Sprayed water microdroplets containing dissolved pyridine spontaneously generate pyridyl anions.

The anion of pyridine, C5H5N−, has been thought to be short lived in the gas phase and was only previously observed indirectly. In the condensed phase, C5H5N− is known to be stabilized by solvation with other molecules. We provide in this study striking results for the formation of isolated C5H5N− from microdroplets of water containing dissolved pyridine observed in the negative ion mass spectrum. The gas-phase lifetime of C5H5N− is estimated to be at least 50 ms, which is much longer than previously thought. The generated C5H5N− captured CO2 molecules to form a stable (Py-CO2)− complex, further confirming the existence of C5H5N−. We propose that the high electric field at the air­water interface of a microdroplet helps OH− to transfer an electron to pyridine to form C5H5N− and the hydroxyl radical •OH. Oxidation products of the Py reacting with •OH are also observed in the mass spectrum recorded in positive mode, which further supports this mechanism. The present study pushes the limits of the reducing and oxidizing power of water microdroplets to a new level, emphasizing how different the behavior of microdroplets can be from bulk water. We also note that the easy formation of C5H5N− in water microdroplets presents a green chemistry way to synthesize value-added chemicals.

Fast Hydroxyl Radical Generation at the Air-Water Interface of Aerosols Mediated by Water-Soluble PM2.5 under Ultraviolet A Radiation.

Due to the adverse health effects and the role in the formation of secondary organic aerosols, hydroxyl radical (OH) generation by atmospheric fine particulate matter (PM) has been of particular research interest in both bulk solutions and the gas phase. However, OH generation by PM at the air-water interface of atmospheric water droplets, a unique environment where reactions can be accelerated by orders of magnitude, has long been overlooked. Using the field-induced droplet ionization mass spectrometry methodology that selectively samples molecules at the air-water interface, here, we show significant oxidation of amphiphilic lipids and isoprene mediated by water-soluble PM2.5 at the air-water interface under ultraviolet A irradiation, with the OH generation rate estimated to be 1.5 × 1016 molecule·s-1·m-2. Atomistic molecular dynamics simulations support the counter-intuitive affinity for the air-water interface of isoprene. We opine that it is the carboxylic chelators of the surface-active molecules in PM that enrich photocatalytic metals such as iron at the air-water interface and greatly enhance the OH generation therein. This work provides a potential new heterogeneous OH generation channel in the atmosphere.

High Electric Field on Water Microdroplets Catalyzes Spontaneous and Ultrafast Oxidative C-H/N-H Cross-Coupling.

Oxidative C-H/N-H cross-coupling has emerged as an atom-economical method for the construction of C-N bonds. Conventional oxidative C-H/N-H coupling requires at least one of the following: high temperatures, strong oxidizers, transition metal catalysts, organic solvents, light, and electrochemical cells. In this study, by merely spraying the water solutions of the substrates into microdroplets at room temperature, we show a series of oxidative C-H/N-H coupling products that are strikingly produced in a spontaneous and ultrafast manner. The reactions are accelerated by six orders of magnitude compared to the same reactions in the bulk. It has been previously proposed by fluorescence microscopy and theory that the spontaneously generated electric field at the microdroplets peripheries can be in the ∼109 V/m range. Based on mass spectrometric analysis of key radical intermediates, we opine that the ultrahigh electric field catalytically oxidizes the substrates by removing an electron, which further promotes C/N coupling. Taken together, we anticipate that microdroplet chemistry will be an avenue rich in green opportunities of constructing C-heteroatom bonds.

Spontaneous Reduction-Induced Degradation of Viologen Compounds in Water Microdroplets and Its Inhibition by Host-Guest Complexation.

Water serves as an inert environment for the dispersion and application of many kinds of herbicides. Viologen compounds, a type of widely used but highly toxic herbicide, are stable in bulk water, whose half-life can be up to 23 weeks in natural water, imposing a severe health risk to mammals. In this study, we present the striking results of the spontaneous and ultrafast reduction-induced degradation of three viologen compounds in water microdroplets and provide the concentration, time, temperature dependence, mechanism, and scale-up of the reactions. We postulate that the electrons existing at the air-water interface of the microdroplets due to the unique redox potential therein initiate the reduction, from which further degradation occurs. The host-guest complexation between cucurbit[7]uril and viologens only slightly changes the redox potential of viologens in the bulk but completely inhibits the reactions in microdroplets, adding to the uniqueness of the redox potentials at the air-water interfaces of microdroplets. Taken together, microdroplets might have been functioning as naturally occurring ubiquitous tiny electrochemical cells for a plethora of unique redox reactions that were thought to be impossible in the bulk water.

Fast Sulfate Formation Initiated by the Spin-Forbidden Excitation of SO2 at the Air-Water Interface.

The multiphase oxidation of SO2 to sulfate in aerosol particles is a key process in atmospheric chemistry. However, there is a large gap between the observed and simulated sulfate concentrations during severe haze events. To fill in the gaps in understanding SO2 oxidation chemistry, a combination of experiments and theoretical calculations provided evidence for the direct, spin-forbidden excitation of SO2 to its triplet states using UVA photons at an air-water interface, followed by reactions with water and O2 that facilitate the rapid formation of sulfate. The estimated reaction energy for the whole process, 3SO2 + H2O + 1/2O2 → HSO4- + H+ (298 K, 1 M), was ΔGr = -107.8 kcal·mol-1. Moreover, calculations revealed that this was a multistep reaction involving submerged, small energy barriers (∼10 kcal·mol-1). These results indicate that photochemical oxidation of SO2 at the air-water interface with solar actinic light may be an important unaccounted source of sulfate aerosols under polluted haze conditions.

Certification of Genuine Multipartite Entanglement with General and Robust Device-Independent Witnesses.

Genuine multipartite entanglement represents the strongest type of entanglement, which is an essential resource for quantum information processing. Standard methods to detect genuine multipartite entanglement, e.g., entanglement witnesses, state tomography, or quantum state verification, require full knowledge of the Hilbert space dimension and precise calibration of measurement devices, which are usually difficult to acquire in an experiment. The most radical way to overcome these problems is to detect entanglement solely based on the Bell-like correlations of measurement outcomes collected in the experiment, namely, device independently. However, it is difficult to certify genuine entanglement of practical multipartite states in this way, and even more difficult to quantify it, due to the difficulty in identifying optimal multipartite Bell inequalities and protocols tolerant to state impurity. In this Letter, we explore a general and robust device-independent method that can be applied to various realistic multipartite quantum states in arbitrary finite dimension, while merely relying on bipartite Bell inequalities. Our method allows us both to certify the presence of genuine multipartite entanglement and to quantify it. Several important classes of entangled states are tested with this method, leading to the detection of genuinely entangled states. We also certify genuine multipartite entanglement in weakly entangled Greenberger-Horne-Zeilinger states, showing that the method applies equally well to less standard states.

ThH5 : An Actinide-Containing Superhalogen Molecule.

Thorium and its compounds have been widely investigated as important nuclear materials. Previous research focused on the potential use of thorium hydrides, such as ThH2 , ThH4 , and Th4 H15 , as nuclear fuels. Here, we report studies of the anion, ThH5- , by anion photoelectron spectroscopy and computations. The resulting experimental and theoretical vertical detachment energies (VDE) for ThH5- are 4.09 eV and 4.11 eV, respectively. These values and the agreement between theory and experiment facilitated the characterization of the structure of the ThH5- anion and showed its neutral counterpart, ThH5 to be a superhalogen. ThH5- , which exhibits a C4v structure with five Th-H single bonds, possesses the largest known H/M ratio among the actinide elements, M. The adaptive natural density partitioning (AdNDP) method was used to further analyze the chemical bonding of ThH5- and to confirm the existence of five Th-H single bonds in the ThH5- molecular anion.

BMSC-derived exosomes ameliorate sulfur mustard-induced acute lung injury by regulating the GPRC5A-YAP axis.

Sulfur mustard (SM) is a highly toxic chemical warfare agent that causes acute lung injury (ALI) and/or acute respiratory distress syndrome (ARDS). There are no effective therapeutic treatments or antidotes available currently to counteract its toxic effects. Our previous study shows that bone marrow-derived mesenchymal stromal cells (BMSCs) could exert therapeutic effects against SM-induced lung injury. In this study, we explored the therapeutic potential of BMSC-derived exosomes (BMSC-Exs) against ALI and the underlying mechanisms. ALI was induced in mice by injection of SM (30 mg/kg, sc) at their medial and dorsal surfaces. BMSC-Exs (20 µg/kg in 200 µL PBS, iv) were injected for a 5-day period after SM exposure. We showed that BMSC-Exs administration caused a protective effect against pulmonary edema. Using a lung epithelial cell barrier model, BMSC-Exs (10, 20, 40 µg) dose-dependently inhibited SM-induced cell apoptosis and promoted the recovery of epithelial barrier function by facilitating the expression and relocalization of junction proteins (E-cadherin, claudin-1, occludin, and ZO-1). We further demonstrated that BMSC-Exs protected against apoptosis and promoted the restoration of barrier function against SM through upregulating G protein-coupled receptor family C group 5 type A (GPRC5A), a retinoic acid target gene predominately expressed in the epithelial cells of the lung. Knockdown of GPRC5A reduced the antiapoptotic and barrier regeneration abilities of BMSC-Exs and diminished their therapeutic effects in vitro and in vivo. BMSC-Exs-caused upregulation of GPRC5A promoted the expression of Bcl-2 and junction proteins via regulating the YAP pathway. In summary, BMSC-Exs treatment exerts protective effects against SM-induced ALI by promoting alveolar epithelial barrier repair and may be an alternative approach to stem cell-based therapy.

Beating Standard Quantum Limit with Weak Measurement.

Weak measurements have been under intensive investigation in both experiment and theory. Numerous experiments have indicated that the amplified meter shift is produced by the post-selection, yielding an improved precision compared to conventional methods. However, this amplification effect comes at the cost of a reduced rate of acquiring data, which leads to an increasing uncertainty to determine the level of meter shift. From this point of view, a number of theoretical works have suggested that weak measurements cannot improve the precision, or even damage the metrology information due to the post-selection. In this review, we give a comprehensive analysis of the weak measurements to justify their positive effect on prompting measurement precision. As a further step, we introduce two modified weak measurement protocols to boost the precision beyond the standard quantum limit. Compared to previous works beating the standard quantum limit, these protocols are free of using entangled or squeezed states. The achieved precision outperforms that of the conventional method by two orders of magnitude and attains a practical Heisenberg scaling up to n=106 photons.

Extracting information from single qubits among multiple observers with optimal weak measurements.

In the context of quantum information, major efforts have been made to maximize the mutual information by measuring single copies of signal states. In general, one execution of optimal projective measurement extracts all the accessible mutual information. However, in some scenarios, weak measurements are preferred because of kinds of specific requirements, e.g., to distribute secret keys to multi-observers. In this study, we propose a method to construct optimal weak measurements for multi-party quantum communications. Utilizing the method in [Physical Review Letters 120, 160501 (2018)] to classify the mutual information, the theoretical study shows that by successively performing this optimal weak measurement, all accessible information can be obtained by multiple observers. This conclusion is experimentally verified by a cascaded measurement apparatus that can perform six successive weak measurements on heralded single photons. The experimental results clearly indicate that almost all accessible mutual information is extracted by this sequence of optimal weak measurements; meanwhile, none of the information is destroyed or residual. Thus, this optimal weak measurement is an efficient and reliable tool for performing quantum communication tasks. The consistence between the experimental and theoretical results verifies that the classifying method in [Phys. Rev. Lett.120, 160501 (2018)] can be applied to characterize realistic quantum measurements.

Magic Clusters PtMg2,3 H5 - Facilitated by Local σ-Aromaticity.

The concept of local aromaticity has been successfully utilized in understanding the stability of certain atomic clusters. However, all the skeleton atoms in these clusters are covered by at least one local aromatic feature, collectively making the multiple local aromaticities coexist globally. Herein we show the robustness of local aromaticity as a tool for the discovery of novel magic clusters: not all of the skeleton atoms need to be covered by an aromatic feature to make the cluster magic. In this study, the PtMg2,3 H5 - cluster anions are generated by a unique high-current pulsed discharge ion source and found to be magic numbers using mass spectrometry. Photoelectron spectroscopy and calculations confirm that only the PtH4 2- kernels in these clusters are locally aromatic. Based on these results, we propose that local aromaticity can be gainfully utilized as a new potential magic rule in the search for magic numbers.

Probe-Free Direct Identification of Type†I and Type†II Photosensitized Oxidation Using Field-Induced Droplet Ionization Mass Spectrometry.

While Type I and Type II photosensitizers are often carefully tailored to achieve their respective advantages in treating different cancers, the identifications of the Type I and II mechanisms as such, the key reaction intermediates, and the consequent oxidation products of the substrates have never been easy. Using our unique home-built field-induced droplet ionization mass spectrometry (FIDI-MS) method that selectively samples molecules at the air-water interface, here we show the facile determination of both Type I and II mechanisms of a poster-child photosensitizer, temoporfin, without the addition of any probes. The unstable doublet radical resulting from the hydrogen abstraction by the triplet temoporfin through the Type I mechanism is captured, manifesting the in situ advantage of FIDI-MS. We anticipate that the method developed in this study can be widely utilized in the future designs of novel photosensitizers and the screening of their photosensitization mechanisms.

Host-Guest Complexation of Amphiphilic Molecules at the Air-Water Interface Prevents Oxidation by Hydroxyl Radicals and Singlet Oxygen.

The oxidation of antioxidants by oxidizers imposes great challenges to both living organisms and the food industry. Here we show that the host-guest complexation of the carefully designed, positively charged, amphiphilic guanidinocalix[5]arene pentadodecyl ether (GC5A-12C) and negatively charged oleic acid (OA), a well-known cell membrane antioxidant, prevents the oxidation of the complex monolayers at the air-water interface from two potent oxidizers hydroxyl radicals (OH) and singlet delta oxygen (SDO). OH is generated from the gas phase and attacks from the top of the monolayer, while SDO is generated inside the monolayer and attacks amphiphiles from a lateral direction. Field-induced droplet ionization mass spectrometry results have demonstrated that the host-guest complexation achieves steric shielding and prevents both types of oxidation as a result of the tight and "sleeved in" physical arrangement, rather than the chemical reactivity, of the complexes.

Spectroscopic Measurement of a Halogen Bond Energy.

Halogen bonding (XB) has emerged as an important bonding motif in supramolecules and biological systems. Although regarded as a strong noncovalent interaction, benchmark measurements of the halogen bond energy are scarce. Here, a combined anion photoelectron spectroscopy and density functional theory (DFT) study of XB in solvated Br- anions is reported. The XB strength between the positively-charged σ-hole on the Br atom of the bromotrichloromethane (CCl3 Br) molecule and the Br- anion was found to be 0.63 eV (14.5 kcal mol-1 ). In the neutral complexes, Br(CCl3 Br)1,2 , the attraction between the free Br atom and the negatively charged equatorial belt on the Br atom of CCl3 Br, which is a second type of halogen bonding, was estimated to have interaction strengths of 0.15 eV (3.5 kcal mol-1 ) and 0.12 eV (2.8 kcal mol-1 ).

A study of anaesthesia-related cardiac arrest from a Chinese tertiary hospital.

BACKGROUND: The present survey evaluated the incidence of perioperative cardiac arrests in a Chinese tertiary general teaching hospital over ten years. METHODS: The incidence of cardiac arrest that occurred within 24 h of anaesthesia administration was retrospectively identified in the Third Affiliated Hospital of Sun Yat-Sen University between August 2007 and October 2017. Overall, 152,513 anaesthetics were included in the study period. Data collected included patient characteristics, American Society of Anaesthesiologists (ASA) physical status score, surgical specialty and anaesthesia technique. Cardiac arrests were assigned to one of three groups: "anaesthesia-related", "anaesthesia-contributing" or "anaesthesia-unrelated". RESULTS: In total, 104 cardiac arrests (6.8:10,000) and 34 deaths (2.2:10,000) were obtained. Among them, eleven cardiac arrests events were anaesthesia-related, resulting in an incidence of 0.7 per 10,000 anaesthetics. Sixteen cardiac arrests events were found to be anaesthesia-contributing, resulting in an incidence of 1.0 per 10,000 anaesthetics. Cardiovascular adverse events were the major events that contributed to anaesthesia-related cardiac arrest. Differences were found between events related and unrelated to anaesthesia with regard to ASA physical status and anaesthesia technique (P < 0.05). CONCLUSIONS: Anaesthesia-related cardiac arrest occurred in 11 of 104 cardiac arrests within 24 h of anaesthesia administration. Most cardiac arrests related to anaesthesia were due to cardiovascular events, including arrhythmia and hypotension after intravenous narcotic, as well as haemorrhage. ASA physical status of at least 3 and subarachnoid block appeared to be relevant risk factors for anaesthesia-related cardiac arrest.

Composite antibacterial hydrogels based on two natural products pullulan and ε-poly-l-lysine for burn wound healing.

Antibacterial hydrogels as burn wound dressings are capable of efficaciously defending against bacterial infection and accelerating burn wound healing. Thus far, a large plethora of antibacterial hydrogels have adopted numerous components and intricate preparation processes, yet restricting their practical industrialization applications. Simple and effective preparation methods of antibacterial hydrogels are hence urgently needed. Herein, an easy but efficacious strategy with the employment of two natural products pullulan and ε-poly-l-lysine (ε-PL) was designed to fabricate composite antibacterial hydrogels for burn wound healing for the first time. The hydrogel crosslinking networks were formed through amidation reactions between carboxylated pullulan derivative (CP) and ε-poly-l-lysine hydrochloride (ε-PL·HCl). The resulting hydrogels possessed high transparency, porous structures, tunable gelation time and gel content, relatively low swelling ratios, appropriate self-degradability, proper mechanical properties, strong in vitro bacteriostatic activities, non-cytotoxicity, capacities of facilitating cell migration and excellent hemocompatibility. In the infected burn model of mice, the hydrogels were observed to display prominent in vivo antibacterial activities and enable the acceleration of burn wound healing. We opine the simply and effectively prepared antibacterial hydrogels as promising dressings for burn wound recovery have broad industrialization prospects.

The Spontaneous Electron-Mediated Redox Processes on Sprayed Water Microdroplets.

Water is considered as an inert environment for the dispersion of many chemical systems. However, by simply spraying bulk water into microsized droplets, the water microdroplets have been shown to possess a large plethora of unique properties, including the ability to accelerate chemical reactions by several orders of magnitude compared to the same reactions in bulk water, and/or to trigger spontaneous reactions that cannot occur in bulk water. A high electric field (∼109 V/m) at the air-water interface of microdroplets has been postulated to be the probable cause of the unique chemistries. This high field can even oxidize electrons out of hydroxide ions or other closed-shell molecules dissolved in water, forming radicals and electrons. Subsequently, the electrons can trigger further reduction processes. In this Perspective, by showing a large number of such electron-mediated redox reactions, and by studying the kinetics of these reactions, we opine that the redox reactions on sprayed water microdroplets are essentially processes using electrons as the charge carriers. The potential impacts of the redox capability of microdroplets are also discussed in a larger context of synthetic chemistry and atmospheric chemistry.

Mass Spectrometry and Cryogenic Electron Microscopy Illuminate Molecular-Level Mechanisms of the Oxidative and Structural Damage to Lipid Membranes by Radical-Bearing Graphene Oxide.

Biomedical applications of graphene in tumor and bacterial treatment have become cutting-edge fields due to its unique physical and chemical properties. However, a mechanistic understanding of the interactions and reactions between graphene-based material and biological systems such as lipid membranes remains elusive, especially at the molecular level. By using the unique field-induced droplet ionization mass spectrometry and cryogenic electron microscopy methodologies, we reveal the oxidation products of monolayer lipid membranes at the air-water interface and the change in the morphology of bilayer lipid membranes in an aqueous solution caused by the incorporation of graphene oxide bearing π-conjugated carbon radicals [hydrated graphene oxide (hGO)]. We discovered that hGO is an efficient source of hydroxyl radicals and that it is not only the incorporation of the hGO sheets but also the irregular packing of the lipid oxides from the hydroxyl radical oxidation that causes the structural distortions of the liposomes.

Beyond lipid peroxidation: Distinct mechanisms observed for POPC and POPG oxidation initiated by UV-enhanced Fenton reactions at the air-water interface.

Fenton or Fenton-like reactions are ubiquitous in nature, and the hydroxyl radicals (·OH) generated in these reactions are accountable for a plethora of oxidation processes both in the environment and in vivo. Among these oxidation reactions, lipid oxidation initiated by ·OH radicals has long been oversimplified as a peroxidation mechanism, but in reality, it is a highly complicated process that can result in a large variety of products. Using the unique field-induced droplet ionization mass spectrometry (FIDI-MS) methodology that is capable of selective sampling of amphiphilic molecules that reside at the air-water interface, here, we show distinct mechanisms from the ultraviolet (UV)-enhanced Fenton oxidations of two phospholipids, POPC and POPG, even though these two lipids possess the same functional groups that are vulnerable to ·OH attack. We postulate that it is the different packing densities that determine the permeability of ambient NO molecules into the monolayers, resulting in highly distinct reaction pathways and products. We anticipate that this work will be a wake-up call that the lipid peroxidation mechanism is sometimes taken for granted and that lipid oxidation can be subtly affected by various factors that deserves deeper investigations.