Integrated Transmission Electron and Single‐Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle

Establishing structure–activity relationships in complex, hierarchically structured nanomaterials, such as fluid catalytic cracking (FCC) catalysts, requires characterization with complementary, correlated analysis techniques. An integrated setup has been developed to perform transmission electron microscopy (TEM) and single‐molecule fluorescence (SMF) microscopy on such nanostructured samples. Correlated structure–reactivity information was obtained for 100 nm thin, microtomed sections of a single FCC catalyst particle using this novel SMF‐TEM high‐resolution combination. High reactivity in a thiophene oligomerization probe reaction correlated well with TEM‐derived zeolite locations, while matrix components, such as clay and amorphous binder material, were found not to display activity. Differences in fluorescence intensity were also observed within and between distinct zeolite aggregate domains, indicating that not all zeolite domains are equally active.     

New Solutions for Cooperative Relaying Implementation of OSTBC with 3/4 Code Rate

In this paper we propose two new cooperative relaying schemes which enable distributed implementation of the orthogonal space time block coding (OSTBC) with 3/4 code rate. These proposed schemes are compared with cooperative relaying scheme with virtual OSTBC and 1/2 code rate. The considered schemes are used for creating virtual 4 × 1 multiple input–single output (MISO) channel, and include one base station with two antennas, two relay stations each with a single antenna and one mobile station with a single antenna. Obtained results show that in the case of the same bit rate the proposed schemes provide better bit error rate (BER) performances than virtual OSTBC with 1/2 code rate. On the other side, for the same symbol constellations the proposed schemes have almost identical BER performances as virtual OSTBC with 1/2 code rate, but with a benefit of 1.5 times increased code rate.     

Last step of the para route of the Kolbe-Schmitt reaction

This work is an extension of our investigations of the Kolbe--Schmitt reaction mechanism. The last step in the para route of the carboxylation reaction of alkali metal phenoxides is investigated at the B3LYP/LANL2DZ level of theory. Among several examined pathways, two mechanisms are proposed: the one involving a successive rearrangement of hydrogen and the other one based on the formation of free radicals. The former pathway is energetically comparable to the last step of the carboxylation reaction in the ortho position, whereas the latter pathway requires higher activation energy. Bearing in mind that the Kolbe--Schmitt reaction is performed at high temperatures, we assume that both reaction paths are plausible.     

Synthesis, Raman spectra and crystal structures of [Cu(XeF2)n](SbF6)2 (n=2, 4)

Pure [Cu(XeF2)2](SbF6)2 was prepared by the reaction of Cu(SbF 6) 2 with a stoichiometric amount of XeF2 in anhydrous hydrogen fluoride (aHF) at ambient temperature. The reaction between Cu(SbF6)2 and XeF2 (1:4 molar ratio) in aHF yielded [Cu(XeF2)4](SbF6)2 contaminated with traces of Xe 2F 3SbF6 and CuF2. The 6-fold coordination of Cu(2+) in [Cu(XeF2)2](SbF6)2 includes two fluorine atoms from two XeF2 ligands and four fluorine atoms provided by four [SbF6](-) anions. The neighboring [Cu(XeF 2)2](2+) moieties are connected via two [SbF6] units, with the bridging fluorine atoms in cis positions, into infinite [Cu(eta(1)-XeF2)2](cis-eta(2)-SbF 6)2[Cu(eta(1)-XeF 2)2] chains. Because of the high electron affinity of Cu(2+), coordinated XeF2 shows the highest distortion (Xe-Fb=210.2(5) pm, Xe-Ft=190.6(5) pm) observed so far among all known [M(x+)(XeF2)n](A)x (A=BF4, PF6, etc.) complexes. The four equatorial coordination sites of the Cu(2+) ion in [Cu(XeF 2) 4](SbF6)2 are occupied by four XeF 2 ligands. Two fluorine atoms belonging to two [SbF6] units complete the Cu (2+) coordination environment. The neighboring [Cu(XeF2)4](2+) species are linked via one [SbF6] unit, with bridging fluorine atoms in trans positions, into linear infinite [Cu(eta(1)-XeF2)4](trans-eta(2)-SbF6)[Cu(eta(1)-XeF2)4] chains. To compensate for the remaining positive charge, crystallographically independent [SbF6](-) anions are located between the chains and are fixed in the crystal space by weak Xe...F(Sb) interactions.     

Formation of sodium 6-hydroxy-2-naphthoate in the <Emphasis Type="Italic">Kolbe-Schmitt</Emphasis> reaction

This work is an extension of our investigation of the mechanism of the Kolbe-Schmitt reaction of sodium 2-naphthoxide. The carboxylation reaction of sodium 2-naphthoxide in the position 6 is examined by means of the B3LYP/LANL2DZ method. After the initial formation of sodium 2-naphthoxide-CO₂ complex, the carbon of the CO₂ moiety performs an electrophilic attack on the naphthalene ring in position 8. Further transformations lead to the formation of sodium 6-hydroxy-2-naphthoate. Our findings are in good agreement with the experimental results on the carboxylation reaction of sodium 2-naphthoxide. Correspondence: Svetlana Marković, Faculty of Science, University of Kragujevac, 34000 Kragujevac, Serbia.     

Crystal Growth and Crystal Structures of Gold(V) Compounds: Cu(AuF6)2, Ag(AuF6)2, and O2(CuF)3(AuF6)4 ⋅ HF

Crystal growth from anhydrous hydrogen fluoride solutions of M²⁺ (M=Cu, Ag) and [AuF₆]⁻ gave M(AuF₆)₂ salts (M=Cu, Ag). Similar attempts to prepare single crystals of the corresponding nickel, zinc and magnesium salts failed. The crystal structure of Cu(AuF₆)₂ consists of layers of Cu²⁺ cations connected by [AuF₆]⁻ anions, thus forming slabs. Only van der Waals interactions exist between adjacent slabs. The crystal structure of Ag(AuF₆)₂ consists of a three-dimensional framework in which Ag⁺ cations are linked by [AuF₆]⁻ anions. Both structures are members of the M^II(X^VF₆)₂ family, in which seven different structure types have been observed to date. In the crystal structure of O₂(CuF)₃(AuF₆)₄ ⋅ HF, the bridging AuF₆ units connect [−Cu−F−Cu−F−]_∞ chains to form stacks between which O₂⁺ cations and HF molecules are located.     

Acetylcholinesterase: mechanisms of covalent inhibition of wild-type and H447I mutant determined by computational analyses

The reaction mechanisms of two inhibitors TFK+ and TFK0 binding to both the wild-type and H447I mutant mouse acetylcholinesterase (mAChE) have been investigated by using a combined ab initio quantum mechanical/molecular mechanical (QM/MM) approach and classical molecular dynamics (MD) simulations. In the wild-type mAChE, the binding reactions of TFK+ and TFK0 are both spontaneous processes, which proceed through the nucleophilic addition of the Ser203-Ogamma to the carbonyl-C of TFK+ or TFK0, accompanied with a simultaneous proton transfer from Ser203 to His447. No barrier is found along the reaction paths, consistent with the experimental reaction rates approaching the diffusion-controlled limit. By contrast, TFK+ binding to the H447I mutant may proceed with a different reaction mechanism. A water molecule takes over the role of His447 and participates in the bond breaking and forming as a "charge relayer". Unlike in the wild-type mAChE case, Glu334, a conserved residue from the catalytic triad, acts as a catalytic base in the reaction. The calculated energy barrier for this reaction is about 8 kcal/mol. These predictions await experimental verification. In the case of the neutral ligand TFK0, however, multiple MD simulations on the TFK0/H447I complex reveal that none of the water molecules can be retained in the active site as a "catalytic" water. Furthermore, our alchemical free energy calculation also suggests that the binding of TFK0 to H447I is much weaker than that of TFK+. Taken together, our computational studies confirm that TFK0 is almost inactive in the H447I mutant and also provide detailed mechanistic insights into the experimental observations.     

Whether the Support Region of Three-Bit Uniform Quantizer Has a Strong Impact on Post-Training Quantization for MNIST Dataset?

Driven by the need for the compression of weights in neural networks (NNs), which is especially beneficial for edge devices with a constrained resource, and by the need to utilize the simplest possible quantization model, in this paper, we study the performance of three-bit post-training uniform quantization. The goal is to put various choices of the key parameter of the quantizer in question (support region threshold) in one place and provide a detailed overview of this choice’s impact on the performance of post-training quantization for the MNIST dataset. Specifically, we analyze whether it is possible to preserve the accuracy of the two NN models (MLP and CNN) to a great extent with the very simple three-bit uniform quantizer, regardless of the choice of the key parameter. Moreover, our goal is to answer the question of whether it is of the utmost importance in post-training three-bit uniform quantization, as it is in quantization, to determine the optimal support region threshold value of the quantizer to achieve some predefined accuracy of the quantized neural network (QNN). The results show that the choice of the support region threshold value of the three-bit uniform quantizer does not have such a strong impact on the accuracy of the QNNs, which is not the case with two-bit uniform post-training quantization, when applied in MLP for the same classification task. Accordingly, one can anticipate that due to this special property, the post-training quantization model in question can be greatly exploited.     

Tris(3,5‐di­methyl‐1H‐pyrazole‐1‐thio­carboxamidato‐κ2N2,N)­cobalt(III)

In the crystal structure of the title complex, [Co(C₆H₈N₃S)₃], the Co^III atom is octahedrally coordinated by three monodeprotonated bidentate 3,5‐di­methyl‐1H‐pyrazole‐1‐thio­carbox­amide ligands with two thio­carbox­amide N atoms in axial positions. The asymmetric unit contains two mol­ecules (A and B) and these mol­ecules are arranged in chains in an alternating fashion connected by N—H⋯S interactions.     

Polyaniline “Nanotube” Self‐Assembly: The Stage of Granular Agglomeration on Nanorod Templates

The identification and control of a critical stage of polyaniline “nanotube” self‐assembly is presented, namely the granular agglomeration or growth onto nanorod templates. When the synthesis pH is held above 2.5, smooth insulating nanorods exhibiting hydrogen bonding and containing phenazine structures are produced, while below pH 2.5, small 15–30 nm granular polyaniline nanoparticles appear to agglomerate onto the available nanorod surface, apparently improving conductivity of the resulting structures by three orders of magnitude. This finding affects both fundamental theories of polyaniline nanostructure self‐assembly and their practical applications.