4,5-Bis(isopropyl­sulfan­yl)benzene-1,2-dicarbonitrile

In the title compound, C14H16N2S2, the C atoms of the aromatic ring, the two cyanide groups and the two S atoms of the isopropyl­sulfanyl groups are almost coplanar [maximum deviation from the mean plane = 0.042 (7) Å]. In the crystal, inversion dimers linked by aromatic π–π stacking occur, with a centroid–centroid separation of 3.7543 (8) Å

Bis{1-[(4-methyl­phen­yl)imino­meth­yl]-2-naphtho­lato-κ2 N,O}nickel(II)

In the title complex, [Ni(C18H14NO)2], the NiII ion lies on an inversion center and is coordinated in a slightly distorted square-planar environment. The 1-[(4-methyl­phen­yl)imino­meth­yl]-2-naphtho­late ligands are coordinated in a trans arrangement with respect to the N and O atoms. In the symmetry-unique ligand, the dihedral angle between the naphthalene ring system and the benzene ring of the methyl­phenyl group is 49.03 (7)°

4-(4,4-Difluoro-1,3,5,7-tetra­methyl-3a-aza-4a-azonia-4-borata-s-indacen-8-yl)benzonitrile

The title compound, C20H18BF2N3, contains one C9BN2 (Bodipy) framework and one cyano­benzyl group. The Bodipy framework is essentially planar with a maximum deviation of 0.041 (2) Å. The introduction of two methyl groups at positions 1 and 7 of s-indacene in the Bodipy unit results in almost orthogonal configuration between the mean plane of the Bodipy unit and the cyano­benzyl group [dihedral angle = 89.78 (4)°]

3,3′-(m-Phenyl­enedi­oxy)diphthalonitrile

In the title compound, C22H10N4O2, the dihedral angles between the mean planes of the central benzene ring and the pendant rings are 79.20 (6) and 80.29 (6)°. The dihedral angle between the pendant rings is 10.27 (7)°

4,5-Diamino­benzene-1,2-dicarbonitrile

The mol­ecular skeleton of the title mol­ecule, C8H6N4, is essentially planar [maximum deviation from the mean plane of 0.037 (2) Å]. All N atoms are involved in the formation of inter­molecular N—H⋯N hydrogen bonds. The crystal packing exhibits also dipole–dipole inter­actions between the cyano groups of neighbouring mol­ecules [C⋯C 3.473 (2) Å]

Bayesian Optimized 1-Bit CNNs

Deep convolutional neural networks (DCNNs) have dominated the recent developments in computer vision through making various record-breaking models. However, it is still a great challenge to achieve powerful DCNNs in resource-limited environments, such as on embedded devices and smart phones. Researchers have realized that 1-bit CNNs can be one feasible solution to resolve the issue; however, they are baffled by the inferior performance compared to the full-precision DCNNs. In this paper, we propose a novel approach, called Bayesian optimized 1-bit CNNs (denoted as BONNs), taking the advantage of Bayesian learning, a well-established strategy for hard problems, to significantly improve the performance of extreme 1-bit CNNs. We incorporate the prior distributions of full-precision kernels and features into the Bayesian framework to construct 1-bit CNNs in an end-to-end manner, which have not been considered in any previous related methods. The Bayesian losses are achieved with a theoretical support to optimize the network simultaneously in both continuous and discrete spaces, aggregating different losses jointly to improve the model capacity. Extensive experiments on the ImageNet and CIFAR datasets show that BONNs achieve the best classification performance compared to state-of-the-art 1-bit CNNs

Comparative Spectroscopic and Electrochemical Properties of Bis (octakis (dodecylthio) naphthalocyaninato) europium (III) and Bis (tetra-tert-butylnaphthalocyaninato) europium (III) Complexes

Bis(substituted-2,3-naphthalocyaninato)europium(III) complexes:  bis(octakis(dodecylthio)-2,3-naphthalocyaninato)europium(III) {Eu[2,3-Nc(SC12H25)8]2, 1} and bis(tetra-tert-butyl-2,3-naphthalocyaninato)europium(III) {Eu[2,3-Nc(t-Bu)4]2, 2} have been synthesized by cyclic tetramerization of naphthalonitriles with Eu(acac)3·H2O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in refluxing n-octanol. These compounds were characterized by UV−visible, magnetic circular dichroism (MCD), near-IR, IR, EPR, and mass spectroscopies. The absorption and MCD spectra of 1 showed splitting of the Q band, with peaks at 700 and 784 nm, red shifted from the Q band of 2 at 763 nm. The absorption and MCD spectral band deconvolution calculations of complex 1 gave two A terms in the Q-band region. The A terms are assigned to 2A2 → 2E1 transitions. Cyclic voltammograms of 1 and 2 showed reversible oxidation couples at E1/2 = −0.28 V (for 2) and −0.25 V (for 1) vs ferrocenium/ferrocene (Fc+/Fc). The second oxidation exhibited a complicated behavior for both complexes. The reduction couples for 2 were observed at E1/2 = −0.61, −1.64, −1.97, and −2.42 V, and for 1 they were observed at E1/2 = −0.62, −1.60, −1.86, and −2.27 V vs Fc+/Fc. Spectral changes observed on chemical oxidation and reduction of the complexes are presented, and the behaviors of 1 and 2 are compared

Functional Supramolecular Gels Based on the Hierarchical Assembly of Porphyrins and Phthalocyanines

Supramolecular gels containing porphyrins and phthalocyanines motifs are attracting increased interests in a wide range of research areas. Based on the supramolecular gels systems, porphyrin or phthalocyanines can form assemblies with plentiful nanostructures, dynamic, and stimuli-responsive properties. And these π-conjugated molecular building blocks also afford supramolecular gels with many new features, depending on their photochemical and electrochemical characteristics. As one of the most characteristic models, the supramolecular chirality of these soft matters was investigated. Notably, the application of supramolecular gels containing porphyrins and phthalocyanines has been developed in the field of catalysis, molecular sensing, biological imaging, drug delivery and photodynamic therapy. And some photoelectric devices were also fabricated depending on the gelation of porphyrins or phthalocyanines. This paper presents an overview of the progress achieved in this issue along with some perspectives for further advances

RUNX2 Plays An Oncogenic Role in Esophageal Carcinoma by Activating the PI3K/AKT and ERK Signaling Pathways

Background/Aims: Esophageal carcinoma is a frequently occurring cancer at upper gastrointestinal tract. We aimed to evaluate the roles and possible mechanism of Runt Related Transcription Factor 2 (RUNX2) in the development of esophageal cancer. Methods: The expression of RUNX2 in esophageal carcinoma tissues and cells was investigated by qRT-PCR. Effects of RUNX2 on cell viability, apoptosis, migration and invasion were assessed using MTT assay, flow cytometry assay/western blot analysis, and Transwell assays, respectively. Afterwards, effects of RUNX2 on of the activation of the PI3K/AKT and ERK pathways were explored by Western blot analysis. In addition, a PI3K/AKT pathway inhibitor LY294002 and an ERK inhibitor U0126 were applied to further verify the regulatory relationship between RUNX2 and the PI3K/AKT and ERK signaling pathways. Besides, the RUNX2 function on tumor formation in vivo was investigated by tumor xenograft experiment. Results: The result showed that RUNX2 was highly expressed in esophageal carcinoma tissues and cells. Knockdown of RUNX2 significantly inhibited TE-1 and EC-109 cell viability, repressed TE-1 cell migration and invasion, and increased TE-1 cell apoptosis. RUNX2 overexpression showed the opposite effects on HET-1A cells. Moreover, RUNX2-mediated TE-1 cell viability, migration and invasion were associated with the activation of the PI3K/AKT and ERK pathways. Besides, knockdown of RUNX2 markedly suppressed tumor formation in vivo. Conclusion: Our results indicate that RUNX2 may play an oncogenic role in esophageal carcinoma by activating the PI3K/ AKT and ERK pathways. RUNX2 may serve as a potent target for the treatment of esophageal carcinoma

Spin Crossover in a Series of Non-Hofmann-Type Fe(II) Coordination Polymers Based on [Hg(SeCN)3]-; or [Hg(SeCN)4]2-; Building Blocks

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00802.[EN] Self-assembly of [Hg(SeCN)(4)](2)-tetrahedral building blocks, iron(II) ions, and a series of bis-monodentate pyridyltype bridging ligands has afforded the new heterobimetallic Hg-II-Fe-II coordination polymers {Fe[Hg(SeCN)(3)](2)(4,4'-bipy)(2)}(n) (1), {Fe[Hg(SeCN)(4)](tvp)}(n) (2), {Fe[Hg(SeCN)(3)](2)(4,4'-azpy)(2)}(n) (3), {Fe[Hg(SeCN)(4)](4,4'-azpy)(MeOH)} n (4), {Fe[Hg(SeCN)(4)](3,3'- bipy)} n (5) and {Fe[Hg(SeCN)4](3,3'-azpy)}(n) (6) (4,4-bipy = 4,4'-bipyridine, tvp = trans-1,2-bis(4-pyridyl)ethylene, 4,4'-azpy = 4,4'-azobispyridine, 3,3-bipy = 3,3'bipyridine, 3,3'-azpy = 3,3'-azobispyridine). Single-crystal X-ray analyses show that compounds 1 and 3 display a two-dimensional robust sheet structure made up of infinite linear [(FeL)n]2n+ (L = 4,4'-bipy or 4,4'-azpy) chains linked by in situ formed {[Hg(L)(SeCN)(3)](2)}(2)-anionic dimeric bridges. Complexes 2 and 4-6 define three-dimensional networks with different topological structures, indicating, in combination with complexes 1 and 3, that the polarity, length, rigidity, and conformation of the bridging organic ligand play important roles in the structural nature of the products reported here. The magnetic properties of complexes 1 and 2 show the occurrence of temperature-and light-induced spin crossover (SCO) properties, while complexes 4-6 are in the high-spin state at all temperatures. The current results provide a new route for the design and synthesis of new SCO functional materials with non-Hofmann-type traditional structures.This work was supported by the Natural Science Foundation of China (21671121and 21773006), the Spanish Ministerio de Ciencia e Innovacion (MICINN) and FEDER funds (PID2019-106147GB-I00), and Unidad de Excelencia Maria de Maeztu (CEX2019-000919-M).Cao, T.; Valverde-Muñoz, FJ.; Duan, X.; Zhang, M.; Wang, P.; Xing, L.; Sun, F.... (2021). Spin Crossover in a Series of Non-Hofmann-Type Fe(II) Coordination Polymers Based on [Hg(SeCN)3]-; or [Hg(SeCN)4]2-; Building Blocks. Inorganic Chemistry. 60(15):11048-11057. https://doi.org/10.1021/acs.inorgchem.1c008021104811057601