In recent years, α‐imino rhodium carbene complexes derived by ring‐opening of N‐sulfonyl‐1,2,3‐triazoles have attracted much attention from organic chemists. Many transformations of these species ...have been reported that involve, in most cases, nucleophilic attack at the carbene center of the α‐imino rhodium carbene, facilitating the synthesis of a wide range of novel and useful compounds, particularly heterocycles. This Minireview mainly focuses on advances in the transformation of N‐sulfonyl‐1,2,3‐triazoles during the past two years.
In recent years, α‐imino rhodium carbene complexes derived from N‐sulfonyl‐1,2,3‐triazoles have attracted much attention for their application in the synthesis of heterocycles and related species. In most cases, ring‐opening of the triazole to afford the α‐imino rhodium carbene is followed by nucleophilic attack at the carbene center to afford a wide range of useful compounds.
The basic helix-loop-helix (bHLH) proteins, a large transcription factors family, are involved in plant growth and development, and defensive response to various environmental stresses. The ...resurrection plant Myrothamnus flabellifolia is known for its extremely strong drought tolerance, but few bHLHs taking part in abiotic stress response have been unveiled in M. flabellifolia.
In the present research, we cloned and characterized a dehydration-inducible gene, MfbHLH38, from M. flabellifolia. The MfbHLH38 protein is localized in the nucleus, where it may act as a transcription factor. Heterologous expression of MfbHLH38 in Arabidopsis improved the tolerance to drought and salinity stresses, as determined by the studies on physiological indexes, such as contents of chlorophyll, malondialdehyde (MDA), proline (Pro), soluble protein, and soluble sugar, water loss rate of detached leaves, reactive oxygen species (ROS) accumulation, as well as antioxidant enzyme activities. Besides, MfbHLH38 overexpression increased the sensitivity of stomatal closure to mannitol and abscisic acid (ABA), improved ABA level under drought stress, and elevated the expression of genes associated with ABA biosynthesis and ABA responding, sucha as NCED3, P5CS, and RD29A.
Our results presented evidence that MfbHLH38 enhanced tolerance to drought and salinity stresses in Arabidopsis through increasing water retention ability, regulating osmotic balance, decreasing stress-induced oxidation damage, and possibly participated in ABA-dependent stress-responding pathway.
To report long‐term results of a randomized controlled trial that compared cisplatin/fluorouracil/docetaxel (TPF) induction chemotherapy (IC) plus concurrent chemoradiotherapy (CCRT) with CCRT alone ...in locoregionally advanced nasopharyngeal carcinoma (NPC). Patients with stage III–IVB (except T3–4 N0) NPC were randomly assigned to receive IC plus CCRT (n = 241) or CCRT alone (n = 239). IC included three cycles of docetaxel (60 mg/m2 d1), cisplatin (60 mg/m2 d1), and fluorouracil (600 mg/m2/d civ d1–5) every 3 weeks. Patients from both groups received intensity‐modulated radiotherapy concurrently with three cycles of 100 mg/m2 cisplatin every 3 weeks. After a median follow‐up of 71.5 months, the IC plus CCRT group showed significantly better 5‐year failure‐free survival (FFS, 77.4% vs. 66.4%, p = 0.019), overall survival (OS, 85.6% vs. 77.7%, p = 0.042), distant failure‐free survival (88% vs. 79.8%, p = 0.030), and locoregional failure‐free survival (90.7% vs. 83.8%, p = 0.044) compared to the CCRT alone group. Post hoc subgroup analyses revealed that beneficial effects on FFS were primarily observed in patients with N1, stage IVA, pretreatment lactate dehydrogenase ≥170 U/l, or pretreatment plasma Epstein–Barr virus DNA ≥6000 copies/mL. Two nomograms were further developed to predict the potential FFS and OS benefit of TPF IC. The incidence of grade 3 or 4 late toxicities was 8.8% (21/239) in the IC plus CCRT group and 9.2% (22/238) in the CCRT alone group. Long‐term follow‐up confirmed that TPF IC plus CCRT significantly improved survival in locoregionally advanced NPC with no marked increase in late toxicities and could be an option of treatment for these patients.
What's new?
Despite advances in the treatment of nasopharyngeal carcinoma, approximately 30% of high‐risk patients experience recurrence after treatment. Here the authors find that combining the conventional chemoradiotherapy with a triple induction chemotherapy (cisplatin/fluorouracil/docetaxel) prolonged survival of patients with locoregionally advanced cancer, even after more than 70 months of follow‐up. The combination treatment increased acute, but not late, toxicities, and the authors propose that it could present a new treatment option for this patient group.
New rhodium(II)‐catalyzed or thermally induced intramolecular alkoxy group migration of N‐sulfonyl‐1,2,3‐triazoles has been developed, affording divergent synthesis of 1,2‐dihydroisoquinoline and ...1‐indanone derivatives according to different conditions. N‐Sulfonyl keteneimine is the key intermediate for the synthesis of dihydroisoquinoline, whereas the aza‐vinyl carbene intermediate results in the formation of 1‐indanone.
Synthesis of privileged structures: A new rhodium(II)‐catalyzed or thermally induced intramolecular alkoxy group migration of N‐sulfonyl‐1,2,3‐triazoles has been developed, affording different migration products depending on the reaction conditions (see scheme).
A dual system of redox additive by incorporating Na2MoO4 and KI into H2SO4 solution has been developed to highly elevate the capacitance of supercapacitors primarily owing to the synergistic effect ...between them at the superposed redox voltage. Furthermore, the synergistic effect therein is attributed to the formation of complex substance of (MoxIyO4x)n−Cz, which can promote redox reaction of Mon+ and In− at the interface of carbon electrode and electrolyte. On the other hand, many crucial factors mainly including the molar ratio, concentration of redox additive and voltage window strongly determine the final capacitive behaviors. For example, when adding Na2MoO4 and KI into H2SO4 with the same concentration of 0.1 mol L−1, the resultant capacitance has remarkably increased by 17.4 times, compared with the one without any redox additive, at 3 A g−1 in a two-electrode system. What's more, the homologous energy density can reach up to 65.3 Wh kg−1 at the suitable voltage window (0–1 V). Hence, the present synergism of various kinds of redox additives is intriguing and easily extended to other systems, which could highly elevate the capacitive performances of supercapacitors.
•Synergistic effect exists between Na2MoO4 and KI due to overlapping redox voltage window.•Adjusting the ratio of Na2MoO4 and KI can greatly affect the capacitive behaviors.•The capacitance has remarkably increased by 17.4 times.•A high energy density can reach up to 65.3 Wh kg−1.
We show herein the phosphatase‐like catalytic activity of coordination polymers obtained after adding Ag+‐ions to thiols bearing hydrophobic alkyl chains terminated with a 1,4,7‐triazacyclononane ...(TACN) group. The subsequent addition of Zn2+ ‐ions to the self‐assembled polymers resulted in the formation of multivalent metal coordination polymers capable of catalysing the transphosphorylation of an RNA‐model compound (2‐hydroxypropyl‐4‐nitrophenyl phosphate, HPNPP) with high reactivity. Analysis of a series of metal ions showed that the highest catalytic activity was obtained when Ag+‐ions were used as the first metal ions to construct the backbone of the coordination polymer through interaction with the ‐SH group followed by Zn2+‐ions as the second metal ions complexed by the TACN‐macrocycle. Furthermore, it was demonstrated that the catalytic activity could be modulated by changing the length of the hydrophobic alkyl chain.
A series of self‐assembled multivalent Ag‐SR coordination polymers with high phosphatase‐like activity have been developed. This work represents a new alternative for the future rational design of highly efficient catalysts for hydrolysis of phosphates and carboxylates.
Using thiocarbanilide and Mg(OH)2 powders as carbon precursor and template, respectively, novel 2D carbon nanosheets with large area have been produced. Next, based on the cooperative effect, 1, ...4-dihydroxyanthraquinone (DQ) and hydroquinone (HQ) regarded as efficient dual redox additives have been incorporated into the electrode carbon material and H2SO4 electrolyte, respectively, to largely elevate the capacitive performance of supercapacitors. More importantly, the cooperative effect results from the redox processes of DQ and HQ consecutively occurring in the electrode carbon material and aqueous H2SO4 electrolyte, respectively. Besides, the molar ratio of DQ and HQ exerts a crucial role in the determination of the electrochemical behaviors and eventually the optimum condition is the mass ratio of 1:1 concerning the DQ and porous carbon within solid electrode while retaining the HQ concentration as 20 mmol L−1 in 1 mol L−1 H2SO4 electrolyte. As a result, the maximum specific capacitance is achieved of 239 F g−1 at 3 A g−1, and furthermore the maximum energy density up to 21.1 Wh kg−1 is almost 3.5 times larger than that of the one without introducing any redox additive.
•2D carbon nanosheets are obtained by carbonizing thiocarbanilide mixed with Mg(OH)2.•DQ and HQ serve as dual redox additives.•The consecutive redox processes of DQ and HQ are contributed to the capacitive performance.•A high energy density of 21.1 Wh kg−1 is achieved.
Cu MOF-based catalytic sensing for formaldehyde Gao, Ping; Sun, Xiang-Ying; Liu, Bin ...
Journal of materials chemistry. C, Materials for optical and electronic devices,
2018, Letnik:
6, Številka:
30
Journal Article
Recenzirano
Developing a catalyst with a uniform and well-defined crystal structure is very important to establish a catalytic sensing system with high efficiency. In this work, Cu-BTC metal–organic frameworks ...(MOFs) without a crystalline CuO or Cu 2 O phase were successfully synthesized by using a low temperature synthesis method, and the as-prepared Cu-BTC MOFs were found to have outstanding catalytic activity towards the traditional oxidase substrate, o -phenylenediamine (OPD), to generate a colored and fluorescent product. The results of the kinetics analysis revealed that the catalytic behavior of Cu-BTC MOFs towards OPD could well follow the typical Michaelis–Menten equation, indicative of a strong affinity between Cu-BTC MOFs and OPD. On the basis of these findings, taken together the condensation reaction between the –CHO group of formaldehyde and the –NH 2 group of OPD to form Schiff base compounds, a novel Cu-BTC MOF-based catalytic sensing system for detecting gaseous formaldehyde could be successfully established.
Invading pathogens have unique molecular signatures that are recognized by Toll-like receptors (TLRs) resulting in either activation of antigen-presenting cells (APCs) and/or costimulation of T cells ...inducing both innate and adaptive immunity. TLRs are also involved in T-cell development and can reprogram Treg cells to become helper cells. T cells consist of various subsets, that is, Th1, Th2, Th17, T follicular helper (Tfh), cytotoxic T lymphocytes (CTLs), regulatory T cells (Treg) and these originate from thymic progenitor thymocytes. T-cell receptor (TCR) activation in distinct T-cell subsets with different TLRs results in differing outcomes, for example, activation of TLR4 expressed in T cells promotes suppressive function of regulatory T cells (Treg), while activation of TLR6 expressed in T cells abrogates Treg function. The current state of knowledge of regarding TLR-mediated T-cell development and differentiation is reviewed.
Objectives
The aim of this research was to explore the origin, diversification, and demographic history of O1a‐M119 over the past 10,000 years, as well as its role during the formation of East Asian ...and Southeast Asian populations, particularly the Han, Tai‐Kadai‐speaking, and Austronesian‐speaking populations.
Materials and Methods
Y‐chromosome sequences (n = 141) of the O1a‐M119 lineage, including 17 newly generated in this study, were used to reconstruct a revised phylogenetic tree with age estimates, and identify sub‐lineages. The geographic distribution of 12 O1a‐M119 sub‐lineages was summarized, based on 7325 O1a‐M119 individuals identified among 60,009 Chinese males.
Results
A revised phylogenetic tree, age estimation, and distribution maps indicated continuous expansion of haplogroup O1a‐M119 over the past 10,000 years, and differences in demographic history across geographic regions. We propose several sub‐lineages of O1a‐M119 as founding paternal lineages of Han, Tai‐Kadai‐speaking, and Austronesian‐speaking populations. The sharing of several young O1a‐M119 sub‐lineages with expansion times less than 6000 years between these three population groups supports a partial common ancestry for them in the Neolithic Age; however, the paternal genetic divergence pattern is much more complex than previous hypotheses based on ethnology, archeology, and linguistics.
Discussion
Our analyses contribute to a better understanding of the demographic history of O1a‐M119 sub‐lineages over the past 10,000 years during the emergence of Han, Austronesians, Tai‐Kadai‐speaking populations. The data described in this study will assist in understanding of the history of Han, Tai‐Kadai‐speaking, and Austronesian‐speaking populations from ethnology, archeology, and linguistic perspectives in the future.
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