Crystalline Radical Anion of a Diboratriazole and Its Conversion to a Neutral Radical Driven by a Carbene.

One-electron reduction of diboratriazole 1 with potassium graphite (KC8) generates the radical anion 1•-•K+, which undergoes a salt (KCl) elimination reaction upon addition of an N-heterocyclic carbene (NHC) to afford the neutral diboratriazole radical 3. An X-ray diffraction analysis, electron paramagnetic resonance spectroscopy, and computational studies revealed that an unpaired electron in radical species 1•-•K+ and 3 is delocalized over the π-system of the B2N3 and carbene rings. Reversible oxidation of 3 gives rise to a diboratriazole cation 4 featuring a 6π aromatic character. Moreover, treating 1•-•K+ with a half equivalent of a bis(NHC) produces a biradical species 5, in which there is little interaction between two radical moieties separated by the bis(NHC) linker, suggesting the dis-biradical property. 5 undergoes stepwise and reversible two-electron oxidation, establishing three formal oxidation states.

Reactivity of Cyclic (Alkyl)(amino)germylene towards Copper(I) and Gold(I) Complexes.

The reactions of cyclic (alkyl)(amino)germylenes (CAAGe) with copper(I) and gold(I) complexes were investigated. CAAGe (1) reacts with CuBr(SMe2 ) leading to a tetrameric germylene complex [CAAGeCuBr]4 (2), whereas CAAGe (3) undergoes Au-Cl bond insertion with LAuCl (L=phosphine or N-heterocyclic carbene) to afford germanium gold(I) complexes (5 and 6). Chlorine abstraction of 6 gives the cationic germylene gold(I) complex 7.

Recent advances in stable main group element radicals: preparation and characterization.

Radical species are significant in modern chemistry. Their unique chemical bonding and novel physicochemical properties play significant roles not only in fundamental chemistry, but also in materials science. Main group element radicals are usually transient due to their high reactivity. Highly stable radicals are often stabilized by π-delocalization, sterically demanding ligands, carbenes and weakly coordinating anions in recent years. This review presents the recent advances in the synthesis, characterization, reactivity and physical properties of isolable main group element radicals.

The genome of the recretohalophyte Limonium bicolor provides insights into salt gland development and salinity adaptation during terrestrial evolution.

Halophytes have evolved specialized strategies to cope with high salinity. The extreme halophyte sea lavender (Limonium bicolor) lacks trichomes but possesses salt glands on its epidermis that can excrete harmful ions, such as sodium, to avoid salt damage. Here, we report a high-quality, 2.92-Gb, chromosome-scale L. bicolor genome assembly based on a combination of Illumina short reads, single-molecule, real-time long reads, chromosome conformation capture (Hi-C) data, and Bionano genome maps, greatly enriching the genomic information on recretohalophytes with multicellular salt glands. Although the L. bicolor genome contains genes that show similarity to trichome fate genes from Arabidopsis thaliana, it lacks homologs of the decision fate genes GLABRA3, ENHANCER OF GLABRA3, GLABRA2, TRANSPARENT TESTA GLABRA2, and SIAMESE, providing a molecular explanation for the absence of trichomes in this species. We identified key genes (LbHLH and LbTTG1) controlling salt gland development among classical trichome homologous genes and confirmed their roles by showing that their mutations markedly disrupted salt gland initiation, salt secretion, and salt tolerance, thus offering genetic support for the long-standing hypothesis that salt glands and trichomes may share a common origin. In addition, a whole-genome duplication event occurred in the L. bicolor genome after its divergence from Tartary buckwheat and may have contributed to its adaptation to high salinity. The L. bicolor genome resource and genetic evidence reported in this study provide profound insights into plant salt tolerance mechanisms that may facilitate the engineering of salt-tolerant crops.

The catenation of a singlet diradical dication and modulation of diradical character by metal coordination.

A singlet bis(triarylamine) diradical dication and its zigzag 1D magnetic chain catenated by silver cations were isolated and characterized by single-crystal X-ray crystallography, EPR spectroscopy, SQUID measurements, cyclic voltammetry, and UV-Vis-NIR absorption spectroscopy in conjunction with DFT calculations. The ΔEOS-T has significantly changed due to the coordination of carbonyls (Lewis base) with Ag+ (Lewis acid), revealing that the diradical character can be modulated by Lewis acid-base coordination and interchain intermolecular coupling interactions.

Crystalline radical cations of bis-BN-based analogues of Thiele's hydrocarbon.

Two radical cations of bis-BN-based analogues of Thiele's hydrocarbons were facilely synthesized, fully characterized, and theoretically investigated. One-electron oxidation leads to the reduced bond length alternation and NICS values of the central C4N2 rings, suggesting the decreasing antiaromatic character. The spin density of the radical cations is significantly delocalized over the central linkers with a small contribution from two terminal N-heterocyclic boryl units.

A stable triplet diradical emitter.

Molecules with luminescence have been extensively investigated, but the luminescence of a stable molecule with a triplet ground state has not been observed. Synthesis of boron-containing radicals has attracted lots of interest because of their unique electronic structures and potential applications in organic semiconductors. Though some boron-based diradicals have been reported, neutral boron-containing diradicals with triplet ground states are rare. Herein two borocyclic diradicals with different substituents (3 and 4) have been isolated. Their electronic structures were investigated by EPR and UV spectroscopy, and SQUID magnetometry, in conjunction with DFT calculations. Both experiment and calculation suggest that 3 is an open shell singlet diradical while 4 is a triplet ground state diradical with a large singlet-triplet gap (0.25 kcal mol-1). Both diradicals show multi fluorescence peaks (3: 414, 431, and 470 nm; 4: 420, 433, and 495 nm). 3 displays multiple redox steps and is a potential material towards the design of high-density memory devices. 4 represents the first example of a neutral triplet boron-containing diradical with a strong ferromagnetic interaction, and also is the first stable triplet diradical emitter.

Controlling the unpaired electron by electrostatic attraction in the solid state.

One-electron reduction of 2,7-tBu2-pyrene-4,5,9,10-tetraone (1) with potassium afforded two monoradicals 1K(cryp) and 1K(18c6), a radical tetramer [1K(15c5)]4 and a radical polymer (1K)2n. Using 1K(cryp) and 1K(18c6), we demonstrated large spin density modulation of an organic radical anion in the solid state by electrostatic attraction, without alternation of the molecular skeletons.

Yttrium germole dianion complexes with Y-Ge bonds.

The reactions of dipotassium 3,4-dimethyl-2,5-bis(trimethylsilyl)-germole dianion K2[1] with YCl3 and Cp*YCl2 (Cp* = cyclopentadienyl) in THF at room temperature afforded the dianion salt [(K-cryptand-222)2][1-YCl3] (K2[2]) and the dimeric complex [1-Y-Cp*]2 (3), respectively. While the polymeric complex {[(1)2-Y-K(toluene)]2}n (4) was obtained from the reaction of K2[1] and half molar equivalent of YCl3(THF)3.5 in toluene at 80 °C. The germole dianions in complexes 3 and 4 feature η5/η1 coordination interactions with the yttrium atoms. They represent the first examples of rare earth (RE) complexes containing RE-Ge bonds other than the RE-GeR3 structural type.

Persistent 2c-3e σ-bonded heteronuclear radical cations centered on S/Se and P/As atoms.

The two-center three-electron (2c-3e) bonded species are important in chemical and biological science. Reported isolable 2c-3e σ-bonded species are usually constructed in homoatomic radicals. The one-electron oxidation of main-group heteronuclear species Nap(SPh)(P(Mes)2) (1), Nap(SePh)(P(Mes)2) (2), Nap(SPh)(As(Mes)2) (3) and Nap(SePh)(As(Mes)2) (4) produced persistent radical cations 1˙+-4˙+ in solution. Large couplings of heteroatoms in EPR spectra of 1˙+-4˙+, shorter bond distances and bigger Wiberg bond orders of Ch-Pn in 1˙+-4˙+ than those in 1-4 in DFT calculations indicate large amounts of spin densities over heteroatoms and the formation of 2c-3e σ-bonds between chalcogen and pnicogen atoms. This work provides evidence of 2c-3e σ-bonds constructed between main-group heteronuclears and rare examples of radical cations involving three-electron σ-bonds between S/Se and P/As atoms.

New and old adjuvants in allergen-specific immunotherapy: With a focus on nanoparticles.

Allergic diseases have remarkably increased in recent years. Nowadays, efforts for curing and management of these disorders are an important concern worldwide. Allergen-specific immunotherapy (ASIT) has recently gained more attention as a means for the management of allergic diseases. Adjuvants or helper agents are materials applied for better stimulating and shifting of protective responses, and these belong to an extremely diverse collection of complexes. The main function of adjuvants includes acting as depot foundations, transferring vehicles, and immunostimulators. Immunostimulatory adjuvants have gained increasing attention for ASIT. In this regard, the present study provides a review of old and new adjuvants used in allergen immunotherapy.

Crystalline Diradical Dianions of Pyrene-Fused Azaacenes.

Although diradicals and azaacenes have been greatly attractive in fundamental chemistry and functional materials, the isolable diradical dianions of azaacenes are still unknown. Herein, we describe the first isolation of pyrene-fused azaacene diradical dianion salts [(18-c-6)K(THF)2 ]+ [(18-c-6)K]+ ⋅12-.. and [(18-c-6)K(THF)]2+ ⋅22-.. by reduction of the neutral pyrene-fused azaacene derivatives 1 and 2 with excess potassium graphite in THF in the presence of 18-crown-6. Their electronic structures were investigated by various experiments, in conjunction with theoretical calculations. It was found that both dianions are open-shell singlets in the ground state and their triplet states are thermally readily accessible owing to the small singlet-triplet energy gap. This work provides the first examples of crystalline diradical dianions of azaacenes with considerable diradical character.

Stable Radical Cation and Dication of an N-Heterocyclic Carbene Stabilized Digallene: Synthesis, Characterization and Reactivity.

One- and two-electron oxidation of a digallene stabilized by an N-heterocyclic carbene afforded the first stable gallium-based radical cation and dication salts, respectively. Structural analysis and theoretical calculations reveal that the oxidation occurs at the Ga=Ga double bond, leading to removal of π electrons of the double bond and a decrease of the bond order. The spin density of the radical cation mainly locates at the two gallium centers as demonstrated by EPR spectroscopy and theoretical calculations. Moreover, the reactivity of the radical cation salt toward nBu3 SnH and cyclo-S8 was studied; a digallium-hydride cation salt containing a Ga-Ga single bond and a gallium sulfide cluster bearing an unprecedented ladder-like Ga4 S4 core structure were obtained, respectively.

A diamidinatogermylene as a Z-type ligand in a nickel(0) complex.

The reaction of the phosphine functionalized chlorogermylene 1 with Ni(COD)2 (COD = 1,5-cyclooctadiene) afforded the bis-chlorogermylene ligated nickel(0) complex 2 in high yield. The dechlorination reaction of 2 with elemental potassium serendipitously yielded the diamidinatogermylene nickel(0) complex 3. Single-crystal X-ray diffraction analysis reveals that the germanium center in 3 features a pyramidalized geometry, suggesting the germylene moiety in 3 acts as a Z-type ligand, which is further supported by theoretical calculations. Complex 3 represents the first example bearing a Z-type diaminogermylene ligand.

Tricoordinate Nontrigonal Pnictogen-Centered Radical Anions: Isolation, Characterization, and Reactivity.

The search for main-group element-based radicals is one of the main research topics in contemporary chemistry because of their fascinating chemical and physical properties. The Group 15 element-centered radicals mainly feature a V-shaped two coordinate structure, with a couple of radical cations featuring trigonal tricoordinated geometry. Now, nontrigonal compounds R3 E (E=P, As, Sb) were successfully synthesized by introducing a new rigid tris-amide ligand. The selective one-electron reduction of R3 E afforded the first stable tricoordinate pnictogen-centered radical anion salts; the pnictogen atoms retain planar T-shaped structures. EPR spectroscopy and calculations reveal that the spin density mainly resides at the p orbitals of the pnictogen atoms, which is perpendicular to the N3 E planes.

Retracted: Epigallocatechin gallate ameliorates morphological changes of pancreatic islets in diabetic mice and downregulates blood sugar level by inhibiting the accumulation of AGE-RAGE.

This study aimed to elucidate the key mechanisms and effects of the functional component of green tea, epigallocatechin gallate (EGCG) on a diabetic mouse model. The detected relationship between compounds and genes recorded in the STITCH database highlighted an interaction network between the direct target genes of EGCG and the known diabetes-related genes, which was made apparent through the analysis of gene-gene interactions and signaling pathways, revealing that a key AGE-RAGE signaling pathway in diabetes was enriched in the network. By means of systematic supplementary analyses on diabetic mice, provided evidence suggested that EGCG could significantly enhance the morphology of pancreatic tissues in diabetic mice and downregulate the blood glucose level in a clear dose effect manner, and increased insulin receptor (IR), insulin receptor substrate (IRS1 and IRS2) expression in the liver. Through the detection of protein expression, EGCG was observed to possess the ability to downregulate the accumulation of AGE-RAGE in pancreatic tissues as well as in the transcription factor nuclear factor-κB (NF-κB), which represents a potentially significant method by which EGCG influences diabetes. The results of this study provided evidence indicating that EGCG can effectively improve the morphology of pancreatic tissues, but notably reduce blood glucose levels in diabetic mice, which may be related to its inhibition of AGE-RAGE signaling pathway and activation of transcription factor NF-κB pathway.

POZ/BTB and AT-Hook-Containing Zinc Finger Protein 1 (PATZ1) Suppresses Progression of Ovarian Cancer and Serves as an Independent Prognosis Factor.

BACKGROUND The POZ/BTB and AT-hook-containing Zinc finger protein 1 (PATZ1) is a ubiquitously expressed transcription factor belonging to the POZ domain Krüppel-like zinc finger (POK) family. It is involved in the pathogenesis of a growing list of human diseases, including cancer. The effect of PATZ1 on serous ovarian carcinoma (SOC) remains unclear. This study initially explored the clinical significance of PATZ1 in patients with SOC, the relationship between its expression and the prognosis of SOC patients, and its role in tumor proliferation and invasion. MATERIAL AND METHODS Immunohistochemistry and quantitative real-time polymerase chain reaction (qPCR) were performed to characterize the expression of PATZ1 in SOC tissues. The relationship between PATZ1 expression and the clinicopathological features of patients with SOC was analyzed by chi-square test. Kaplan-Meier method and Cox regression analyses were utilized to evaluate the prognosis of SOC. PATZ1-constructed transfection-mediated overexpression was conducted. The CCK-8 assay was performed to examine the proliferation, while Transwell assay was used to detect the invasive capability. RESULTS The results of IHC and qPCR analyses showed that the expression of PATZ1 in cancerous tissue was significantly lower than that in non-cancerous tissues. Meanwhile, PATZ1 expression was significantly associated with tumor differentiation and LN metastasis. Survival analysis showed that PATZ1 expression was one of the independent prognosis factors for overall survival of SOC patients. In addition, overexpression of PATZ1 inhibited the proliferation and invasion of OVCAR3 cells by in vitro experiments. CONCLUSIONS Our data suggest that PATZ1 is a novel prognostic marker in SOC.

Identification and functional analysis of the autofluorescent substance in Limonium bicolor salt glands.

Limonium bicolor is a typical recretohalophyte with salt glands for the secretion of excess salts into the environment. We observed that L. bicolor salt glands showed obvious blue autofluorescence under UV excitation (330-380 nm). The aim of the present study was to identify and clarify a role for this autofluorescent substance in salt secretion. Sudan IV staining showed that the autofluorescent substance was localized in the cuticle of the salt glands. Moreover, the primary autofluorescent substance was identified as ferulic acid after treatment with 0.1 M ammonium hydroxide solution, alkaline and enzymatic hydrolysis. Additional experiments using two mutants exhibiting increased (fii) and decreased (fid) salt gland fluorescence indicated that the fluorescence intensity of salt glands under UV excitation was positively correlated with the content of ferulic acid in the cuticle, strongly suggesting that the primary autofluorescent substance in the salt glands was ferulic acid. Salt gland secretion was determined using leaf discs, and the results showed that the Na(+) secretion rate per single salt gland was also positively correlated with the content of ferulic acid in the cuticle, suggesting that ferulic acid in the cuticle was directly involved in salt secretion of salt gland.

K(+) accumulation in the cytoplasm and nucleus of the salt gland cells of Limonium bicolor accompanies increased rates of salt secretion under NaCl treatment using NanoSIMS.

Recretohalophytes with specialized salt-secreting structures (salt glands) can secrete excess salts from plant, while discriminating between Na(+) and K(+). K(+)/Na(+) ratio plays an important role in plant salt tolerance, but the distribution and role of K(+) in the salt gland cells is poorly understood. In this article, the in situ subcellular localization of K and Na in the salt gland of the recretohalophyte Limonium bicolor Kuntze is described. Samples were prepared by high-pressure freezing (HPF), freeze substitution (FS) and analyzed using NanoSIMS. The salt gland of L. bicolor consists of sixteen cells. Higher signal strength of Na(+) was located in the apoplast of salt gland cells. Compared with control, 200 mM NaCl treatment led to higher signal strength of K(+) and Na(+) in both cytoplasm and nucleus of salt gland cells although K(+)/Na(+) ratio in both cytoplasm and nucleus were slightly reduced by NaCl. Moreover, the rate of Na(+) secretion per salt gland of L. bicolor treated with 200 mM NaCl was five times that of controls. These results suggest that K(+) accumulation both in the cytoplasm and nucleus of salt gland cells under salinity may play an important role in salt secretion, although the exact mechanism is unknown.

Comparative transcriptome analysis of developmental stages of the Limonium bicolor leaf generates insights into salt gland differentiation.

With the expansion of saline land worldwide, it is essential to establish a model halophyte to study the salt-tolerance mechanism. The salt glands in the epidermis of Limonium bicolor (a recretohalophyte) play a pivotal role in salt tolerance by secreting excess salts from tissues. Despite the importance of salt secretion, nothing is known about the molecular mechanisms of salt gland development. In this study, we applied RNA sequencing to profile early leaf development using five distinct developmental stages, which were quantified by successive collections of the first true leaves of L. bicolor with precise spatial and temporal resolution. Specific gene expression patterns were identified for each developmental stage. In particular, we found that genes controlling salt gland differentiation in L. bicolor may evolve in a trichome formation, which was also confirmed by mutants with increased salt gland densities. Genes involved in the special ultrastructure of salt glands were also elucidated. Twenty-six genes were proposed to participate in salt gland differentiation. Our dataset sheds light on the molecular processes underpinning salt gland development and thus represents a first step towards the bioengineering of active salt-secretion capacity in crops.