiO2, Fe2O3, CeO2, and Mn2O3, are exceptionally effective catalysts for CO oxidation, at low temperatures, with stoichiometric conversions and chemical selectivities (to CO2). In part A of this Series, we delineate and discuss the rational methods for synthesis of small metallic Au particles, including colloidal methods, micelles and inverse micelles, microemulsions, and deposition-precipitation (D.-P.) method, and examine their catalytic applications, significant from scientific and commercial perspectives. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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13. Rational Synthesis
- Author
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Fisman, Dana, Kupferman, Orna, Lustig, Yoad, Hutchison, David, editor, Kanade, Takeo, editor, Kittler, Josef, editor, Kleinberg, Jon M., editor, Mattern, Friedemann, editor, Mitchell, John C., editor, Naor, Moni, editor, Nierstrasz, Oscar, editor, Pandu Rangan, C., editor, Steffen, Bernhard, editor, Sudan, Madhu, editor, Terzopoulos, Demetri, editor, Tygar, Doug, editor, Vardi, Moshe Y., editor, Weikum, Gerhard, editor, Esparza, Javier, editor, and Majumdar, Rupak, editor
- Published
- 2010
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14. Tailoring shape and phase formation: Rational synthesis of single-phase BiFeWOx nanooctahedra and phase separated Bi2WO6-Fe2WO6 microflower heterojunctions and visible light photocatalytic performances.
- Author
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Wang, Yanan, Zeng, Yiqing, Chen, Xuanyu, Wang, Qiuyang, Wan, Shipeng, Wang, Dongyu, Cai, Wei, Song, Fujiao, Zhang, Shule, and Zhong, Qin
- Subjects
- *
PHASE transitions , *SINGLE-phase flow , *HYDROTHERMAL synthesis , *BISMUTH compounds , *HETEROJUNCTIONS , *PHOTOCATALYSIS - Abstract
In this work, a novel Bi 2 WO 6 -Fe 2 WO 6 heterojunction (BWFO-10) was designed and fabricated by a facile hydrothermal process for the first time, in which rational synthesis of single-phase BiFeWO x and phase separated Bi 2 WO 6 -Fe 2 WO 6 heterojunction was achieved by adjusting the pH value. More importantly, the 3D flower-like BWFO-10 superstructures was successfully synthesized at pH 10, which overcame the challenge of developing methods to synthesize Bi 2 WO 6 superstructures under strong alkaline condition. Compared with pure BiFeWO x (62%), FWO (47%) and BWO (51%), the as-synthesized BWFO-10 composites exhibited a superior photocatalytic oxidation NO (∼400 ppm) activity (91%) under visible light (λ > 400 nm) irradiation, which was ascribed to the effective separation of the photoinduced charge carriers, evinced by transient photocurrent and EIS measurements. The radical trapping experiment revealed that the h + and OH were the important active species. And the test of stability revealed that the BWFO-10 composite could act as a desired photocatalyst for the oxidation of NO generated from fossil fuel combustion. A possible mechanism of the PCO of NO over BWFO-10 composites and the different evolution of crystal structures, growth and phase-change process had been concisely discussed. The study filled the gap of the currently reported synthesis method that 3D flower-like Bi 2 WO 6 superstructure is not synthesized in alkaline conditions. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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15. Rational synthesis of highly uniform hollow core–shell Mn3O4/CuO@TiO2 submicroboxes for enhanced lithium storage performance.
- Author
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Liu, Peng, Xia, Xifeng, Lei, Wu, and Hao, Qingli
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- *
LITHIUM , *TITANIUM dioxide , *HYDROLYSIS , *HEAT treatment , *METALLIC oxides - Abstract
Highly uniform Mn 3 O 4 /CuO@TiO 2 submicroboxes with hollow and core – shell structure have been synthesized for the first time by a facile and feasible multi-step method. A detail formation mechanism has been proposed based on the chemical and structural characterization, which consists of the part self sacrificing, in situ growth, etching, in situ hydrolysis coating and heat treatment process. The unique firm hollow core – shell structure of Mn 3 O 4 /CuO@TiO 2 made itself exhibit an enhanced lithium storage performance compared to the hollow Mn 3 O 4 /CuO. The TiO 2 coatings not only reinforce the hollow structure but also improve the conductivity, which result in the improved electrochemical performance. Typically, a specific capacity of 583 mA h g −1 (92.8% of the theoretical capacity of 628 mA h g −1 ) and 97.1% capacity retention (compared with the 2nd discharge capacity) after 150 cycles at 0.2 A g −1 were obtained from the hollow core – shell Mn 3 O 4 /CuO@TiO 2 . This work not only provides a promising strategy to solve the rapid capacity fading and large structure damage of metal oxides but also makes a contribution to the design and synthesis of metal oxides with hollow or core – shell structures for various structure-based applications, such as gas sensors, catalysis and energy storage. [ABSTRACT FROM AUTHOR]
- Published
- 2017
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16. Reactions and Dynamics of Ruthenium Clusters
- Author
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Vrieze, K., Elsevier, C. J., and Farrugia, Louis J., editor
- Published
- 1995
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- View/download PDF
17. The rational synthetic parameter analysis for subclasses of microporous aluminophosphates based on hierarchical feature selection model.
- Author
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Guo, Yuting, Tian, Zhenhua, Gao, Na, Qi, Miao, and Wang, Jianzhong
- Subjects
- *
POROUS materials synthesis , *ALUMINOPHOSPHATES , *FEATURE selection , *PARAMETER estimation , *CRYSTAL structure - Abstract
Open-framework aluminophosphates (AlPOs) is an important family of porous crystal materials. But the synthetic chemistry of this kind of materials is very complicated, and the synthesis mechanism has not been clearly understood yet. In this paper, we propose a Hierarchical Feature Selection Model (HFSM) composed of two layers to analyze the rational synthetic parameters for the subclass of microporous aluminophosphates (AlPOs) containing (6,8)-rings. In the first layer, we select a feature subset that could separate the (6,8)-ring-containing microporous AlPOs from other AlPOs. In the second layer, we further analyze which of these selected features are critical for the formation of each special subclass in (6,8)-ring-containing microporous AlPOs. With the optimal feature subset selected by the proposed model, we can obtain the highest accuracy rates as 94.28%, 94.03%, 91.27% and 92.20% for the classification of AEN, AWO, CHA and ERI, respectively. Extensive analysis is presented for the synthetic parameters selected by the hierarchical model, which could provide a useful guidance to the rational synthesis of such materials. [ABSTRACT FROM AUTHOR]
- Published
- 2016
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18. 'Like Straw': Religion and Psychoanalysis
- Author
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Richardson, William J., van Tongeren, Paul, editor, Sars, Paul, editor, Bremmers, Chris, editor, and Boey, Koen, editor
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- 1992
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19. Dry ice-mediated rational synthesis of edge-carboxylated crumpled graphene nanosheets for selective and prompt hydrolysis of cellulose and eucalyptus lignocellulose under ambient reaction conditions
- Author
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Abdu, Hassan Idris, Eid, Kamel, Abdullah, Aboubakr M., Sliem, Mostafa H., Elzatahry, Ahmed, and Lu, Xiaoquan
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Rational synthesis ,Green manufacturing ,Xylose ,Lignin ,Fabrication method ,law.invention ,Catalysis ,Ball milling ,Electrocardiography ,Hydrolysis ,chemistry.chemical_compound ,Nanosheets ,law ,Oxidizing agent ,Selective hydrolysis ,Environmental Chemistry ,Graphite ,Cellulose ,Reaction kinetics ,Catalytic performance ,Grinding ,Refrigerants ,Chemistry ,Graphene ,Carbon Dioxide ,Reaction conditions ,Pollution ,Chlorine compounds ,Efficient catalysts ,Glucose ,Chemical engineering ,Mechanism and kinetics ,Catalyst activity ,Synergistic effect ,Surface modification - Abstract
Edge-selectively carboxylated graphene (ECG) crumpled nanosheets are of great importance in potential applications; however, their catalytic activity towards biomass hydrolysis is not yet highlighted. Herein, we rationally designed two-dimensional ECG nanosheets with tunable COOH content via the ball-milling of graphite with dry ice as an efficient catalyst for selective hydrolysis of cellulose and lignocellulose. The fabrication method is simple, one pot, productive (up to gram-scale), green (no hazardous oxidizing agents), and allows selective edge functionalization without damaging the graphitic basal plane. The as-formed ECG are water-dispersable and self-exfoliated two-dimensional crumpled nanosheets with a high surface area (94.1 m2 g−1) and abundant COOH (26.45%) at the edges. These peculiar structural and compositional merits of ECG lead to the hydrolysis of cellulose to glucose in high yield (87%) alongside the hydrolysis of eucalyptus to xylose (89%) and glucose (65%) within 20 min at 180 °C in the presence of HCl (120 ppm). Meanwhile, ECG hydrolyzed eucalyptus into xylose (98%) in water, owing to its layered structure, hydrophilicity, and synergistic effect. The catalytic performance of the ECG catalyst was benchmarked as a function of COOH content relative to pristine graphite and HCl. The hydrolysis mechanism and kinetics of ECG over cellulose were deciphered via various reaction experiments, conditions, and pretreatments. The present study may open new horizons towards the utilization of ECG in the hydrolysis of biomass. Scopus
- Published
- 2020
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20. Bottom-Up C60 Fullerene Construction from a Fluorinated C60H21F9 Precursor by Laser-Induced Tandem Cyclization.
- Author
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Kabdulov, Mikhail, Jansen, Martin, and Amsharov, Konstantin Yu.
- Subjects
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POLYCYCLIC aromatic hydrocarbons , *CORANNULENE , *FULLERENES , *GRAPHENE synthesis , *CARBON-carbon bonds , *HYDROGEN fluoride , *NANOSTRUCTURED materials synthesis , *NANOTUBES - Abstract
Wrap up: A specially fluorinated C60 fullerene precursor (see figure) was converted to the target C60 cage by laser ionization, resulting in highly selective HF elimination without any detectable side reactions or undesired fragmentation. The fully selective transformation to the target fullerene has been unambiguously demonstrated from a 13C‐labeled precursor. In general the findings open new horizons for the synthesis of carbon‐based nanomaterials, which cannot be obtained by any conventional alternative method. [ABSTRACT FROM AUTHOR]
- Published
- 2013
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21. AlPOs Synthetic Factor Analysis Based on Maximum Weight and Minimum Redundancy Feature Selection.
- Author
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Yuting Guo, Jianzhong Wang, Na Gao, Miao Qi, Ming Zhang, Jun Kong, and Yinghua Lv
- Subjects
- *
ALUMINOPHOSPHATES , *FACTOR analysis , *ZEOLITES , *CHEMICAL synthesis , *MOLECULAR weights , *FEATURE selection , *MOLECULAR structure - Abstract
The relationship between synthetic factors and the resulting structures is critical for rational synthesis of zeolites and related microporous materials. In this paper, we develop a new feature selection method for synthetic factor analysis of (6,12)-ring-containing microporous aluminophosphates (AlPOs). The proposed method is based on a maximum weight and minimum redundancy criterion. With the proposed method, we can select the feature subset in which the features are most relevant to the synthetic structure while the redundancy among these selected features is minimal. Based on the database of AlPO synthesis, we use (6,12)-ring-containing AlPOs as the target class and incorporate 21 synthetic factors including gel composition, solvent and organic template to predict the formation of (6,12)-ring-containing microporous aluminophosphates (AlPOs). From these 21 features, 12 selected features are deemed as the optimized features to distinguish (6,12)-ring-containing AlPOs from other AlPOs without such rings. The prediction model achieves a classification accuracy rate of 91.12% using the optimal feature subset. Comprehensive experiments demonstrate the effectiveness of the proposed algorithm, and deep analysis is given for the synthetic factors selected by the proposed method. [ABSTRACT FROM AUTHOR]
- Published
- 2013
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- View/download PDF
22. Rational synthesis of 1,3-diolein by enzymatic esterification
- Author
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Duan, Zhang-Qun, Du, Wei, and Liu, De-Hua
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ENZYMATIC analysis , *ESTERIFICATION , *BUTANOL , *CHEMICAL reactions , *ORGANIC synthesis , *CHEMISTRY experiments , *CHEMICAL processes - Abstract
Abstract: t-Butanol was an excellent reaction medium for enzyme-mediated esterification of oleic acid with glycerol for 1,3-diolein preparation which has been proved by our group. Herein, to achieve the rational synthesis of 1,3-diolien, response surface methodology was applied to examine the effects of the significant variables and their reciprocal effects on the product synthesis. Under the optimal conditions (62.4°C, 0.75g Novozym 435, substrate molar ratio (oleic acid/glycerol) 2.4 and 4.8g t-butanol), the diolein yield of 87.4% could be achieved, and the value of 1,3-diolien/diolein was as high as 87.8%, which were quite close to the predicted values. Compared with the results of our previous single factor experiment, although the values of diolein yield and 1,3-diolien/diolein could not be improved markedly, the enzyme dosage and the reaction medium were spared by 25% and 20%, respectively, which was a remarkable improvement of the enzymatic process. [Copyright &y& Elsevier]
- Published
- 2012
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23. Phenylene-linked tetrapyrrole arrays containing free base and diverse metal chelate forms – Versatile synthetic architectures for catalysis and artificial photosynthesis.
- Author
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Jing, Haoyu, Rong, Jie, Taniguchi, Masahiko, and Lindsey, Jonathan S.
- Subjects
- *
ARTIFICIAL photosynthesis , *METALWORK , *MACROCYCLIC compounds , *CATALYSIS , *CHLORINS , *PORPHYRINS , *METALLOPORPHYRINS - Abstract
[Display omitted] • Phenylene linkers between tetrapyrrole macrocycles afford defined 3-D architectures. • Phenylene linkers afford rapid rates of energy-, electron-, and hole-transfer processes. • Eight synthetic routes enable construction of phenylene linkers with porphyrins. • Two of the routes are suitable for (bacterio)chlorins for red and NIR applications. • Diverse arrays of metallotetrapyrroles (Mg, Fe, Co, Ni, Cu, Zn, etc.) are accessible. Tetrapyrrole macrocycles are central to photosynthesis yet a single macrocycle does not carry out photosynthesis; rather, assemblies of tetrapyrrole macrocycles work in concert in antenna complexes, reaction centers, and electron-transport chains to harvest sunlight, funnel excited-state energy and separate charge for biological use. A longstanding theme in artificial photosynthesis has been to construct covalently linked "arrays" of metalated and free base tetrapyrrole macrocycles for fundamental studies of such processes, which entail excited-state and ground-state interactions. Among linkers in arrays chemistry, the 1,2-, 1,3-, or 1,4-disubstituted phenylene unit has proved very attractive owing to the resulting short distance, defined architecture, and appropriate extent of electronic coupling of adjacent macrocycles to give rapid electron and/or energy transfer while largely retaining desired spectral features. Eight distinct strategies to construct phenylene-linked tetrapyrrole arrays are identified in a review with comprehensive coverage since inception in the early 1970s through mid-year 2021. The arrays predominantly incorporate porphyrins with very few chlorins and bacteriochlorins, reflecting historic availability of synthetic methods for macrocycle formation. Of the eight strategies, only two appear applicable to (bacterio)chlorins. While studies in artificial photosynthesis have largely fueled this field, applications in catalysis have also been examined. Altogether >400 arrays are covered. The review delves into synthesis and molecular design, sketches photophysical properties, and suggests unrealized opportunities in arrays chemistry. [ABSTRACT FROM AUTHOR]
- Published
- 2022
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24. The use of in silico models for the rationalization of molecularly imprinted polymer synthesis.
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Silva, Weida Rodrigues, Soté, William Oliveira, da Silveira Petruci, João Flávio, Batista, Alex Domingues, and Junior, Moacyr Comar
- Subjects
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IMPRINTED polymers , *MOLECULAR dynamics , *METHACRYLIC acid , *ACRYLIC acid , *POLYMERIZATION , *ACRYLAMIDE - Abstract
[Display omitted] • Theoretical-experimental integrated approach for MIP development. • In silico models were evaluated by molecular dynamics simulation. • Correlated insight about ligand screening and mechanism of interaction. • Successful drug of abuse functional imprinting and recognition selectivity. • Polymer characterization with FT-IR, MEV, and BET. Molecularly imprinted polymers (MIPs) represent an advance in sample preparation techniques due to their inherent functionalized cavities with great rebinding capacity, leading to significant selectivity improvement for the desired target. However, the pursue of optimized MIPs is a very time-consuming process, especially in relation to monomer selection, which demands a considerable amount of synthesis. One strategy to reduce time and consequently minimize the waste of chemicals is to use reliable computational tools capable of providing suitable indications about the most optimal synthesis conditions, including the most appropriate monomer and solvent. These computational tools should accurately describe all parameters involved in the real scenario, such as the number of molecules, solvents, etc. Molecular dynamics methodology was employed in this work to select the most suitable functional monomer for imprinting scopolamine, a known drug of abuse molecule used as the template. The evaluated monomers were acrylic acid (AAC), methacrylic acid (MAA), and acrylamide (ACR). The interactions between template and monomers were characterized in terms of spatial distribution, hydrogen bonds, interaction energy, and crosslinker influence. Additionally, their mechanism of interaction was also discussed. The theoretical results identified acrylamide as the most interactive ligand and the one that suffers less competitive influence from the crosslinker. Imprinted and non-imprinted polymers were synthesized by bulk polymerization. The polymers were characterized by FT-IR, MEV, and BET. The imprinting factors (IF) calculated for acrylic acid, methacrylic acid, and acrylamide ligands were 1.2, 1.1, and 3.2, respectively, confirming a higher interaction between template and acrylamide, as suggested by simulations. The selectivity of the MIP with acrylamide was tested against atropine and hyoscine. The calculated selectivity factors (β) were 3.40 and 5.25 for atropine and hyoscine, respectively. The theoretical and experimental approaches showed great correlation. In conclusion, this paper offers a comprehensive and integrated protocol for the rational design and synthesis of molecularly imprinted polymers. [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
- View/download PDF
25. Made to Measure: Ecological Rationality in Structured Environments.
- Author
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Bullock, Seth and Todd, Peter
- Abstract
A working assumption that processes of natural and cultural evolution have tailored the mind to fit the demands and structure of its environment begs the question: how are we to characterize the structure of cognitive environments? Decision problems faced by real organisms are not like simple multiple-choice examination papers. For example, some individual problems may occur much more frequently than others, whilst some may carry much more weight than others. Such considerations are not taken into account when (i) the performance of candidate cognitive mechanisms is assessed by employing a simple accuracy metric that is insensitive to the structure of the decision-maker's environment, and (ii) reason is defined as the adherence to internalist prescriptions of classical rationality. Here we explore the impact of frequency and significance structure on the performance of a range of candidate decision-making mechanisms. We show that the character of this impact is complex, since structured environments demand that decision-makers trade off general performance against performance on important subsets of test items. As a result, environment structure obviates internalist criteria of rationality. Failing to appreciate the role of environment structure in shaping cognition can lead to mischaracterising adaptive behavior as irrational. [ABSTRACT FROM AUTHOR]
- Published
- 1999
- Full Text
- View/download PDF
26. Rational Synthesis of Porous Graphitic-like Carbon Nitride Nanotubes Codoped with Au and Pd as an Efficient Catalyst for Carbon Monoxide Oxidation
- Author
-
Mostafa H. Sliem, H. Al-Kandari, Kamel Eid, Aboubakr M. Abdullah, and M. A. Sharaf
- Subjects
Materials science ,02 engineering and technology ,Nitride ,010402 general chemistry ,01 natural sciences ,Catalysis ,chemistry.chemical_compound ,Electrochemistry ,Au ,Pd ,General Materials Science ,Carbon nitride ,Spectroscopy ,Carbonization ,Energy conversion efficiency ,Surfaces and Interfaces ,Rational Synthesis ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,0104 chemical sciences ,Porous Graphitic-like Carbon Nitride Nanotubes Codoped ,chemistry ,Polymerization ,Chemical engineering ,0210 nano-technology ,Ethylene glycol ,Carbon monoxide - Abstract
The precise fabrication of efficient catalysts for CO oxidation is of particular interest in a wide range of industrial and environmental applications. Herein, a scalable method is presented for the controlled synthesis of graphitic-like porous carbon nitride nanotubes (gC 3 N 4 NTs) codoped with Au and Pd (Au/Pd/gC 3 N 4 NTs) as efficient catalysts for carbon monoxide (CO) conversion. This includes the activation of melamine with nitric acid in the presence of ethylene glycol and metal precursors followed by consecutive polymerization and carbonization. This drives the formation of porous one-dimensional gC 3 N 4 NT with an outstanding surface area of (320.6 m 2 g -1 ) and an atomic-level distribution of Au and Pd. Intriguingly, the CO conversion efficiency of Au/Pd/gC 3 N 4 NTs was substantially greater than that for gC 3 N 4 NTs. The approach thus presented may provide new avenues for the utilization of gC 3 N 4 doped with multiple metal-based catalysts for CO conversion reactions which had been rarely reported before. Scopus
- Published
- 2019
27. Rational Synthesis under Imperfect Information
- Author
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Filiot, E., Gentilini, R., Raskin, and J. -F.
- Subjects
TheoryofComputation_MISCELLANEOUS ,rational synthesis ,Computer Science::Computer Science and Game Theory ,Computer science ,ComputingMilieux_PERSONALCOMPUTING ,Perfect information ,TheoryofComputation_GENERAL ,Rationality ,0102 computer and information sciences ,02 engineering and technology ,imperfect information ,01 natural sciences ,omega-regular objectives ,State of the Environment ,Undecidable problem ,non zero-sum multiplayer games ,symbols.namesake ,010201 computation theory & mathematics ,Nash equilibrium ,non zero-sum multiplayer games, rational synthesis, imperfect information, omega-regular objectives ,0202 electrical engineering, electronic engineering, information engineering ,symbols ,Natural (music) ,020201 artificial intelligence & image processing ,Mathematical economics - Abstract
In this paper, we study the rational synthesis problem for turn-based multiplayer non zero-sum games played on finite graphs for omega-regular objectives. Rationality is formalized by the concept of Nash equilibrium (NE). Contrary to previous works, we consider here the more general and more practically relevant case where players are imperfectly informed. In sharp contrast with the perfect information case, NE are not guaranteed to exist in this more general setting. This motivates the study of the NE existence problem. We show that this problem is ExpTime-C for parity objectives in the two-player case (even if both players are imperfectly informed) and undecidable for more than 2 players. We then study the rational synthesis problem and show that the problem is also ExpTime-C for two imperfectly informed players and undecidable for more than 3 players. As the rational synthesis problem considers a system (Player 0) playing against a rational environment (composed of k players), we also consider the natural case where only Player 0 is imperfectly informed about the state of the environment (and the environment is considered as perfectly informed). In this case, we show that the ExpTime-C result holds when k is arbitrary but fixed. We also analyse the complexity when k is part of the input.
- Published
- 2018
28. Optimized synthesis of N-heterocyclic dronic acids; closing a black-box era
- Author
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Keglevich, György, Grün, Alajos, Aradi, Klára, Garadnay, Sándor, and Greiner, István
- Subjects
- *
ORGANIC synthesis , *HETEROCYCLIC chemistry , *ACETIC acid , *PHOSPHORIC acid , *CHEMICAL reagents , *SOLVENTS - Abstract
Abstract: To clarify the inconsistent patent literature, the synthesis of Zoledronic and Risedronic acids involving a heterocyclic acetic acid (HAA), phosphorous acid (PA) and phosphorus trichloride (PC) as the reagents, and methanesulfonic acid as the solvent was studied in detail. It was found that the best synthesis can be accomplished at 80°C using HAA and PC in a 1:3.1 molar ratio without any PA. [Copyright &y& Elsevier]
- Published
- 2011
- Full Text
- View/download PDF
29. Rational synthesis of TS-1 zeolite to direct both particle size and framework Ti in favor of enhanced catalytic performance.
- Author
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Shakeri, Mozaffar and Dehghanpour, Safoura Bakhodaye
- Subjects
- *
PARTICLES , *ZEOLITES , *BASE catalysts - Abstract
Simultaneous control over particle size and framework Ti content are the major challenges of synthesis of efficient TS-1 catalysts. Here we firstly report control over the particle size and framework Ti content of TS-1 catalysts in a wide range through conventional hydrothermal approach, evaluate catalytic performances of obtained TS-1 catalysts, and then rationally design a novel procedure of synthesis. The characterization of TS-1 catalysts by several techniques revealed that synthesis conditions through conventional hydrothermal approach to reach minimum particle size is different than that to reach maximum framework Ti content. The catalytic study of TS-1 catalysts showed that conversion of phenol (kinetic diameter of 0.57 nm) increased with increase in the particle size, reached a maximum of 29.9% for the TS-1 with particle size of 270 nm, and then dropped significantly for the TS-1 with biggest particle size. The conversion of dibenzothiophene (kinetic diameter of 0.9 nm), however, decreased with increase in the particle size and maximum conversion of 69.0% was achieved by the TS-1 with smallest particle size of 130 nm. No TS-1 catalyst synthesized through conventional approach was efficient in oxidation of the both substrates as the catalyst lacks either small particle size or enhanced framework Ti. Based on the property-function results from conventional synthesis, we rationally designed a novel synthesis of TS-1 with minimum water and optimum pH by (NH 4) 2 CO 3 addition to minimize the particle size and maximize framework Ti content, respectively. The resultant TS-1 with both features of small particle size of 185 nm and enhanced framework Ti resulted in full conversions of phenol and bulky substrate of dibenzothiophene and generates the least amount of wastewater. The new approach applied here is promising and applicable to make efficient Lewis-acid zeolites. Image 1 • Systematic synthesis to understand how framework Ti and crystal size of TS-1 changes upon synthesis conditions. • Evaluation of TS-1 in oxidation of various substrates to clarify contribution of internal and external framework Ti. • Design of TS-1 catalyst based on property-function results from systematic study. • Synthesis of efficient TS-1 catalyst with minimum amount of wastewater generation. • Rational synthesis of TS-1 with superior catalytic performance toward oxidation of substrates with different sizes. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
- View/download PDF
30. AlPOs Synthetic Factor Analysis Based on Maximum Weight and Minimum Redundancy Feature Selection
- Author
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Na Gao, Ming Zhang, Yuting Guo, Jun Kong, Lv Yinghua, Jianzhong Wang, and Miao Qi
- Subjects
Computer science ,Feature selection ,Article ,Catalysis ,Phosphates ,Inorganic Chemistry ,lcsh:Chemistry ,Redundancy (information theory) ,feature selection ,Minimum redundancy feature selection ,Physical and Theoretical Chemistry ,Molecular Biology ,lcsh:QH301-705.5 ,Spectroscopy ,rational synthesis ,business.industry ,Organic Chemistry ,Pattern recognition ,General Medicine ,Microporous material ,data mining ,Computer Science Applications ,lcsh:Biology (General) ,lcsh:QD1-999 ,AlPOs ,Artificial intelligence ,Factor Analysis, Statistical ,business ,Porosity ,Algorithms ,Aluminum - Abstract
The relationship between synthetic factors and the resulting structures is critical for rational synthesis of zeolites and related microporous materials. In this paper, we develop a new feature selection method for synthetic factor analysis of (6,12)-ring-containing microporous aluminophosphates (AlPOs). The proposed method is based on a maximum weight and minimum redundancy criterion. With the proposed method, we can select the feature subset in which the features are most relevant to the synthetic structure while the redundancy among these selected features is minimal. Based on the database of AlPO synthesis, we use (6,12)-ring-containing AlPOs as the target class and incorporate 21 synthetic factors including gel composition, solvent and organic template to predict the formation of (6,12)-ring-containing microporous aluminophosphates (AlPOs). From these 21 features, 12 selected features are deemed as the optimized features to distinguish (6,12)-ring-containing AlPOs from other AlPOs without such rings. The prediction model achieves a classification accuracy rate of 91.12% using the optimal feature subset. Comprehensive experiments demonstrate the effectiveness of the proposed algorithm, and deep analysis is given for the synthetic factors selected by the proposed method.
- Published
- 2013
31. Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates
- Author
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Juan M. Gutiérrez-Zorrilla, Jose I. Martínez, Leire San Felices, Pablo Vitoria, Santiago Reinoso, Beñat Artetxe, Nerea Andino, and Fernando López Arbeloa
- Subjects
Inorganic chemistry ,organosilyl derivatives ,010402 general chemistry ,01 natural sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,lcsh:Inorganic chemistry ,polyoxometalates ,Isostructural ,heteropolyanions ,building-blocks ,HOMO/LUMO ,approximation ,rational synthesis ,solution stability ,organophosphonates ,010405 organic chemistry ,Chemistry ,charge transfer ,Nuclear magnetic resonance spectroscopy ,fluorescence ,Phosphonate ,lcsh:QD146-197 ,0104 chemical sciences ,Dawson polyoxometalate ,Crystallography ,spectroscopic characterization ,Absorption band ,Polyoxometalate ,functionalization ,Organophosphonates ,Density functional theory ,structural-characterization ,organic-inorganic hybrids - Abstract
New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds [N(C4H9)(4)](3)[H(POC11H9)(2)(-HBW11O39)] (TBA-1) and [N(C4H9)(4)](3)[H(POC11H9)(2)(-SiW11O39)] (TBA-2). Liquid-solution UV-Vis transmittance and solid-state diffuse reflectance spectroscopy studies reveal the presence of a new absorption band in the visible region, the charge transfer character of which has been further confirmed by time-dependent density functional theory (TD-DFT) calculations. The latter evidence that the charge transfer process is dominated by transitions from the highest occupied molecular orbital (HOMO), localized in the aromatic ring of the organic group, to the lowest unoccupied molecular orbital (LUMO), localized in the Keggin anion. Photoluminescence studies show that the fluorescent properties of the 1-naphthylmethylphosphonate group are quenched upon its incorporation into the inorganic oxo-tungstate skeleton. The solution stability of the hybrid clusters has been evaluated by a combination of H-1-, C-13- and P-31-Nuclear Magnetic Resonance spectroscopy and Electrospray Ionization-Mass Spectrometry. The hybrid polyanion [H(POC11H9)(2)(-HBW11O39)](3-) (1) herein constitutes the first structurally characterized organo-p-block containing borotungstate, and hence it confirms that this strategy for the organic functionalization of polyoxometalate clusters can be applied to new platforms belonging to the family of group-13 heteropolyoxotungstates.
- Published
- 2016
32. On the Way to Carbon Nanotubes: The First Synthesis of an Aromatic Nanobelt.
- Author
-
Wegner, Hermann A.
- Subjects
- *
CARBON nanotubes , *NANOTUBES , *NANOBELTS , *NANOSTRUCTURED materials , *FULLERENES - Abstract
Tighten your belt: The first aromatic nanobelt has been prepared by Itami and co‐workers. This synthesis of a truncated Vögtle belt constitutes a milestone in long‐standing efforts of numerous chemists. The realization of such a molecule provides not only new opportunities in materials science, but also paves the way to the rational synthesis of carbon nanotubes. [ABSTRACT FROM AUTHOR]
- Published
- 2017
- Full Text
- View/download PDF
33. Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates
- Author
-
Química física, Química inorgánica, Química orgánica II, Kimika ez-organikoa, Kimika fisikoa, Kimika organikoa II, Andino, Nerea, Artetxe Arretxe, Beñat, Reinoso Crespo, Santiago, Vitoria García, Pablo, San Felices Mateos, Leire, Martínez, José Ignacio, López Arbeloa, Fernando, Gutiérrez Zorrilla López, Juan Manuel, Química física, Química inorgánica, Química orgánica II, Kimika ez-organikoa, Kimika fisikoa, Kimika organikoa II, Andino, Nerea, Artetxe Arretxe, Beñat, Reinoso Crespo, Santiago, Vitoria García, Pablo, San Felices Mateos, Leire, Martínez, José Ignacio, López Arbeloa, Fernando, and Gutiérrez Zorrilla López, Juan Manuel
- Abstract
New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds [N(C4H9)(4)](3)[H(POC11H9)(2)(-HBW11O39)] (TBA-1) and [N(C4H9)(4)](3)[H(POC11H9)(2)(-SiW11O39)] (TBA-2). Liquid-solution UV-Vis transmittance and solid-state diffuse reflectance spectroscopy studies reveal the presence of a new absorption band in the visible region, the charge transfer character of which has been further confirmed by time-dependent density functional theory (TD-DFT) calculations. The latter evidence that the charge transfer process is dominated by transitions from the highest occupied molecular orbital (HOMO), localized in the aromatic ring of the organic group, to the lowest unoccupied molecular orbital (LUMO), localized in the Keggin anion. Photoluminescence studies show that the fluorescent properties of the 1-naphthylmethylphosphonate group are quenched upon its incorporation into the inorganic oxo-tungstate skeleton. The solution stability of the hybrid clusters has been evaluated by a combination of H-1-, C-13- and P-31-Nuclear Magnetic Resonance spectroscopy and Electrospray Ionization-Mass Spectrometry. The hybrid polyanion [H(POC11H9)(2)(-HBW11O39)](3-) (1) herein constitutes the first structurally characterized organo-p-block containing borotungstate, and hence it confirms that this strategy for the organic functionalization of polyoxometalate clusters can be applied to new platforms belonging to the family of group-13 heteropolyoxotungstates.
- Published
- 2016
34. Rational synthesis and structural engineering of two-dimensional inorganic nanosheets for electrochemical energy storage
- Author
-
Peng, Lele
- Subjects
- Two-dimensional nanosheets, Rational synthesis, Structural engineering, Energy storage, Interlayer engineering, Porosity engineering
- Abstract
Lithium-ion batteries have dominated the portable electronics industry and solid-state electrochemical R&D for the past two decades due to the relatively high energy density. However, the limited lithium resources and their non-uniform distribution are becoming big concerns. Therefore, exploring high-performance, safe rechargeable batteries based on abundant resources is urgent. Sodium-ion batteries are of great interest as a potentially low-cost and safe alternative to the prevailing lithium-ion battery technology owing to the high abundance of sodium in earth crust, even distribution in nature and its favorable redox potential (only ~0.3 V above that of lithium). Figures of merit for future SIBs call for a breakthrough in energy (>200 Wh kg⁻¹) and power density (>2000 W kg⁻¹) as well as the cycle life (>4000 cycles) by designing new electrode structures, materials engineering and identifying new chemistries, to satisfy the requirements of many potential applications ranging from ubiquitous portable electronics to grid energy storage. Two-dimensional (2D) inorganic nanosheets offer exciting opportunities for fundamental studies and many technological applications due to their unique and fascinating physical and chemical properties. Preparation of 2D materials via exfoliation/delamination from intrinsically layered materials has been greatly limited by the categories of materials with such suitably layered host crystals. It is critically challenging to obtain 2D nanocrystals from the materials of non-layered structures. This dissertation focuses on the rational synthesis and structural engineering of 2D inorganic nanosheets for high-performance electrochemical energy storage. Several 2D energy materials, such as MnO₂, LiFePO₄, VOPO₄ nanosheets, for electrochemical energy storage are presented. The synthesis and characterizations of these 2D energy materials are discussed in details. Their electrochemical characteristics for H⁺, Li⁺ and Na⁺ storage and the corresponding energy storage mechanisms are also investigated for each case. 2D energy materials have proven effective in constructing kinetically favorable ion channels, but the irreversible restacking of the individual 2D nanosheets during materials processing or device fabrication may lead to the decrease of active sites for ion storage and the sluggish ion transport. To address this issue, two possible strategies are developed in this dissertation to improve the ion transport in 2D nanomaterials. One possible strategy is to increase the interlayer spacing to facilitate ion transport by creating a lower energy barrier for ion transport through the interlayer space. A general interlayer-engineering strategy to improve the sodium-ion transport in VOPO₄ nanosheets via organic molecules intercalation is presented in Chapter 5. Another strategy is to make porous/holey materials to facilitate the ion transport. Chapter 6 summarizes the porosity engineering of 2D transition metal oxide nanosheets for improved rate capability and cycling stability for both lithium and sodium-ion storage. Rational synthesis and structural engineering of 2D inorganic nanosheets has allowed us to make progress on (i) understanding the materials chemistry of 2D energy materials for electrochemical energy storage, (ii) developing promising strategies to address the key problems in 2D nanomaterials for energy-related applications, and (iii) fabricating high-performance lithium- and sodium-ion batteries for the next generation
- Published
- 2017
35. Synthesis of controllable Nash equilibria in quantitative objective games
- Author
-
Orna Kupferman, Giuseppe Perelli, and Shaull Almagor
- Subjects
symbols.namesake ,Computer science ,Nash equilibrium ,0202 electrical engineering, electronic engineering, information engineering ,symbols ,020207 software engineering ,020201 artificial intelligence & image processing ,02 engineering and technology ,Strategic Reasoning ,Rational Synthesis ,Quantitative Temporal Logics ,Mathematical economics - Abstract
In Rational Synthesis, we consider a multi-agent system in which some of the agents are controllable and some are not. All agents have objectives, and the goal is to synthesize strategies for the controllable agents so that their objectives are satisfied, assuming rationality of the uncontrollable agents. Previous work on rational synthesis considers objectives in LTL, namely ones that describe on-going behaviors, and in Objective-LTL, which allows ranking of LTL formulas. In this paper, we extend rational synthesis to LTL[F] -- an extension of LTL by quality operators. The satisfaction value of an LTL[F] formula is a real value in [0,1], where the higher the value is, the higher is the quality in which the computation satisfies the specification. The extension significantly strengthens the framework of rational synthesis and enables a study its game- and social-choice theoretic aspects. In particular, we study the price of stability and price of anarchy of the rational-synthesis game and use them to explain the cooperative and non-cooperative settings of rational synthesis. Our algorithms make use of strategy logic and decision procedures for it. Thus, we are able to handle the richer quantitative setting using existing tools. In particular, we show that the cooperative and non-cooperative versions of quantitative rational synthesis are 2EXPTIME-complete and in 3EXPTIME, respectively -- not harder than the complexity known for their Boolean analogues.
36. A Simple, Transition Metal Catalyst-Free Method for the Design of Complex Organic Building Blocks Used to Construct Porous Metal-Organic Frameworks
- Author
-
Kochetygov, Ilia, Roth, Jocelyn, Espin, Jordi, Pache, Sophia, Justin, Anita, Schertenleib, Till, Taheri, Nazanin, Chernyshov, Dmitry, and Queen, Wendy L.
- Subjects
rational synthesis ,hydrogen adsorption ,synthesis ,ligands ,pore-size ,ligand ,piperazine ,surface-areas ,gas-storage ,high-capacity ,co2 capture ,series ,metal-organic frameworks ,large pore ,scalability - Abstract
The design of metal-organic frameworks (MOFs) having large pore sizes and volumes often requires the use of complex organic ligands, currently synthesized using costly and time-consuming palladium-catalyzed coupling chemistry. Thus, in the present work, a new strategy for ligand design is reported, where piperazine and dihydrophenazine units are used as substitutes for benzene rings, which are the basic building block of most MOF ligands. This chemistry, which is based on simple, nucleophilic aromatic substitution (SNAr) reactions, is used for the transition metal catalyst-free construction of 21 new, carboxylate-based ligands with varying sizes, shapes, and denticity and 15 linear di- and tetra-nitriles. Moreover, to demonstrate the utility of the ligands as building blocks, 16 new structurally diverse MOFs having surface areas up to 3100 m(2) g(-1) were also synthesized.
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