Timing Correlated-Electron Emission from Strong Field Atomic Double Ionization with Polarization-Gated Attoclock.

Attoclock provides a powerful tool for probing the ultrafast electron dynamics in strong laser fields. However, this technique has remained restricted to single electron or sequential double ionized electron dynamics. Here, we propose a novel attoclock scheme with a polarization-gated few-cycle laser pulse and demonstrate its application in timing the correlated-electron emission in strong field double ionization of argon. Our experimental measurements reveal that the correlated-electron emission occurs mainly through two channels with time differences of 234±22 as and 1043±73 as, respectively. Classical model calculations well reproduce the experimental results and deepen our understanding of ultrafast electron correlation dynamics.

Surface Engineering and Programmed Self-Assembly of Silica Nanoparticles with Controllable Polystyrene/Poly(4-vinybenzyl azide) Patches.

The programmed self-assembly of patchy nanoparticles (NPs) through a bottom-up approach is an efficient strategy for producing highly organized materials with a predetermined architecture. Herein, we report the preparation of di- and trivalent silica NPs with polystyrene (PS)/poly(4-vinylbenzyl azide) (PVBA) patches and assemble them in a THF mixture by lowering the solvent quality. Silica-PS/PVBA colloidal hybrid clusters were synthesized through the seeded growth emulsion copolymerization of styrene and 4-vinylbenzyl azide (VBA) in varying ratios. Subsequently, macromolecules on silica NPs originating from the copolymerization of growing PS or PVBA chains with the surface-grafted MMS compatibilizer are engineered by fine-tuning of polymer compositions or adjustment of solvent qualities. Moreover, multistage silica regrowth of tripod and tetrapod allowed a fine control of the patch-to-particle size ratio ranging from 0.69 to 1.54. Intriguingly, patchy silica NPs (1-, 2-, 3-PSNs) rather than hybrid clusters are successfully used as templates for multistep regrowth experiments, leading to the formation of silica NPs with a new morphology and size controllable PVBA/PS patches. Last but not least, combined with mesoscale dynamics simulations, the self-assembly kinetics of 2-PSN and 3-PSN into linear colloidal polymers and honeycomb-like lattices are studied. This work paves a new avenue for constructing colloidal polymers with a well-defined sequence and colloidal crystals with a predetermined architecture.

Advances for Triangular and Sandwich-Shaped All-Metal Aromatics.

Much experimental work has been contributed to all-metal σ, π and δ-aromaticity among transition metals, semimetallics and other metals in the past two decades. Before our focused investigations on the properties of triangular and sandwich-shaped all-metal aromatics, A. I. Boldyrev presented general discussions on the concepts of all-metal σ-aromaticity and σ-antiaromaticity for metallo-clusters. Schleyer illustrated that Nucleus-Independent Chemical Shifts (NICS) were among the most authoritative criteria for aromaticity. Ugalde discussed the earlier developments of all-metal aromatic compounds with all possible shapes. Besides the theoretical predictions, many stable all-metal aromatic trinuclear clusters have been isolated as the metallic analogues of either the σ-aromatic molecule's [H3]+ ion or the π-aromatic molecule's [C3H3]+ ion. Different from Hoffman's opinion on all-metal aromaticity, triangular all-metal aromatics were found to hold great potential in applications in coordination chemistry, catalysis, and material science. Triangular all-metal aromatics, which were theoretically proved to conform to the Hückel (4n + 2) rule and possess the smallest aromatic ring, could also play roles as stable ligands during the formation of all-metal sandwiches. The triangular and sandwich-shaped all-metal aromatics have not yet been specifically summarized despite their diversity of existence, puissant developments and various interesting applications. These findings are different from the public opinion that all-metal aromatics would be limited to further applications due to their overstated difficulties in synthesis and uncertain stabilities. Our review will specifically focus on the summarization of theoretical predictions, feasible syntheses and isolations, and multiple applications of triangular and sandwich shaped all-metal aromatics. The appropriateness and necessities of this review will emphasize and disseminate their importance and applications forcefully and in a timely manner.

A Benzothiadiazole-Based Zn(II) Metal-Organic Framework with Visual Turn-On Sensing for Anthrax Biomarker and Theoretical Calculation.

2,6-pyridine dicarboxylic acid (DPA) is an exceptional biomarker of notorious anthrax spores. Therefore, the rapid, sensitive, and selective quantitative detection of DPA is extremely significant and urgent. This paper reports a Zn(II) metal-organic framework with the formula of {[Zn6(NDA)6(DPBT)3] 2H2O·3DMF}n (MOF-1), which consists of 2,6-naphthalenedicarboxylic acid (2,6-NDA), 4,7-di(4-pyridyl)-2,1,3-benzothiadiazole (DPBT), and Zn(II) ions. Structural analysis indicated that MOF-1 is a three-dimensional (3D) network which crystallized in the monoclinic system with the C2/c space group, revealing high pH, solvent, and thermal stability. Luminescence sensing studies demonstrated that MOF-1 had the potential to be a highly selective, sensitive, and recyclable fluorescence sensor for the identification of DPA. Furthermore, fluorescent test paper was made to detect DPA promptly with color changes. The enhancement mechanism was established by the hydrogen-bonding interaction and photoinduced electron transfer transition between MOF-1 and DPA molecules.

Facile Synthesis of Tetraphenylethene (TPE)-Based Fluorophores Derived by π-Extended Systems: Opposite Mechanofluorochromism, Anti-Counterfeiting and Bioimaging.

Although remarkable progresses are achieved in the design and development of the mono-shift in photoluminescence for mechanofluorochromic materials, it is still a severe challenge to explore the opposite mechanofluorochromic materials with both blue- and red-shifted photoluminescence. Herein, two unprecedented 4,5-bis(TPE)-1H-imidazole fused pyridine or quinoline-based fluorophores X-1 and X-2 were designed and synthesized, and X-1 and X-2, exhibit completely opposite mechanofluorochromic behavior. Under UV lamp, the color of pristine X-1 changed from blue to green with reversible redshifted 27 nm in fluorescence emission spectra after ground, while the color of pristine X-2 changed from red to yellow with reversible blue-shifted 74 nm after ground. The detailed characterizations (including PXRD, SEM and DSC) confirmed that this opposite mechanofluorochromism was attributed to the transformation of order-crystalline and amorphous states. The crystal structure analysis and theoretical calculation further explain that opposite mechanofluorochromic behavior take into account different π-π stacking mode by induced π-extended systems. In addition, these TPE-based fluorophores (X-1 and X-2) exhibited excellent bio-compatibility and fluorescence properties for bio-imaging, writable data storage and anti-counterfeiting materials.

Preparation of Vinylphosphonates from Ketones Promoted by Tf2O.

An efficient triflic anhydride promoted phosphorylation of ketone was disclosed, and vinylphosphorus compounds were prepared under solvent- and metal-free conditions. Both aryl and alkyl ketones could perform smoothly to give vinyl phosphonates in high to excellent yields. In addition, the reaction was easy to carry out and easy to scale up. Mechanistic studies suggested that this transformation might involve nucleophilic vinylic substitution or a nucleophilic addition-elimination mechanism.

Boosting the Catalytic Performance of NiMoO4 Nanorods in H2 Generation upon NH3BH3 Hydrolysis via a Reduction Process.

Although a range of noble metal catalysts, including Ru, Rh, Pd, Pt, and Au, have been developed for efficient H2 generation upon NH3BH3 hydrolysis at room temperature, this is a highly urgent need for exploring earth-abundant metal nanocatalysts for H2 generation upon NH3BH3 hydrolysis. Herein, a NaBH4 reduction strategy was developed to boost the catalytic performance of NiMoO4 nanorods in H2 generation upon NH3BH3 hydrolysis. Indeed, the pristine NiMoO4 nanorods were catalytically inert in NH3BH3 hydrolysis. Significantly, the reduced NiMoO4 nanorods presented excellent catalytic activity in H2 generation upon NH3BH3 hydrolysis, with a turnover frequency (TOF) of 31.2 L(H2)·gcat-1·h-1. Interestingly, the TOF of NH3BH3 hydrolysis over reduced NiMoO4 nanorods significantly increased from 31.2 to 53.6 L(H2)·gcat-1·h-1 under 0.3 M NaOH. The boosting catalytic performance of NiMoO4 nanorods via NaBH4 reduction in H2 generation might be attributed to the higher content of Oads and the formation of nickel boride in the reduced NiMoO4 nanorods. In this work, NH3BH3 hydrolysis over reduced NiMoO4 nanorods was not only used for safe H2 generation but also for its in situ tandem hydrogenation in organic chemistry.

"On-Off" Control for On-Demand H2 Release upon Dimethylamineborane Hydrolysis over Ru0.8Ni0.2/MoS2 Nanohybrids.

In spite of the fact that remarkable developments are achieved in the design and development of novel nanocatalysts for H2 release upon dimethylamineborane hydrolysis, the development of an "on-off" switch for demand-based H2 evolution upon dimethylamineborane hydrolysis is still a matter of supreme importance, however. Herein, we synthesized a string of MoS2 nanosheet-supported RuNi bimetallic nanohybrids (RuxNi1-x/MoS2), by fixation of RuNi nanoparticles at the MoS2 surface, for the H2 evolution upon the hydrolysis of dimethylamineborane at 30 °C. For safely and effectively generating, transporting, and storing H2 gas, the selective "on-off" switch for on-demand H2 evolution upon dimethylamineborane hydrolysis over the Ru0.8Ni0.2/MoS2 nanohybrid has been successfully realized by the Zn2+/EDTA-2Na system. In particular, the H2 evolution is totally switched off by adding Zn(NO3)2. It seems that Zn2+ ions are attached and anchored at the Ru0.8Ni0.2/MoS2 surface, inhibiting their surface-active sites, leading to the termination of H2 evolution. Then, the H2 generation is subsequently reactivated by adding the EDTA-2Na solution because of its excellent coordination ability with Zn2+ ions. This study not only offers a new and efficient RuNi nanocatalyst for dimethylamineborane hydrolysis but also proposes a new method for the demand-based H2 production.

Interactions between Layered Double Hydroxide Nanoparticles and Egg Yolk Lecithin Liposome Membranes.

The burgeoning need to study the applications of nanoparticles (NPs) in biomedical and pharmaceutical fields requires an understanding of their interactions with lipid membranes for further in vivo studies. In this paper, negatively charged egg yolk lecithin liposome (EYL) has been prepared and used as model lipid membranes. Positively charged Mg3Al-layered double hydroxides (LDHs) are viewed as models of clay particles. The ability of the LDH NPs, a two-dimensional nanostructure with an average diameter of 100 nm (LDHs-100) or 500 nm (LDHs-500) to cross the membranes, has been thoroughly investigated via (high-resolution) transmission electron microscopy (TEM), optical microscopy (OM), scanning electron microscopy (SEM), confocal fluorescence microscopy (CLSM), and dynamic light scattering (DLS). The liposomes with an average diameter of 1.5 µm were prepared by the thin-film rehydration method followed by an extrusion technique. A calcein leakage assay and steady-state fluorescence measurement displayed the variation of membrane integrity and polarity of the pyrene-located microenvironment during the interaction between EYL and calcein-interacted LDH NPs (CE-LDHs) or LDH NPs, respectively. These results imply that not only spherical particles but also even more sophisticated nanostructured materials are able to effectively cross the lipid bilayers, thereby engineering new compounds that may be encapsulated for safe and potential use in biomedical applications.

Visible-Light-Induced Difunctionalization of Alkenyl Ketones with α-Carbonyl Alkyl Bromide: Concomitant Installation of C-C Bonds.

The visible-light-promoted difunctionalization of alkenyl ketones has been developed for easy access of various tetralones, cyclopropane, or alkenyl migration compounds. With fac-[Ir(ppy)3] as the photocatalyst, alkenyl ketones captured the α-carbonyl alkyl radical and evolved through intramolecular cyclization and the elimination of a proton to give the difunctionalized products. This strategy is characterized by good yields, mild reaction conditions, and outstanding functional group tolerance.

The stereoselective conversion of epimerized alkoxyl phosphine-borane to P,C, axial-stereogenic tertiary phosphine via cleavage of P-O bond.

The P-O bond of epimerized alkoxyl phosphine-borane was cleaved by naphthalene-lithium, to form two diastereomers of P-anions in a ratio of 86 : 14, which was then converted to secondary phosphine-borane via acidification, and to tertiary phosphines with alkyl halides with enhanced 96 : 4 dr. The isolated tertiary phosphine containing hydroxyl (in >99 : 1 dr) was converted to multi-stereogenic tertiary phosphines via O-alkylation with alkylene dihalides.

Genetic diversity and epidemiology of human rhinovirus among children with severe acute respiratory tract infection in Guangzhou, China.

BACKGROUND: Human rhinovirus (HRV) is one of the major viruses of acute respiratory tract disease among infants and young children. This work aimed to understand the epidemiological and phylogenetic features of HRV in Guangzhou, China. In addition, the clinical characteristics of hospitalized children infected with different subtype of HRV was investigated. METHODS: Hospitalized children aged < 14 years old with acute respiratory tract infections were enrolled from August 2018 to December 2019. HRV was screened for by a real-time reverse-transcription PCR targeting the viral 5'UTR. RESULTS: HRV was detected in 6.41% of the 655 specimens. HRV infection was frequently observed in children under 2 years old (57.13%). HRV-A and HRV-C were detected in 18 (45%) and 22 (55%) specimens. All 40 HRV strains detected were classified into 29 genotypes. The molecular evolutionary rate of HRV-C was estimated to be 3.34 × 10-3 substitutions/site/year and was faster than HRV-A (7.79 × 10-4 substitutions/site/year). Children who experienced rhinorrhoea were more common in the HRV-C infection patients than HRV-A. The viral load was higher in HRV-C detection group than HRV-A detection group (p = 0.0148). The median peak symptom score was higher in patients with HRV-C infection as compared to HRV-A (p = 0.0543), even though the difference did not significance. CONCLUSION: This study revealed the molecular epidemiological characteristics of HRV in patients with respiratory infections in southern China. Children infected with HRV-C caused more severe disease characteristics than HRV-A, which might be connected with higher viral load in patients infected with HRV-C. These findings will provide valuable information for the pathogenic mechanism and treatment of HRV infection.

Is Aromaticity a Driving Force in Catalytic Cycles? A Case from the Cycloisomerization of Enynes Catalyzed by All-Metal Aromatic Pd3+ Clusters and Carboxylic Acids.

The work details a mechanistic study based on density functional theory modeling on the cycloisomerization of polyunsaturated substrates catalyzed by all-metal aromatic tripalladium complexes and carboxylic acids. These clusters are an emerging class of catalysts for a variety of relevant transformations, including C-C forming processes that occur under mild conditions and display synthetic features complementary to those of established mononuclear complexes. This study is the first computational one devoted to the comprehension of the series of elementary steps involved in a synthetic transformation catalyzed by an all-metal aromatic complex. Present results confirm previous experimental hints on the striking mechanistic differences exerted by these clusters with respect to the usual cyclization pathways of related substrates. Moreover, the catalytic cycle involving present all-metal aromatic clusters closely parallels the mechanism of the aromatic substitution of regular arenes.

Laser-Induced Electron Transfer in the Dissociative Multiple Ionization of Argon Dimers.

We report on an experimental and theoretical study of the ionization-fragmentation dynamics of argon dimers in intense few-cycle laser pulses with a tagged carrier-envelope phase. We find that a field-driven electron transfer process from one argon atom across the system boundary to the other argon atom triggers subcycle electron-electron interaction dynamics in the neighboring atom. This attosecond electron-transfer process between distant entities and its implications manifests itself as a distinct phase-shift between the measured asymmetry of electron emission curves of the Ar^{+}+Ar^{2+} and Ar^{2+}+Ar^{2+} fragmentation channels. This letter discloses a strong-field route to controlling the dynamics in molecular compounds through the excitation of electronic dynamics on a distant molecule by driving intermolecular electron-transfer processes.

Metallopolymers for advanced sustainable applications.

Since the development of metallopolymers, there has been tremendous interest in the applications of this type of materials. The interest in these materials stems from their potential use in industry as catalysts, biomedical agents in healthcare, energy storage and production as well as climate change mitigation. The past two decades have clearly shown exponential growth in the development of many new classes of metallopolymers that address these issues. Today, metallopolymers are considered to be at the forefront for discovering new and sustainable heterogeneous catalysts, therapeutics for drug-resistant diseases, energy storage and photovoltaics, molecular barometers and thermometers, as well as carbon dioxide sequesters. The focus of this review is to highlight the advances in design of metallopolymers with specific sustainable applications.

Tomographic Extraction of the Internuclear Separation Based on Two-Center Interference with Aligned Diatomic Molecules.

We experimentally investigate the two-dimensional photoelectron momentum spectra of aligned diatomic molecules in an intense laser field. Our results reveal a novel prominent valley structure in the molecular alignment dependence of the high-energy photoelectron spectra along the laser polarization. Resorting to the molecular strong-field approximation and a simple semiclassical analysis, we show that this valley structure stems from the destructive two-center interference of the laser-driven rescattered electrons in diatomic molecules. Based on this two-center interference with aligned diatomic molecules, we demonstrate for the first time a tomographic method to extract the molecular internuclear separation, providing a more straightforward approach of molecular imaging, in comparison with, e.g., laser-induced electron diffraction and fixed-angle broadband laser-driven electron scattering.

Attosecond Molecular Angular Streaking with All-Ionic Fragments Detection.

Attosecond angular streaking (or "attoclock") is an insightful technique for probing the ultrafast electron dynamics in strong laser fields. Up until recently, this technique relied solely on an accurate measurement of the photoelectron momentum distribution and has remained restricted to atomic targets. Here, we propose a novel attosecond angular streaking scheme applicable to molecules, for which the ionic fragments of dissociative ionization are detected in the polarization plane of a close-to-circular polarized laser light. Our ionic attoclock measurements are consistent with theoretical results from a numerical solution of the time-dependent Schrödinger equation and an upper bound of 10 as on the tunneling time from the attoclock readings in the H_{2} molecule has been given, which is significantly smaller than any definitions of tunneling time available in the literatures.

[A new spirocyclic cycloartane triterpenoid from Souliea vaginata].

The 70% ethanol extract of the whole plant of Souliea vaginata was purified by multi-chromatographic methods including macroporous resin,silica gel,Sephadex LH-20,and C18-reversed-phase column chromatography. A new spirocyclic cycloartane triterpenoid was isolated and identified as( 16 R*,20 R*,23 S*,24 R*,25 S*)-16,23: 23,26-diepoxy-15α,24,25-trihydroxy-9,19-cycloart-3ß-O-ß-D-xylopyranoside( 1),and named as soulieoside S. Its planar structure and relative configuration were determined by spectroscopic techniques including 2 D NMR and HRESI-MS. As one of the main components of S. vaginata,compound 1 was evaluated for its anti-inflammatory activity by a lipopolysaccharide( LPS)-stimulated NO production model in RAW264. 7 macrophages,but it didn't show NO production inhibitory effect.

18F-Trifluoromethylation of Unmodified Peptides with 5-18F-(Trifluoromethyl)dibenzothiophenium Trifluoromethanesulfonate.

The 18F-labeling of 5-(trifluoromethyl)-dibenzothiophenium trifluoromethanesulfonate, commonly referred to as the Umemoto reagent, has been accomplished applying a halogen exchange 18F-fluorination with 18F-fluoride, followed by oxidative cyclization with Oxone and trifluoromethanesulfonic anhydride. This new 18F-reagent allows for the direct chemoselective 18F-labeling of unmodified peptides at the thiol cysteine residue.

Dentromers, a Family of Super Dendrimers with Specific Properties and Applications.

Dentromers (from dentro, δεντρο: tree in Greek), and meros (µÎµροσ, in greek: part) are introduced as a family of dendrimers constructed according to successive divergent 1 → 3 branching. The smaller dentromers have 27 terminal branches. With alcohol termini they were originally named arborols by Newkome, who pioneered 1 → 3 constructions of dendrimers and dendrons. Giant dentromers have been constructed and decorated in particular with ferrocene and other redox active groups. The synthesis, specific properties, and applications are examined in this mini review article dedicated to Don Tomalia, with an emphasis on dense peripheral packing favoring the functions of encapsulation, redox sensing, and micellar template for catalysis in water and aqueous solvents.