Homologation of selenoesters to (phenylseleno)- or (methylseleno)methyl ketones with diazomethane

The copper or cuprous iodide-catalyzed insertion of diazomethane into the acylselenium linkage of selenoesters $\text{1a}$– $\text{1f}$ and selenocarbonate $\text{1g}$ afforded the corrresponding ketones $\text{2a}$– $\text{2f}$ and the ester $\text{2g}$, respectively, as the chief products.     

Visible-Light-Curable Solvent-Free Acrylic Pressure-Sensitive Adhesives via Photoredox-Mediated Radical Polymerization

Owing to their excellent properties, such as transparency, resistance to oxidation, and high adhesivity, acrylic pressure-sensitive adhesives (PSAs) are widely used. Recently, solvent-free acrylic PSAs, which are typically prepared via photopolymerization, have attracted increasing attention because of the current strict environmental regulations. UV light is commonly used as an excitation source for photopolymerization, whereas visible light, which is safer for humans, is rarely utilized. In this study, we prepared solvent-free acrylic PSAs via visible light-driven photoredox-mediated radical polymerization. Three α-haloesters were used as additives to overcome critical shortcomings, such as the previously reported low film curing rate and poor transparency observed during additive-free photocatalytic polymerization. The film curing rate was greatly increased in the presence of α-haloesters, which lowered the photocatalyst loadings and, hence, improved the film transparency. These results confirmed that our method could be widely used to prepare general-purpose solvent-free PSAs—in particular, optically clear adhesives for electronics.     

Suppression of Rice Cryptochrome 1b Decreases Both Melatonin and Expression of Brassinosteroid Biosynthetic Genes Resulting in Salt Tolerance

We investigated the relationship between the blue-light photoreceptor cryptochrome (CRY) and melatonin biosynthesis by generating RNA interference (RNAi) transgenic rice plants that suppress the cryptochrome 1b gene (CRY1b). The resulting CRY1b RNAi rice lines expressed less CRY1b mRNA, but not CRY1a or CRY2 mRNA, suggesting that the suppression is specific to CRY1b. The growth of CRY1b RNAi rice seedlings was enhanced under blue light compared to wild-type growth, providing phenotypic evidence for impaired CRY function. When these CRY1b RNAi rice plants were challenged with cadmium to induce melatonin, wild-type plants produced 100 ng/g fresh weight (FW) melatonin, whereas CRY1b RNAi lines produced 60 ng/g FW melatonin on average, indicating that melatonin biosynthesis requires the CRY photoreceptor. Due to possible feedback regulation, the expression of melatonin biosynthesis genes such as T5H, SNAT1, SNAT2, and COMT was elevated in the CRY1b RNAi lines compared to the wild-type plants. In addition, laminar angles decreased in the CRY1b RNAi lines via the suppression of brassinosteroid (BR) biosynthesis genes such as DWARF. The main cause of the BR decrease in the CRY1b RNAi lines seems to be the suppression of CRY rather than decreased melatonin because the melatonin decrease suppressed DWARF4 rather than DWARF.     

Aza-Morita-Baylis-Hillman reactions and cyclizations of conjugated dienes activated by sulfone, ester, and keto groups

The aza-Morita-Baylis-Hillman reactions of aldimines 2 with several activated conjugated dienes were found to proceed smoothly in DMF in the presence of 3-hydroxyquinuclidine (HQD). Imines 2 reacted with 1-(p-toluenesulfonyl)-1,3-butadiene (3), methyl 2,4-pentadienoate (6), hexa-3,5-dien-2-one (7), and 1-phenylpenta-2,4-dien-1-one (8) to afford adducts 4, 13, 14, and 15, respectively. While products 4, 13, and 15 were formed as E,Z mixtures, adducts 14 were obtained as essentially pure E-isomers. Cyclization of the E-isomers of the products derived from the dienyl sulfone 3 and the dienoate ester 6 occurred via intramolecular conjugate addition under base-catalyzed conditions to afford functionalized piperidines 5 and 16, respectively. The aza-Morita-Baylis-Hillman reaction and subsequent cyclization of the imine 2a with 3 were also carried out as a one-pot reaction, while the reaction mixture was simultaneously irradiated at 300 nm to effect the photoisomerization of the unreactive Z-adduct of the corresponding 4 to the more reactive E-isomer.     

Improving the use of mercury bis(phenyltellurolate) as efficient start for the synthesis of ternary clusters and polymers

Hg(TePh)₂ reacts with AgCl/PMe₂Ph and AgClO₄/PPh₃ to give the ternary clusters [(PhTe)₄Ag₂Hg₂(Cl)₂]_n (1) and [(PhTe)₁₆Ag₄Hg₆Py₄] · H₂O (2). While 1 assembles polymeric, bidimensional layers, 2 attains high symmetric moieties in which the occupational relationship is 40%/60% for the Ag⁺ and Hg²⁺ ions, respectively.     

Estimating Sentence-like Structure in Synthetic Languages Using Information Topology

Estimating sentence-like units and sentence boundaries in human language is an important task in the context of natural language understanding. While this topic has been considered using a range of techniques, including rule-based approaches and supervised and unsupervised algorithms, a common aspect of these methods is that they inherently rely on a priori knowledge of human language in one form or another. Recently we have been exploring synthetic languages based on the concept of modeling behaviors using emergent languages. These synthetic languages are characterized by a small alphabet and limited vocabulary and grammatical structure. A particular challenge for synthetic languages is that there is generally no a priori language model available, which limits the use of many natural language processing methods. In this paper, we are interested in exploring how it may be possible to discover natural ‘chunks’ in synthetic language sequences in terms of sentence-like units. The problem is how to do this with no linguistic or semantic language model. Our approach is to consider the problem from the perspective of information theory. We extend the basis of information geometry and propose a new concept, which we term information topology, to model the incremental flow of information in natural sequences. We introduce an information topology view of the incremental information and incremental tangent angle of the Wasserstein-1 distance of the probabilistic symbolic language input. It is not suggested as a fully viable alternative for sentence boundary detection per se but provides a new conceptual method for estimating the structure and natural limits of information flow in language sequences but without any semantic knowledge. We consider relevant existing performance metrics such as the F-measure and indicate limitations, leading to the introduction of a new information-theoretic global performance based on modeled distributions. Although the methodology is not proposed for human language sentence detection, we provide some examples using human language corpora where potentially useful results are shown. The proposed model shows potential advantages for overcoming difficulties due to the disambiguation of complex language and potential improvements for human language methods.     

Charge transfer complexes of electron-rich naphthalene peri-dichalcogenides with TCNQ

The electronic structures of several highly electron-rich 2,7-dimethoxynaphthalene peri-dichalcogenides were evaluated using optical and electrochemical methods, as well as by DFT calculations. Charge transfer complexes were formed with tetracyanoquinodimethane and resulted in absorption features that span from 300 nm to 1600 nm and HOMO–LUMO energy gaps as low as 0.8 eV.     

Synthesis and Structural Features of New Schiff Base Complexes of Mononuclear MnIV,Dinuclear CoIICoIII,and Tetranuclear CuII

2‐(((2‐Hydroxy‐3‐methoxyphenyl)methylene)amino)‐2(hydroxymethyl)‐1,3‐propanediol (LH₄, as abbreviation) reacts with MnCl₂ · 4H₂O, CoCl₂ · 6H₂O, and Cu(ClO₄)₂ · 6H₂O to give the new complexes [Mn(LH₂)₂] ( 1 ), [Co₂Cl(H₂O)(LH₂)₂] · 4H₂O ( 2 ), and [Cu₄(LH₂)₄(H₂O)₄] ( 3 ). Complex 1 is formed by the assembly of two molecules of the ligand with one manganese(IV) ion. In the mixed‐valence cobalt complex 2 there is an asymmetry between the coordination spheres of cobalt(II) and cobalt(III). In the tetramer 3 four copper(II) ions attain a distorted tetrahedral configuration surrounded by four molecules of the ligand.