Continuous ultra-wideband signal regeneration in random optoelectronic oscillators through injection locking.

By using an external injection locking method, for what we believe to be the first time, we experimentally demonstrate continuous ultra-wideband signal regeneration in random optoelectronic oscillators, achieving more adaptable signal processing capabilities than self-oscillation methods. Supported by theoretical analysis and experimental evidences, this system can regenerate any signal with sufficient gain in a random-feedback cavity, independent of cavity filters. Remarkably, enhanced phase noise performance with over 35.2 dB side mode suppression and a phase noise better than -86 dBc@1 kHz at higher injecting powers are demonstrated. Additionally, we successfully process complex multi-frequency communication signals, indicating potential applications in radar, remote sensing, and data communications.

Facile Friedel-Crafts alkylation of arenes under solvent-free conditions.

The Friedel-Crafts alkylation of arenes is an important part of electrophilic aromatic substitution reactions. However, the reactivity of arenes is weakened by electron-withdrawing substituents, leading to limited substrate scopes and applications. Herein, we developed an efficient HOTf-promoted Friedel-Crafts alkylation reaction of broad arenes with α-aryl-α-diazoesters under metal-free and solvent-free conditions.

B(9)-OH-o-Carboranes: Synthesis, Mechanism, and Property Exploration.

Herein, we present a chemically robust and efficient synthesis route for B(9)-OH-o-carboranes by the oxidation of o-carboranes with commercially available 68% HNO3 under the assistance of trifluoromethanesulfonic acid (HOTf) and hexafluoroisopropanol (HFIP). The reaction is highly efficient with a wide scope of carboranes, and the selectivity of B(9)/B(8) is up to 98:2. The success of this transformation relies on the strong electrophilicity and oxidizability of HNO3, promoted through hydrogen bonds of the Brønsted acid HOTf and the solvent HFIP. Mechanism studies reveal that the oxidation of o-carborane involves an initial electrophilic attack of HNO3 to the hydrogen atom at the most electronegative B(9) of o-carborane. In this transformation, the hydrogen atom of the B-H bond is the nucleophilic site, which is different from the electrophilic substitution reaction, where the boron atom is the nucleophilic site. Therefore, this is an oxidation-reduction reaction of o-carborane under mild conditions in which N(V) → N(III) and H(-I) → H(I). The derivatization of 9-OH-o-carborane was further examined, and the carboranyl group was successfully introduced to an amino acid, polyethylene glycol, biotin, deoxyuridine, and saccharide. Undoubtedly, this approach provides a selective way for the rapid incorporation of carborane moieties into small molecules for application in boron neutron capture therapy, which requires the targeted delivery of boron-rich groups.

Decreased cyclooxygenase-2 associated with impaired megakaryopoiesis and thrombopoiesis in primary immune thrombocytopenia.

BACKGROUND: Cyclooxygenase (COX)-2 is a rate-limiting enzyme in the biosynthesis of prostanoids, which is mostly inducible by inflammatory cytokines. The participation of COX-2 in the maturation of megakaryocytes has been reported but barely studied in primary immune thrombocytopenia (ITP). METHODS: The expressions of COX-2 and Caspase-1, Caspase-3 and Caspase-3 p17 subunit in platelets from ITP patients and healthy controls (HC), and the expressions of COX-2 and CD41 in bone marrow (BM) of ITP patients were measured and analyzed for correlations. The effects of COX-2 inhibitor on megakaryopoiesis and thrombopoiesis were assessed by in vitro culture of Meg01 cells and murine BM-derived megakaryocytes and in vivo experiments of passive ITP mice. RESULTS: The expression of COX-2 was decreased and Caspase-1 and Caspase-3 p17 were increased in platelets from ITP patients compared to HC. In platelets from ITP patients, the COX-2 expression was positively correlated with platelet count and negatively correlated to the expression of Caspase-1. In ITP patients BM, the expression of CD41 was positively correlated with the expression of COX-2. COX-2 inhibitor inhibited the count of megakaryocytes and impaired the maturation and platelet production in Meg01 cells and bone marrow-derived megakaryocytes. COX-2 inhibitor aggravated thrombocytopenia and damaged megakaryopoiesis in ITP murine model. CONCLUSION: COX-2 plays a vital role in the physiologic and pathologic conditions of ITP by intervening the survival of platelets and impairing the megakaryopoiesis and thrombopoiesis of megakaryocytes.

Trifluoromethanesulfonic Acid Promoted Controllable Electrophilic Aromatic Nitration.

In this work, we developed a facile and controllable electrophilic aromatic nitration method with commercially available 68% HNO3 as the nitrating reagent and trifluoromethanesulfonic acid (HOTf) as the catalyst in hexafluoroisopropanol or under solvent-free conditions. The electrophilic nitration products of different arenes can be obtained in almost quantitative yields by tuning the loading of HOTf. The strong acidity and water absorbing property of HOTf allowed this transformation to reach completion in a short time at room temperature.

A Method for Highly Selective Halogenation of o-Carboranes and m-Carboranes.

A facile halogenation method for highly selective synthesis of 9-X-o-carboranes, 9,12-X2-o-carboranes, 9-X-12-X'-o-carboranes, 9-X-m-carboranes, 9,10-X2-m-carboranes, and 9-X-10-X'-m-carboranes (X, X' = Cl, Br, I) has been developed on the basis of our previous work. The success of this transformation relies on the usage of trifluoromethanesulfonic acid (HOTf), the easily available strong Brønsted acid. The addition of HOTf greatly increases the electrophilicity of N-haloamides through hydrogen bonding interaction, resulting in the low loading of N-haloamides, short reaction time, and mild reaction conditions. Additionally, the solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) is also essential to further increase the acidity of HOTf.

Palladium-Catalyzed Regioselective B(9)-Amination of o-Carboranes and m-Carboranes in HFIP with Broad Nitrogen Sources.

Amination of carboranes has a good application prospect in organic and pharmaceutical synthesis. However, the current methods used for this transformation suffer from limitations. Herein, we report a practical method for a highly regioselective formation of a B-N bond by Pd(II)-catalyzed B(9)-H amination of o- and m-carboranes in hexafluoroisopropanol (HFIP) with different nitrogen sources under air atmosphere. The silver salt and HFIP solvent play critical roles in the present protocol. The mechanistic study reveals that the silver salt acts as a Lewis acid to promote the electrophilic palladation step by forming a heterobimetallic active catalyst PdAg(OAc)3; the strong hydrogen-bond-donating ability and low nucleophilicity of HFIP enhance the electrophilic ability of Pd(II). It is believed that these N-containing carboranes are potentially of great importance in the synthesis of new pharmaceuticals.

Thermal-mechanical-photo-activation effect on silica micro/nanofiber surfaces: origination, reparation and utilization.

The exploration relevant to the surface changes on optical micro- and nanofibers (MNFs) is still in infancy, and the reported original mechanisms remain long-standing puzzles. Here, by recognizing the combined interactions between fiber heating, mechanically tapering, and high-power pulsed laser guiding processes in MNFs, we establish a general thermal-mechanical-photo-activation mechanism that can explain the surface changes on MNFs. Our proposed activation mechanism can be well supported by the systematical experimental results using high-intensity nanosecond/femtosecond pulsed lasers. Especially we find large bump-like nanoscale cavities on the fracture ends of thin MNFs. Theoretically, on the basis of greatly increased bond energy activated by the fiber heating and mechanically tapering processes, the energy needed to break the silicon-oxygen bond into dangling bonds is significantly reduced from its intrinsic bandgap of ∼9 eV to as low as ∼4.0 eV, thus high-power pulsed lasers with much smaller photon energy can induce obvious surface changes on MNFs via multi-photon absorption. Finally, we demonstrate that using surfactants can repair the MNF surfaces and exploit them in promising applications ranging from sensing and optoelectronics to nonlinear optics. Our results pave the way for future preventing the performances from degradation and enabling the practical MNF-based device applications.

Synthesis of Six-Membered N-Heterocycle Frameworks Based on Intramolecular Metal-Free N-Centered Radical Chemistry.

The formation of intramolecular C-N bond represents a powerful strategy in organic transformation as the great importance of N-heterocycles in the fields of natural products and bioactive molecules. This personal account describes the synthesis of cyclic phosphinamidation, benzosultam, benzosulfoximine, phenanthridine and their halogenated compounds through transition-metal-free intramolecular oxidative C-N bond formation. Mechanism study reveals that N-X bond is initially formed under the effect of hypervalent halogen, which is very unstable and easily undergoes thermal or light homolytic cleavage to generate nitrogen radical. Then the nitrogen radical is trapped by the arene to give aryl radical. Rearomatization of aryl radical under the oxidant to provide corresponding N-heterocycle. Under suitable conditions, the N-heterocycles can be further transformed to halogenated N-heterocycles.

Practical Synthesis of B(9)-Halogenated Carboranes with N-Haloamides in Hexafluoroisopropanol.

The B(9)-H halogenation of o-carborane and m-carborane was achieved with excellent selectivities in hexafluoroisopropanol (HFIP) under simple reaction conditions: single reagent [trichloroisocyanuric acid (TCCA), tribromoisocyanuric acid (TBCA) or N-iodosuccinimide (NIS)], catalyst-free, air-/moisture-tolerant, and convenient work-up. With this method, a variety of 9-halogenated o-carboranes and m-carboranes were obtained in good to excellent yields with broad tolerance of functional groups.

Hydroboration Reaction and Mechanism of Carboxylic Acids using NaNH2(BH3)2, a Hydroboration Reagent with Reducing Capability between NaBH4 and LiAlH4.

Hydroboration reactions of carboxylic acids using sodium aminodiboranate (NaNH2[BH3]2, NaADBH) to form primary alcohols were systematically investigated, and the reduction mechanism was elucidated experimentally and computationally. The transfer of hydride ions from B atoms to C atoms, the key step in the mechanism, was theoretically illustrated and supported by experimental results. The intermediates of NH2B2H5, PhCH═CHCOOBH2NH2BH3-, PhCH═CHCH2OBO, and the byproducts of BH4-, NH2BH2, and NH2BH3- were identified and characterized by 11B and 1H NMR. The reducing capacity of NaADBH was found between that of NaBH4 and LiAlH4. We have thus found that NaADBH is a promising reducing agent for hydroboration because of its stability and easy handling. These reactions exhibit excellent yields and good selectivity, therefore providing alternative synthetic approaches for the conversion of carboxylic acids to primary alcohols with a wide range of functional group tolerance.

Syntheses of Bromo-N-heterocycles through Dibromohydantoin-Promoted Tandem C-H Amination/Bromination.

Herein, we report a metal-free radical tandem C-H amination and bromination reaction with dibromohydantoin (DBH) as both the amination and bromination reagents and water as the main solvent. The reaction involves in intramolecular C-H amination and electrophilic bromination using cheap commercially available DBH. The products represent heterocyclic building blocks, readily modifiable by classical cross-coupling reactions.

Synthesis of Phenanthridines through Iodine-Supported Intramolecular C-H Amination and Oxidation under Visible Light.

Herein, we report a metal-free and step-economic synthesis of phenanthridines from 2-biarylmethanamines under mild conditions. The reaction involves iodine-supported intramolecular C-H amination and oxidation of 5,6-dihydrophenanthridine under air and benign visible light. The mechanism study reveals that visible light plays a key role in both these steps.

Stress tolerance of Staphylococcus aureus with different antibiotic resistance profiles.

Staphylococcus aureus (S. aureus) is a zoonotic bacterium and is among the most important pathogens causing bacterial foodborne diseases. In recent years, disease caused by antibiotic-resistant S. aureus is a serious clinical problem that poses a great threat to public health. In this study, we examined the drug-resistance phenotypes and genotypes of 9 S. aureus strains. One strain was obtained from the China Center for Type Culture Collection (CCTCC), and the remaining eight strains were isolated from food. Two common methods (the Kirby-Bauer disk diffusion and broth microdilution methods) were used to detect bacterial drug resistance. Then, we analysed the relationship between the bacterial drug resistance phenotypes and genotypes. We found that some S. aureus strains isolated from food were drug-resistant or even multi-drug resistant and that there was not a perfect match between resistance phenotypes and genotypes. The viabilities of the drug-sensitive (DS), drug-resistant (DR), and multi-drug resistant (MDR) S. aureus strains were also compared when they were exposed to conditions of acid (HCl, pH = 1.5), heat (63 °C), and osmotic pressure (30% NaCl). The results showed that the DR and MDR bacterial strains had survival rates similar to or higher than those of the DS strains under environmental stress.

One-Pot Synthesis of Iodo-Dibenzothiazines from 2-Biaryl Sulfides.

Herein, we report a metal-free and step-economic synthesis of iodo-dibenzothiazines from 2-biaryl sulfides under mild reaction conditions. The reaction involves sulfoximination of sulfides, intramolecular C-H amination, and iodization using cheap commercially available reagents. The products represent heterocyclic building blocks, readily modifiable by classical cross-coupling reactions.

New Approaches for Biaryl-Based Phosphine Ligand Synthesis via P═O Directed C-H Functionalizations.

Given the important influence of phosphine ligands in transition metal-catalyzed reactions, chemists have searched for straightforward and efficient methodologies for the synthesis of diverse phosphine ligands. Although significant progress has been made in this aspect over the past decades, the development of new phosphorus-containing ligands with properties superior to their predecessors remains a central task for chemists. Recently, researchers have demonstrated that biphenyl monophosphine ligands function as highly efficient ligands for transition-metal-catalyzed organic transformations, especially for reactions where chelating bisphosphine ligands cannot be used. In 1998, Buchwald introduced a new class of air-stable phosphine ligands based on the dialkylbiaryl phosphine backbone. These ligands have been successfully used for a wide variety of palladium-catalyzed carbon-carbon, carbon-nitrogen, and carbon-oxygen construction processes as well as serving as supporting ligands for a number of other reactions. At the same time, the use of the biphenyl monophosphine ligands often allows reactions to proceed with short reaction times and low catalyst loadings and under mild reaction conditions. However, the synthesis of chiral biphenyl monophosphine ligands, especially those the chirality of which is due to biaryl axial chirality, is very limited. In this Account, we summarize our methodologies for the synthesis of this kind of biphenyl monophosphine ligands including the P═O directed C-H functionalization, P═O directed diastereoselective C-H functionalization, P═O directed enantioselective C-H functionalization, and metal-free diastereoselective radical oxidative C-H amination under mild reaction conditions. With these methods, a series of biphenyl phosphine ligand precursors containing achiral or axially chiral centers and precursors possessing both axial chirality and a chirogenic phosphorus center with different electronic properties and steric effect have been obtained under different reaction conditions. For the preparation of chiral biphenyl monophosphine ligands, which not only possess axial chirality but in many cases also possess chirality at phosphorus, the primary means of introducing chirality is through the use of the menthyl phenylphosphinate. As a chiral auxiliary group, the menthyl phenylphosphinate has some unique features: (i) it is easy to prepare; (ii) the products contain both axial chirality and central chirality on the phosphorus atom; (iii) the menthyl group could easily be transformed into other functional groups, which is crucial for the diversity of the corresponding biphenyl ligands. In our reaction, the P═O group not only acts as the directing group but also facilitates the construction of the phosphine ligands. In addition, the application of these products in asymmetric catalysis has also been studied with good results obtained in some reactions. The further application of these ligands, especially the chiral biphenyl monophosphine ligands in catalysis reactions is underway in our laboratory, and we hope different kinds of reactions will be achieved with these ligands.

Tandem Oxidative C-H Amination and Iodization to Synthesize Difunctional Atropoisomeric P-Stereogenic Phosphinamides.

An efficient metal-free tandem intramolecular oxidative C-H amination and iodization of phosphinamide was performed and a series of new phosphorus heterocyclic compounds was obtained. This method provides a concise and highly valuable pathway for the synthesis of difunctional atropoisomeric P-stereogenic phosphinamides.

Asymmetric Synthesis of Chiral Atropisomeric Bis-Aryl Organophosphorus from Menthyl H-Phosphinate.

This review describes new methods for the synthesis of chiral monophosphine ligands with menthyl phenylphosphinate as a chiral auxiliary through asymmetric Suzuki-Miyaura cross-coupling reactions and asymmetric C-H functionalization. The chiral menthyl phenylphosphinate as a chiral auxiliary is easy to prepare and the menthyl group can easily be transformed into other functional groups, with the chiral center synchronously remaining. These methodologies provide highly efficient and practical strategies for the synthesis of novel axially chiral biaryl monophosphine oxides and their corresponding phosphines. Meanwhile, these reactions are easy to handle and exhibit wide scope for substrates with excellent diastereomeric ratios.

Asymmetric Suzuki-Miyaura cross-coupling for the synthesis of chiral biaryl compounds as potential monophosphine ligands.

Efficient asymmetric Suzuki-Miyaura coupling reactions have been employed for the first time to synthesize chiral biaryl compounds with phosphinate groups as chiral auxiliaries. A series of functionalized chiral biaryls are thereby synthesized in excellent yields and good diastereoselectivities (up to >95:5 d.r.) and axially chiral monophosphorus ligands are obtained through further functionalizations.

Comparison of induced versus natural regulatory T cells of the same TCR specificity for induction of tolerance to an environmental antigen.

Recent evidence shows that natural CD25(+)Foxp3(+) regulatory T cells (nTreg) and induced CD25(+)Foxp3(+) regulatory T cells (iTreg) both contribute to tolerance in mouse models of colitis and asthma, but there is little evidence regarding their relative contributions to this tolerance. We compared the abilities of nTreg and iTreg, both from OVA-TCR-transgenic OTII mice, to mediate tolerance in OVA-asthmatic C57BL/6 mice. The iTreg were differentiated from Th2 effector T cells by exposure to IL-10-differentiated dendritic cells (DC10) in vitro or in vivo, whereas we purified nTreg from allergen-naive mice and exposed them to DC10 before use. Each Treg population was subsequently repurified and tested for its therapeutic efficacy in vitro and in vivo. DC10 engaged the nTreg in a cognate fashion in Forster (or fluorescence) resonance energy transfer assays, and these nTreg reduced in vitro OVA-asthmatic Th2 effector T cell responses by 41-56%, whereas the comparator iTreg reduced these responses by 72-86%. Neutralization of IL-10, but not TGF-ß, eliminated the suppressive activities of iTreg but not nTreg. Delivery of 5 × 10(5) purified nTreg reduced allergen challenge-induced airway IL-4 (p ≤ 0.03) and IL-5 (p ≤ 0.001) responses of asthmatic recipients by ≤ 23% but did not affect airway hyperresponsiveness or IgE levels, whereas equal numbers of iTreg of identical TCR specificity reduced all airway responses to allergen challenge by 82-96% (p ≤ 0.001) and fully normalized airway hyperresponsiveness. These data confirm that allergen-specific iTreg and nTreg have active roles in asthma tolerance and that iTreg are substantially more tolerogenic in this setting.