Towards Organic Zeolites and Inclusion Catalysts: Heptazine Imide Salts Can Exchange Metal Cations in the Solid State

Highly crystalline potassium (heptazine imides) were prepared by the thermal condensation of substituted 1,2,4- triazoles in eutectic salt melts. These semiconducting salts are already known to be highly active photocatalysts, e.g. for the visible light driven generation of hydrogen from water. Herein, we show that within the solid state structure, potassium ions can be exchanged to other metal ions while the crystal habitus is essentially preserved

Triazoles : a new class of precursors for the synthesis of negatively charged carbon nitride derivatives

Carbon nitride polymers were prepared for the first time by the pyrolysis of 3,5-disubstituted-1,2,4-triazole derivatives, namely 3,5-diamino-1,2,4-triazole [1] and 3-amino-1,2,4-triazole-5-thiol [2], in bulk as well as in LiCl/KCl salt melts. The reaction of [1] and [2] in bulk yields condensed heptazine-based polymers, while in LiCl/KCl eutectics it leads to the formation of well-defined potassium poly(heptazine imides), according to the results of 13C NMR and XPS investi-gations, whose formation resembles that of emeraldine salts of polyaniline. The density functional calculations supported the structural model suggested for potassium poly(heptazine imide) polymer. Owing to the specific reaction path, the products obtained from triazoles therefore show electronic properties rather different to known carbon nitrides, such as band gap and conduction and valence bands positions. With the degree of crystallinity of the reference materials, triazole-derived carbon nitrides are characterized by almost complete absence of steady photoluminescence, charge separation and localization upon excitation seems to be improved. As a consequence, photocatalysts prepared from [2] outperform classical carbon nitrides in a model dye degradation reaction and mesoporous graphitic carbon nitride in hydrogen evolution reaction under visible light irradiation. On its turn, [1] can be conveniently used as a co-monomer in order to prepare carbon nitrides with improved visible light absorption

Halogen free 1,2,3- and 1,2,4-triazolide based ionic liquids : synthesis and properties

Triazoles have been successfully used as building blocks to create "fully organic" ILs featuring on both sides organic ions, i.e., 1,2,3- or 1,2,4-triazolide anions and 1,2,4-triazolium or imidazolium cations. Glass transition temperatures, densities and viscosities of these ILs were determined. Their electrochemical and thermal stability, and also conductivity, are higher than those for known ILs

Transport of Explosive Residue Surrogates in Saturated Porous Media

Department of Defense operational ranges may become contaminated by particles of explosives residues (ER) as a result of low-order detonations of munitions. The goal of this study was to determine the extent to which particles of ER could migrate through columns of sandy sediment, representing model aquifer materials. Transport experiments were conducted in saturated columns (2 × 20 cm) packed with different grain sizes of clean sand or glass beads. Fine particles (approximately 2 to 50 μm) of 2,6-dinitrotoluene (DNT) were used as a surrogate for ER. DNT particles were applied to the top 1 cm of sand or beads in the columns, and the columns were subsequently leached with artificial groundwater solutions. DNT migration occurred as both dissolved and particulate phases. Concentration differences between unfiltered and filtered samples indicate that particulate DNT accounted for up to 41% of the mass recovered in effluent samples. Proportionally, more particulate than dissolved DNT was recovered in effluent solutions from columns with larger grain sizes, while total concentrations of DNT in effluent were inversely related to grain size. Of the total DNT mass applied to the uppermost layer of the column, <3% was recovered in the effluent with the bulk remaining in the top 2 cm of the column. Our results suggest there is some potential for subsurface migration of ER particles and that most of the particles will be retained over relatively short transport distances

Active Site Conformational Dynamics in Human Uridine Phosphorylase 1

Uridine phosphorylase (UPP) is a central enzyme in the pyrimidine salvage pathway, catalyzing the reversible phosphorolysis of uridine to uracil and ribose-1-phosphate. Human UPP activity has been a focus of cancer research due to its role in activating fluoropyrimidine nucleoside chemotherapeutic agents such as 5-fluorouracil (5-FU) and capecitabine. Additionally, specific molecular inhibitors of this enzyme have been found to raise endogenous uridine concentrations, which can produce a cytoprotective effect on normal tissues exposed to these drugs. Here we report the structure of hUPP1 bound to 5-FU at 2.3 Å resolution. Analysis of this structure reveals new insights as to the conformational motions the enzyme undergoes in the course of substrate binding and catalysis. The dimeric enzyme is capable of a large hinge motion between its two domains, facilitating ligand exchange and explaining observed cooperativity between the two active sites in binding phosphate-bearing substrates. Further, a loop toward the back end of the uracil binding pocket is shown to flexibly adjust to the varying chemistry of different compounds through an “induced-fit” association mechanism that was not observed in earlier hUPP1 structures. The details surrounding these dynamic aspects of hUPP1 structure and function provide unexplored avenues to develop novel inhibitors of this protein with improved specificity and increased affinity. Given the recent emergence of new roles for uridine as a neuron protective compound in ischemia and degenerative diseases, such as Alzheimer's and Parkinson's, inhibitors of hUPP1 with greater efficacy, which are able to boost cellular uridine levels without adverse side-effects, may have a wide range of therapeutic applications

A flexible loop in yeast ribosomal protein L11 coordinates P-site tRNA binding

High-resolution structures reveal that yeast ribosomal protein L11 and its bacterial/archael homologs called L5 contain a highly conserved, basically charged internal loop that interacts with the peptidyl-transfer RNA (tRNA) T-loop. We call this the L11 ‘P-site loop’. Chemical protection of wild-type ribosome shows that that the P-site loop is inherently flexible, i.e. it is extended into the ribosomal P-site when this is unoccupied by tRNA, while it is retracted into the terminal loop of 25S rRNA Helix 84 when the P-site is occupied. To further analyze the function of this structure, a series of mutants within the P-site loop were created and analyzed. A mutant that favors interaction of the P-site loop with the terminal loop of Helix 84 promoted increased affinity for peptidyl-tRNA, while another that favors its extension into the ribosomal P-site had the opposite effect. The two mutants also had opposing effects on binding of aa-tRNA to the ribosomal A-site, and downstream functional effects were observed on translational fidelity, drug resistance/hypersensitivity, virus maintenance and overall cell growth. These analyses suggest that the L11 P-site loop normally helps to optimize ribosome function by monitoring the occupancy status of the ribosomal P-site

Stabilization of Single Metal Atoms on Graphitic Carbon Nitride

Graphitic carbon nitride (g-C$_{3}$N$_{4}$) exhibits unique properties as a support for single-atom heterogeneous catalysts (SAHCs). Understanding how the synthesis method, carrier properties, and metal identity impact the isolation of metal centers is essential to guide their design. This study compares the effectiveness of direct and postsynthetic routes to prepare SAHCs by incorporating palladium, silver, iridium, platinum, or gold in g-C$_{3}$N$_{4}$ of distinct morphology (bulk, mesoporous and exfoliated). The speciation (single atoms, dimers, clusters, or nanoparticles), distribution, and oxidation state of the supported metals are characterized by multiple techniques including extensive use of aberration-corrected electron microscopy. SAHCs are most readily attained via direct approaches applying copolymerizable metal precursors and employing high surface area carriers. In contrast, although post-synthetic routes enable improved control over the metal loading, nanoparticle formation is more prevalent. Comparison of the carrier morphologies also points toward the involvement of defects in stabilizing single atoms. The distinct metal dispersions are rationalized by density functional theory and kinetic Monte Carlo simulations, highlighting the interplay between the adsorption energetics and diffusion kinetics. Evaluation in the continuous three-phase semihydrogenation of 1-hexyne identifies controlling the metal-carrier interaction and exposing the metal sites at the surface layer as key challenges in designing efficient SAHCs.The authors are grateful to the following people for support: Dr. G. Vilé for fruitful discussion, Dr. R. Verel for NMR measurements, Dr. C. Zaubitzer for TEM training, and Dr. J. Barnard for assistance with microscopy studies. ScopeM at ETH Zurich for use of their facilities. This research has received funding from the Swiss National Science Foundation (grant number 200021_169679) and the European Union’s Seventh Framework Programme (grant numbers 291522 - 3DIMAGE and 31 2483 - ESTEEM2). R.K.L. acknowledges a Junior Research Fellowship from Clare College. The SuperSTEM Laboratory is the UK National Facility for Aberration - Corrected STEM, supported by the Engineering and Physical Sciences Research Council (EPSRC). Thanks to BSC - RES for providing generous computational resources

Stability of the ‘L12 stalk’ in ribosomes from mesophilic and (hyper)thermophilic Archaea and Bacteria

The ribosomal stalk complex, consisting of one molecule of L10 and four or six molecules of L12, is attached to 23S rRNA via protein L10. This complex forms the so-called ‘L12 stalk’ on the 50S ribosomal subunit. Ribosomal protein L11 binds to the same region of 23S rRNA and is located at the base of the ‘L12 stalk’. The ‘L12 stalk’ plays a key role in the interaction of the ribosome with translation factors. In this study stalk complexes from mesophilic and (hyper)thermophilic species of the archaeal genus Methanococcus and from the Archaeon Sulfolobus solfataricus, as well as from the Bacteria Escherichia coli, Geobacillus stearothermophilus and Thermus thermophilus, were overproduced in E.coli and purified under non-denaturing conditions. Using filter-binding assays the affinities of the archaeal and bacterial complexes to their specific 23S rRNA target site were analyzed at different pH, ionic strength and temperature. Affinities of both archaeal and bacterial complexes for 23S rRNA vary by more than two orders of magnitude, correlating very well with the growth temperatures of the organisms. A cooperative effect of binding to 23S rRNA of protein L11 and the L10/L12(4) complex from mesophilic and thermophilic Archaea was shown to be temperature-dependent