One Carbon Ring Expansion of Bipyrrole to Bipyridine Enables Access to a π-Extended, Non-innocent, Corrole-like Ligand.

A π-extended, diaza-triphenylene embedded, mono-anionic corrole analogue and its NiII complex were synthesized from a diaza-triphenylene precursor, which was obtained from a double one-carbon insertion into a naphthobipyrrole diester. Following conversion to the corresponding activated diol and acid-catalyzed condensation with pyrrole, subsequent reaction with pentafluorobenzaldehyde afforded mono-anionic, π-extended bipyricorrole-like macrocycle. Attempted NiII insertion with Ni(OAc)2 ⋅ 4H2 O resulted an ESR active, NiII bipyricorrole radical complex, which was converted to a stable cationic NiII complex upon treatment with [(Et3 O)+ (SbCl6 )- ]. Both complexes were characterized by 1 H and 13 C NMR, UV/Vis spectroscopy and single crystal X-ray diffraction analysis. The NiII bipyricorrole radical complex is converted to a cationic NiII complex by single-electron reduction using cobaltocene. Both the cationic NiII complex and the radical NiII complex exhibited ligand-centered redox behavior, whereas the NiII remains in the +2 oxidation state.

Effect-Directed Analysis Combined with Nontarget Screening to Identify Unmonitored Toxic Substances in the Environment.

Effect-directed analysis (EDA) combined with nontarget screening (NTS) has established a valuable tool for the identification of unmonitored toxic substances in environmental samples. It consists of three main steps: (1) highly potent fraction identification, (2) toxicant candidate selection, and (3) major toxicant identification. Here, we discuss the methodology, current status, limitations, and future challenges of EDA combined with NTS. This method has been applied successfully to various environmental samples, such as sediments, wastewater treatment plant effluents, and biota. We present several case studies and highlight key results. EDA has undergone significant technological advancements in the past 20 years, with the establishment of its key components: target chemical analysis, bioassays, fractionation, NTS, and data processing. However, it has not been incorporated widely into environmental monitoring programs. We provide suggestions for the application of EDA combined with NTS in environmental monitoring programs and management, with the identification of further research needs.

Identification of Mid-Polar and Polar AhR Agonists in Cetaceans from Korean Coastal Waters: Application of Effect-Directed Analysis with Full-Scan Screening.

Major aryl hydrocarbon receptor (AhR) agonists were identified in extracts of blubber, liver, and muscle from six long-beaked common dolphins (Delphinus capensis) and one fin whale (Balaenoptera physalus) collected from Korean coastal waters using effect-directed analysis. Results of the H4IIE-luc bioassay indicated that the polar fractions of blubber and liver extracts from the fin whale exhibited relatively high AhR-mediated potencies. Based on full-scan screening with high-resolution mass spectrometry, 37 AhR agonist candidates, spanning four use categories: pharmaceuticals, pesticides, cosmetics, and natural products, were selected. Among these, five polar AhR agonists were newly identified through toxicological confirmation. Concentrations of polar AhR agonists in cetaceans were tissue-specific, with extracts of blubber and liver containing greater concentrations than muscle extracts. Polar AhR agonists with great log KOA values (>5) were found to biomagnify in the marine food chain potentially. Polar AhR agonists contributed 8.9% of the observed AhR-mediated potencies in blubber and 49% in liver. Rutaecarpine and alantolactone contributed significantly to the total AhR-mediated potencies of blubber, whereas hydrocortisone was a major AhR contributor in the liver of the fin whale. This study is the first to identify the tissue-specific accumulation of polar AhR agonists in blubber and liver extracts of cetaceans.

Encapsulation of Clofazimine by Cyclodextran: Preparation, Characterization, and In Vitro Release Properties.

This study aimed to evaluate and compare the efficacy of cyclodextrans (CIs) and cyclodextrins (CDs) in improving the water solubility of a poorly water-soluble drug, clofazimine (CFZ). Among the evaluated CIs and CDs, CI-9 exhibited the highest percentage of drug inclusion and the highest solubility. Additionally, CI-9 showed the highest encapsulation efficiency, with a CFZ:CI-9 molar ratio of 0.2:1. SEM analysis indicated successful formation of inclusion complexes CFZ/CI and CFZ/CD, accounting for the rapid dissolution rate of the inclusion complex. Moreover, CFZ in CFZ/CI-9 demonstrated the highest drug release ratio, reaching up to 97%. CFZ/CI complexes were found to be an effective means of protecting the activity of CFZ against various environmental stresses, particularly UV irradiation, compared to free CFZ and CFZ/CD complexes. Overall, the findings provide valuable insights into designing novel drug delivery systems based on the inclusion complexes of CIs and CDs. However, further studies are needed to investigate the effects of these factors on the release properties and pharmacokinetics of encapsulated drugs in vivo, in order to ensure the safety and efficacy of these inclusion complexes. In conclusion, CI-9 is a promising candidate for drug delivery systems, and CFZ/CI complexes could be a potential formulation strategy for the development of stable and effective drug products.

Entangling three identical particles via spatial overlap.

Quantum correlations between identical particles are at the heart of quantum technologies. Several studies with two identical particles have shown that the spatial overlap and indistinguishability between the particles are necessary for generating bipartite entanglement. On the other hand, researches on the extension to more than two-particle systems are limited by the practical difficulty to control multiple identical particles in laboratories. In this work, we propose schemes to generate two fundamental classes of genuine tripartite entanglement, i.e., GHZ and W classes, which are experimentally demonstrated using linear optics with three identical photons. We also show that the tripartite entanglement class decays from the genuine entanglement to the full separability as the particles become more distinguishable from each other. Our results support the prediction that particle indistinguishability is a fundamental element for entangling identical particles.

Demonstration of Complete Information Trade-Off in Quantum Measurement.

While an information-disturbance trade-off in quantum measurement has been at the core of foundational quantum physics and constitutes a basis of secure quantum information processing, recently verified reversibility of a quantum measurement requires to refine it toward a complete version of information trade-off in quantum measurement. Here we experimentally demonstrate a trade-off relation among all information contents, i.e., information gain, disturbance, and reversibility in quantum measurement. By exploring quantum measurements applied on a photonic qutrit, we observe that the information of a quantum state is split into three distinct parts accounting for the extracted, disturbed, and reversible information. We verify that such different parts of information are in trade-off relations not only pairwise but also triplewise all at once, and find that the triplewise relation is tighter than any of the pairwise relations. Finally, we realize optimal quantum measurements that inherently preserve quantum information without loss of information, which offer wider applications in measurement-based quantum information processing.

Molecular Characterization of Estrogen Receptor Agonists during Sewage Treatment Processes Using Effect-Directed Analysis Combined with High-Resolution Full-Scan Screening.

Endocrine-disrupting potential was evaluated during the sewage treatment process using in vitro bioassays. Aryl hydrocarbon receptor (AhR)-, androgen receptor (AR)-, glucocorticoid receptor (GR)-, and estrogen receptor (ER)-mediated activities were assessed over five steps of the treatment process. Bioassays of organic extracts showed that AhR, AR, and GR potencies tended to decrease through the sewage treatment process, whereas ER potencies did not significantly decrease. Bioassays on reverse-phase high-performance liquid chromatography fractions showed that F5 (log KOW 2.5-3.0) had great ER potencies. Full-scan screening of these fractions detected two novel ER agonists, arenobufagin and loratadine, which are used pharmaceuticals. These compounds accounted for 3.3-25% of the total ER potencies and 4% of the ER potencies in the final effluent. The well-known ER agonists, estrone and 17ß-estradiol, accounted for 60 and 17% of the ER potencies in F5 of the influent and primary treatment, respectively. Fourier transform ion cyclotron resonance mass spectrometry analysis showed that various molecules were generated during the treatment process, especially CHO and CHOS (C: carbon, H: hydrogen, O: oxygen, and S: sulfur). This study documented that widely used pharmaceuticals are introduced into the aquatic environments without being removed during the sewage treatment process.

All-fiber integrated saturable absorber-tunable wavelength filter for Q-switching laser in both C- and L-bands.

We proposed and experimentally demonstrated combining a nonlinear optic saturable absorber and a wideband-tunable spectral filter in a single graphene oxide (GO) film deposited fiber optic device. The GO film was prepared on the cleaved facet of an optical fiber applying two sequential processes: the electrical deposition to make a thick GO film using an arc fusion splicer, followed by the laser pulse drilling to form a multi-layered GO film. The GO deposited fiber facet and a pristine fiber facet formed an asymmetric Fabry-Perot interferometer (FPI), whose spectral response was flexibly controlled by adjusting the air gap between them. An all-fiber ring laser cavity was built using the proposed device as a tunable saturable absorber along with erbium-doped fiber as a gain medium in the L-band. Stable Q-switching laser pulse trains were successfully generated, whose pulse duration was in the order of a few microseconds and its peak wavelength was tunable over 40nm from 1564 to 1604nm covering both C-and L-bands. At a certain condition, we also obtained Q-switching pulses simultaneously lasing at the double wavelengths, 1573.3 and 1586.7nm. Detailed device fabrication processes and laser characteristics are described to elucidate the high potential of 2-dimensional material films in nonlinear optics.

Implementation of a 3 × 3 directionally-unbiased linear optical multiport.

Linear optical multiports are widely used in photonic quantum information processing. Naturally, these devices are directionally-biased since photons always propagate from the input ports toward the output ports. Recently, the concept of directionally-unbiased linear optical multiports was proposed. These directionally-unbiased multiports allow photons to propagate along a reverse direction, which can greatly reduce the number of required linear optical elements for complicated linear optical quantum networks. Here, we report an experimental demonstration of a 3 × 3 directionally-unbiased linear optical fiber multiport using an optical tritter and mirrors. Compared to the previous demonstration using bulk optical elements which works only with light sources with a long coherence length, our experimental directionally-unbiased 3 × 3 optical multiport does not require a long coherence length since it provides negligible optical path length differences among all possible optical trajectories. It can be a useful building block for implementing large-scale quantum walks on complex graph networks.

Improved cortical activity and reduced gait asymmetry during poststroke self-paced walking rehabilitation.

BACKGROUND: For patients with gait impairment due to neurological disorders, body weight-supported treadmill training (BWSTT) has been widely used for gait rehabilitation. On a conventional (passive) treadmill that runs at a constant speed, however, the level of patient engagement and cortical activity decreased compared with gait training on the ground. To increase the level of cognitive engagement and brain activity during gait rehabilitation, a self-paced (active) treadmill is introduced to allow patients to actively control walking speed, as with overground walking. METHODS: To validate the effects of self-paced treadmill walking on cortical activities, this paper presents a clinical test with stroke survivors. We hypothesized that cortical activities on the affected side of the brain would also increase during active walking because patients have to match the target walking speed with the affected lower limbs. Thus, asymmetric gait patterns such as limping or hobbling might also decrease during active walking. RESULTS: Although the clinical test was conducted in a short period, the patients showed higher cognitive engagement, improved brain activities assessed by electroencephalography (EEG), and decreased gait asymmetry with the self-paced treadmill. As expected, increases in the spectral power of the low γ and ß bands in the prefrontal cortex (PFC), premotor cortex (PMC), and supramarginal gyrus (SG) were found, which are possibly related to processing sensory data and planning voluntary movements. In addition, these changes in cortical activities were also found with the affected lower limbs during the swing phase. Since our treadmill controller tracked the swing speed of the leg to control walking speed, such results imply that subjects made substantial effort to control their affected legs in the swing phase to match the target walking speed. CONCLUSIONS: The patients also showed reduced gait asymmetry patterns. Based on the results, the self-paced gait training system has the potential to train the symmetric gait and to promote the related cortical activities after stroke. Trial registration Not applicable.

Post Synthetic Modification of Planar Antiaromatic Hexaphyrin (1.0.1.0.1.0) by Regio-Selective, Sequential SNAr.

In spite of unique structural, spectroscopic and redox properties, the synthetic variants of the planar, antiaromatic hexaphyrin (1.0.1.0.1.0) derivatives 2, has been limited due to the low yields and difficulty in access to the starting material. A chemical modification of the meso-substituents could be good alternative overcoming the synthetic barrier. Herein, we report a regio-selective nucleophilic aromatic substitution (SNAr) of meso-pentafluorophenyl group in rosarrin 2 with catechol. The reaction afforded benzodioxane fused rosarrin 3 as single product with high yield. The intrinsic antiaromatic character of the starting rosarrin 2 retained throughout the reactions. Clean, two electron reduction was achieved by treatment of 3 with SnCl2•2H2O affording 26π-electron aromatic rosarrin 4. The synthesized compounds exhibited noticeable changes in photophysical and redox properties compared with starting rosarrin 2.

Effects of superfine grinding using ball-milling on the physical properties, chemical composition, and antioxidant properties of Quercus salicina (Blume) leaf powders.

BACKGROUND: Quercus salicina (Blume) leaves are traditionally used as folk medicine in some Asian countries. The aim of this study was to evaluate the effects of ball milling for different periods (0, 6, 12, 18, and 24 h) on the physicochemical properties of superfine Quercus salicina (Blume) leaf (QSL) powders. RESULTS: The particle sizes, water-holding capacity, angle of repose, and redness of the superfine QSL powder decreased with increasing ball-milling times, whereas the water solubility index, bulk density, tapped density, brightness, and yellowness were found to increase. Significantly higher (P > 0.05) total phenolic and flavonoid contents, and antioxidant activities, were observed for the superfine QSL powders obtained after 24 h ball-milling time. A total of 12 phenolic compounds in free and cell-wall-bound forms were quantified in the superfine QSL powder. Free phenolics such as protocatechuic acid, caffeic acid, rutin, and p-coumaric acid were increased and all cell-wall-bound phenolics were decreased with increasing ball-milling times. The antioxidant activity of the free phenolics increased with increasing ball-milling times, and the cell-wall-bound forms decreased. CONCLUSION: Superfine grinding by ball milling for 24 h can thus be used to produce superfine QSL powder with higher free phenolic metabolite content and antioxidant activity, and improved water solubility index, color, bulk, and tapped densities. This study will be useful for the food / nutraceutical / pharmaceutical industries in the manufacturing of active food ingredients or value-added products using QSL powders. © 2020 Society of Chemical Industry.

Reference-frame-independent, measurement-device-independent quantum key distribution using fewer quantum states.

Reference-frame-independent quantum key distribution (RFI-QKD) provides a practical way to generate secret keys between two remote parties without sharing common reference frames. On the other hand, measurement-device-independent QKD (MDI-QKD) offers a high level of security, as it is immune to all quantum hacking attempts to measurement devices. The combination of these two QKD protocols, i.e., RFI-MDI-QKD, is one of the most fascinating QKD protocols, since it holds advantages of both practicality and security. For further practicality of RFI-MDI-QKD, it is beneficial to reduce the implementation complexity. Here, we show that RFI-MDI-QKD can be implemented using fewer quantum states than those of its original proposal. We find that, in principle, the number of quantum states for one of the parties can be reduced from six to three without compromising security. Compared to conventional RFI-MDI-QKD where both parties transmit six quantum states, it significantly simplifies the implementation of the QKD protocol. We also verify the feasibility of the scheme with a proof-of-principle experiment.

Noncovalent Intermolecular Interaction in Cofacially Stacked 24π Antiaromatic Hexaphyrin Dimer.

π-π Stacking is omnipresent not only in nature but in a wide variety of practical fields applied to our lives. Because of its importance in a performance of natural and artificial systems, such as light harvesting system and working layer in device, many researchers have put intensive effort into identifying its underlying nature. However, for the case of π-π stacked systems composed of antiaromatic units, the understanding of the fundamental mechanisms is still unclear. Herein, we synthesized a new type of planar ß,ß'-phenylene-bridged hexaphyrin (1.0.1.0.1.0), referred as naphthorosarin which possesses the 24π-electron conjugated pathway. Especially, the corresponding antiaromatic porphyrinoid shows the unique property to form dimeric species adopting the face-to-face geometry which is unprecedented in cases of known annulated naphthorosarins. In order to elucidate the intriguing properties derived from the stacked dimer, the current study focuses on the experimental support to rationalize the observed π-π interactions between the two subunits.

Multiple Bioassays and Targeted and Nontargeted Analyses to Characterize Potential Toxicological Effects Associated with Sediments of Masan Bay: Focusing on AhR-Mediated Potency.

An enhanced, multiple lines of evidence approach was applied to assess potential toxicological effects associated with polluted sediments. Two in vitro bioassays (H4IIE-luc and Vibrio fischeri) and three in vivo bioassays (microalgae: Isochrysis galbana and Phaeodactylum tricornutum; zebrafish embryo: Danio rerio) were applied. To identify causative chemicals in samples, targeted analyses (polycyclic aromatic hydrocarbons (PAHs), styrene oligomers (SOs), and alkylphenols) and nontargeted full-scan screening analyses (FSA; GC- and LC-QTOFMS) were performed. First, great AhR-mediated potencies were observed in midpolar and polar fractions of sediment extracts, but known and previously characterized AhR agonists, including PAHs and SOs could not fully explain the total potencies of samples. Enoxolone was identified as a novel AhR agonist in a highly potent sediment fraction by use of FSA. Enoxolone has a relative potency of 0.13 compared to benzo[a]pyrene (1.0) in the H4IIE-luc bioassay. Nonylphenols associated with membrane damage that influenced the viability of the microalgae were also observed. Finally, inhibitions of bioluminescence of V. fischeri and lethality of D. rerio embryos were strongly related to nonpolar compounds. Overall, the present work addressed assay- and end point-specific variations and sensitivities for potential toxicities of mixture samples, warranting a significant utility of the "multiple lines of evidence" approach in ecological risk assessment.

Trapping of Stable [4n+1] π-Electron Species from Peripherally Substituted, Conformationally Rigid, Antiaromatic Hexaphyrins.

Peripherally substituted antiaromatic naphthorosarins have been synthesized for the first time. The synthesis was accomplished by acid-catalyzed condensation of naphthobipyrrole building blocks with aromatic aldehydes. The naphthobipyrrole building blocks were synthesized by simple oxidative coupling of the corresponding pyrrole substituted aromatics. Solid-state structural analyses of the synthesized naphthorosarins revealed that the presence of meso-2,6-dichlorophenyl- and 5,6-difluoro-substitution substantially alter the geometry and properties of the naphthorosarins. The substituents affect the redox potentials as well and, in turn, the proton-coupled electron-transfer processes leading to the formation of one- and two-electron reduced forms of the corresponding naphthorosarins. One particular naphthorosarin that bears both peripheral fluorine and meso-2,6-dichlorophenyl substituents forms a stable 25 π-electron species upon treating with TFA that was characterized by single-crystal X-ray diffraction analysis. The current study underscores how structural modifications can be used to fine-tune the electronic features of naphthorosarins, including stabilization of odd electron species.

Newly Identified AhR-Active Compounds in the Sediments of an Industrial Area Using Effect-Directed Analysis.

Effect-directed analysis was used to identify previously unidentified aryl hydrocarbon receptor (AhR) agonists in sediments collected from a highly industrialized area of Ulsan Bay, Korea. The specific objectives were to (i) investigate potent fractions of sediment extracts using the H4IIE-luc bioassay, (ii) determine the concentrations of known AhR agonists (polycyclic aromatic hydrocarbons (PAHs) and styrene oligomers (SOs)), (iii) identify previously unreported AhR agonists in fractions by use of GC-QTOFMS, and (iv) evaluate contributions of individual compounds to overall AhR-mediated potencies, found primarily in fractions containing aromatics with log Kow 5-8. Greater concentrations of PAHs and SOs were also found in those fractions. On the basis of GC-QTOFMS and GC-MSD analyses, 16 candidates for AhR agonists were identified in extracts of sediments. Of these, seven compounds, including 1-methylchrysene, benzo[j]fluoranthene, 3-methylchrysene, 5-methylbenz[a]anthracene, 11H-benzo[b]fluorene, benzo[b]naphtho[2,3-d]furan, and benzo[b]naphtho[2,1-d]thiophene, exhibited significant AhR activity. Relative potency values of newly identified AhR agonists were found to be greater than or comparable to that of benzo[a]pyrene (BaP). The potency balance analysis showed that newly identified AhR agonists explained 0.07-16% of bioassay-derived BaP-EQs. These chemicals were widely distributed in industrial sediments; thus, it is of immediate importance to conduct studies on sources and potential effects of those chemicals.

Evaluation of residual toxicity of hypochlorite-treated water using bioluminescent microbes and microalgae: Implications for ballast water management.

Total residual oxidants (TRO) in treated ballast water can produce various disinfection by-products (DBPs) depending on local conditions, such as salinity and organic matter content in water. Because TRO and DBPs are known to be harmful to aquatic organisms and humans, ecotoxicity tests have been proposed for screening the residual toxicity before discharging treated ballast water. In the present study, we aimed to address the decay rates and toxicity changes of TRO under various conditions in salinity, initial TRO concentrations, and residence time of TRO. In addition, the toxicological sensitivities of bioluminescent bacteria Vibrio fischeri and a commonly-used microalgae Skeletonema costatum relative to the residual toxicity of TRO and six selected DBPs were determined. Decay rate of TRO concentration increased as a function of salinity and was affected by the initial concentrations of TRO. Unexpectedly, significant bioluminescence inhibition was observed for hypochlorite-treated water at < 0.1 mg L-1 TRO (expressed as Cl2), which is a lower concentration than the maximum allowable discharge concentration (MADC) to marine waters established by the International Maritime Organization (IMO). The ecotoxicological thresholds of no observed effective concentration and median effect concentration for all tested DBPs were about 3-10 times lower for V. fischeri than for S. costatum. The results indicate that bioluminescent microbes possess an ecologically-relevant sensitivity to both TRO and DBPs in ballast water. In general, bioassay using V. fischeri was potentially more effective than microalgae for screening the total toxicity of TRO and DBPs in treated ballast water, especially given that ballast water usually contains a highly variable and complex mixture of toxicants.

Multiple evaluation of the potential toxic effects of sediments and biota collected from an oil-polluted area around Abu Ali Island, Saudi Arabia, Arabian Gulf.

After the Gulf War Oil Spill, there have been many investigations about distributions of oil-derived pollutants nearby areas, but lacking in ecotoxicological assessment. We evaluated the potential toxicity of asphalt mats, sediments, and biota (polychaetes, chitons, snapping shrimps, and crabs) by combining two bioassays (H4IIE-luc and Vibrio fischeri) and in situ microbial community (eDNA). Samples were collected from Abu Ali Island, and organic extracts were bioassayed and further fractionated according to the chemical polarity using silica gel column. Great aryl hydrocarbon receptor (AhR)-mediated potencies and inhibition of bioluminescence were mainly found in aromatics (F2) and saturates (F1) fractions of asphalt mat and sediments, respectively, while great toxicological responses in biota samples were found in resins and polar (F3) fraction. We also confirmed that potential toxicities of biota were species-specific; great AhR-mediated potencies were found in polychaetes and great bioluminescence inhibitions were found in crabs. In microbial communities, most genera (up to 90%) were associated with polycyclic aromatic hydrocarbons (PAHs)-degrading bacteria, supporting that PAHs are the primary stressors of the benthic community around Abu Ali Island. The present study provides useful information on the contamination status, risk assessment of environmental matrices and benthic organisms in Abu Ali Island.

Pulse control in a wide frequency range for a quasi-continuous wave diode-pumped cesium atom vapor laser by a pump modulation in the spectral domain.

Diode-pumped alkali-atom laser (DPAL) has attracted intense attention due to its inherently high quantum efficiency, a good beam quality, and a high potential in the power scaling. However, most of DPAL research has been confined to the continuous wave and only a few pulsed operations have been attempted with limited performances. Here, we proposed and experimentally demonstrated a new scheme using a fast mode-hopping in the pump laser diode (LD), which enabled the quasi-continuous-wave (QCW) pulse modulation in a cesium (Cs) DPAL to control both the pulse width and the repetition rate. The pump wavelength was efficiently modulated in a fast cycle within discrete spectral ranges provided by the mode-hopping in the pump LD. The spectral range was successfully adjusted to include the resonant D2 absorption line of Cs atom to result in an effective gain modulation. Using this proposed scheme, we successfully achieved Cs-DPAL QCW modulation, whose pulse width was varied from tens of microseconds to a few milliseconds and the repetition rate was also variable in a wide frequency range from 10 Hz to 7.0 kHz. Detailed pump modulation method and the corresponding laser characteristics are discussed. The proposed method can be readily applied to pulse modulation of other types of alkali vapor lasers overcoming the previous limitations of DPAL to further expand applications in various light-matter interactions.