Enhancing reductive dechlorination of trichloroethylene in bioelectrochemical systems with conductive materials.

The incorporation of conductive materials to enhance electron transfer in bioelectrochemical systems (BES) is considered a promising approach. However, the specific effects and mechanisms of these materials on trichloroethylene (TCE) reductive dechlorination in BES remains are not fully understood. This study investigated the use of magnetite nanoparticles (MNP) and biochars (BC) as coatings on biocathodes for TCE reduction. Results demonstrated that the average dechlorination rates of MNP-Biocathode (122.89 µM Cl·d-1) and BC-Biocathode (102.88 µM Cl·d-1) were greatly higher than that of Biocathode (78.17 µM Cl·d-1). Based on MATLAB calculation, the dechlorination rate exhibited a more significantly increase in TCE-to-DCE step than the other dechlorination steps. Microbial community analyses revealed an increase in the relative abundance of electroactive and dechlorinating populations (e.g., Pseudomonas, Geobacter, and Desulfovibrio) in MNP-Biocathode and BC-Biocathode. Functional gene analysis via RT-qPCR showed the expression of dehalogenase (RDase) and direct electron transfer (DET) related genes was upregulated with the addition of MNP and BC. These findings suggest that conductive materials might accelerate reductive dechlorination by enhancing DET. The difference of physicochemical characteristics (e.g. particle size and specific surface area), electron transfer enhancement mechanism between MNP and BC as well as the reduction of Fe(III) by hydrogen may explain the superior dechlorination rate observed with MNP-Biocathode.

Unveiling Möbius/Hückel Topology and Aromaticity in A Core-Expanded [10]Annulene at Different Oxidation States.

The exploration of annulene's conformation, electronic properties and aromaticity has generated enduring interest over the years, yet it continues to present formidable challenges for annulenes with more than ten carbon atoms. In this study, we present the synthesis of a stable [10]cyclo-para-phenylmethine derivative (1), which bears a resemblance to [10]annulene. 1 can be readily oxidized into its respective cations, wherein electrons are effectively delocalized along the backbone, resulting in different conformations and aromaticity. Both 1 and its tetracation (14+ ⋅ 4SbF6 - ) exhibit a nearly planar conformation with a rectangular shape, akin to the E,Z,E,Z,Z-[10]annulene. In contrast, the radical cation (1⋅+ ⋅ SbCl6 - ) possesses a doubly twisted Hückel topology. Furthermore, the dication (12+ ⋅ 2SbCl6 - ) displays conformational flexibility in solution and crystalizes with the simultaneous presence of Möbius-twisted (1a2+ ⋅ 2SbCl6 - ) and Hückel-planar (1b2+ ⋅ 2SbCl6 - ) isomers in its unit cell. Detailed experimental measurements and theoretical calculations reveal that: (1) 1 demonstrates localized aromaticity with an alternating benzenoid/quinoid structure; (2) 1a2+ ⋅ 2SbCl6 - and 1b2+ ⋅ 2SbCl6 - with 48π electrons are weakly Möbius aromatic and Hückel antiaromatic, respectively; (3) 14+ ⋅ 4SbF6 - exhibits Hückel aromaticity (46π) and open-shell diradical character.

Electrokinetic-Enhanced Bioremediation of Trichloroethylene-Contaminated Low-Permeability Soils: Mechanistic Insight from Spatio-Temporal Variations of Indigenous Microbial Community and Biodehalogenation Activity.

Electrokinetic-enhanced bioremediation (EK-Bio), particularly bioaugmentation with injection of biodehalogenation functional microbes such as Dehalococcoides, has been documented to be effective in treating a low-permeability subsurface matrix contaminated with chlorinated ethenes. However, the spatio-temporal variations of indigenous microbial community and biodehalogenation activity of the background matrix, a fundamental aspect for understanding EK-Bio, remain unclear. To fill this gap, we investigated the variation of trichloroethylene (TCE) biodehalogenation activity in response to indigenous microbial community succession in EK-Bio by both column and batch experiments. For a 195 day EK-Bio column (∼1 V/cm, electrolyte circulation, lactate addition), biodehalogenation activity occurred first near the cathode (<60 days) and then spread to the anode (>90 days), which was controlled by electron acceptor (i.e., Fe(III)) competition and microbe succession. Amplicon sequencing and metagenome analysis revealed that iron-reducing bacteria (Geobacter, Anaeromyxobacter, Geothrix) were enriched within initial 60 d and were gradually replaced by organohalide-respiring bacteria (versatile Geobacter and obligate Dehalobacter) afterward. Iron-reducing bacteria required an initial long time to consume the competitive electron acceptors so that an appropriate reductive condition could be developed for the enrichment of organohalide-respiring bacteria and the enhancement of TCE biodehalogenation activity.

Bioelectrochemical system accelerates reductive dechlorination through extracellular electron transfer networks.

Bioelectrochemical system is considered as a promising approach for enhanced bio-dechlorination. However, the mechanism of extracellular electron transfer in the dechlorinating consortium is still a controversial issue. In this study, bioelectrochemical systems were established with cathode potential settings at -0.30 V (vs. SHE) for trichloroethylene reduction. The average dechlorination rate (102.0 µM Cl·d-1) of biocathode was 1.36 times higher than that of open circuit (74.7 µM Cl·d-1). Electrochemical characterization via cyclic voltammetry illustrated that electrostimulation promoted electrochemical activity for redox reactions. Moreover, bacterial community structure analyses indicated electrical stimulation facilitated the enrichment of electroactive and dechlorinating populations on cathode. Metagenomic and quantitative polymerase chain reaction (qPCR) analyses revealed that direct electron transfer (via electrically conductive pili, multi-heme c-type cytochromes) between Axonexus and Desulfovibrio/cathode and indirect electron transfer (via riboflavin) for Dehalococcoides enhanced dechlorination process in BES. Overall, this study verifies the effectiveness of electrostimulated bio-dechlorination and provides novel insights into the mechanisms of dechlorination process enhancement in bioelectrochemical systems through electron transfer networks.

Fused Indacene Dimers.

Polycyclic hydrocarbons consisting of two or more directly fused antiaromatic subunits are rare due to their high reactivity. However, it is important to understand how the interactions between the antiaromatic subunits influence the electronic properties of the fused structure. Herein, we present the synthesis of two fused indacene dimer isomers: s-indaceno[2,1-a]-s-indacene (s-ID) and as-indaceno[3,2-b]-as-indacene (as-ID), containing two fused antiaromatic s-indacene or as-indacene units, respectively. Their structures were confirmed by X-ray crystallographic analysis. 1 H NMR/ESR measurements and DFT calculations revealed that both s-ID and as-ID have an open-shell singlet ground state. However, while localized antiaromaticity was observed in s-ID, as-ID showed weak global aromaticity. Moreover, as-ID exhibited a larger diradical character and a smaller singlet-triplet gap than s-ID. All the differences can be attributed to their distinct quinoidal substructures.

A Fused [5]Helicene Dimer with a Figure-Eight Topology: Synthesis, Chiral Resolution, and Electronic Properties.

Chiral shape-persistent molecular nanocarbons are promising chiroptical materials; their synthesis, however, remains a big challenge. Herein, we report the facile synthesis and chiral resolution of a double-stranded figure-eight carbon nanobelt 1 in which two [5]helicene units are fused together. Two synthetic routes were developed, and, in particular, a strategy involving Suzuki coupling-mediated macrocyclization followed by Bi(OTf)3 -catalyzed cyclization of vinyl ether turned out to be the most efficient. The structure of 1 was confirmed by X-ray crystallographic analysis. The isolated (P,P)- and (M,M)- enantiomers show persistent chiroptical properties with relatively large dissymmetric factors (|gabs |=5.4×10-3 and |glum |=1.0×10-2 ), which can be explained by the effective electron delocalization along the fully conjugated belt and the unique D2 symmetry. 1 exhibits local aromatic character with a dominant structure containing eight Clar's aromatic sextet rings.

Aromaticity in Fully π-Conjugated Open-Cage Molecules.

Although aromaticity in 2D π-conjugated monocyclic and polycyclic molecules has been intensively studied, aromaticity in 3D fully π-conjugated molecular cages remains largely unexplored mainly due to the synthetic challenges. Herein, we report the facile synthesis of a π-conjugated molecular cage (1) containing four dimethylmethylene-bridged triphenylamine (DTPA) units via platinum-mediated assembly of four molecules of a pinacol borate trisubstituted DTPA derivative, followed by reductive elimination. 1 has an open-cage structure, consisting of two isomeric trimers in trans- and cis-configurations, and an additional macrocycle across four DTPA units. Accordingly, the trans- (2) and cis- (3) macrocyclic trimers were also synthesized for comparison. 1-3 can be facilely oxidized into their respective cations in which electrons are effectively delocalized at two or three dimensions. The detailed experimental measurements and theoretical calculations reveal that (1) the neutral cage 1 shows localized aromaticity in individual benzene rings; (2) the dication 12+·2SbF6- displays bicyclic (anti)aromaticity with one macrocycle being aromatic (38π) and another macrocycle being antiaromatic (28π); on the other hand, the dications of the model compounds 2 and 3 are globally antiaromatic and nonaromatic, respectively; (3) the tetracation 14+·4SbF6- exhibits dominant 2D Hückel antiaromaticity in one of the macrocycles (36π). In addition, 12+·2SbF6-, 14+·4SbF6-, and 22+·2SbF6- possess open-shell singlet ground state with significant diradical character, while 32+·2SbF6- adopts a triplet ground state to release strain.

[8]Cyclo-para-phenylmethine as a Super-Cyclooctatetraene: Dynamic Behavior, Global Aromaticity, and Open-Shell Diradical Character in the Neutral and Dicationic States.

An [8]cyclo-para-phenylmethine derivative ([8]CPPM-Mes) was synthesized. X-ray analysis revealed a tub-shaped geometry similar to the cyclooctatetraene, with alternating benzenoid/quinoid structure. Variable-temperature NMR measurements disclosed a slow valence tautomerization process with an interconversion energy barrier of about 11.7 kcal mol-1 at coalescence temperature (273 K), and two more lower-barrier dynamic processes involving flipping of the 1,4-phenyl rings on the backbone and rotation of the mesityl substituents. Its dication ([8]CPPM-Mes2+ ) adopts a bowl-like geometry with a smaller depth of the cavity, and a slow bowl inversion process was observed by dynamic NMR. The bond lengths of the benzenoid/quinoid rings are more averaged via electron delocalization and the molecule shows global aromaticity, which was further validated by NMR and theoretical analysis. [8]CPPM-Mes2+ exhibits open-shell diradical character with a small singlet-triplet energy gap (-1.8 kcal mol-1 ).

Facile Synthesis of a Fully Fused, Three-Dimensional π-Conjugated Archimedean Cage with Magnetically Shielded Cavity.

The synthesis of molecular cages consisting of fully fused, π-conjugated rings is rare due to synthetic challenges including preorganization, large strain, and poor solubility. Herein, we report such an example in which a tris-2-aminobenzophenone precursor undergoes acid-mediated self-condensation to form a truncated tetrahedron, one of the 13 Archimedean solids. Formation of eight-membered [1,5]diazocine rings provides preorganization and releases the strain while still maintains weak π-conjugation of the backbone. Thorough characterizations were performed by X-ray, NMR, and UV-vis analysis, assisted by theoretical calculations. The cage exhibits a rigid backbone structure with a well-defined cavity that confines a magnetically shielded environment. The solvent molecule, o-dichlorobenzene, is precisely encapsulated in the cavity at a 1:1 ratio with multiple π···π, C-H···π, and halogen···π interactions with the cage skeleton, implying its template effect for the cage closing reaction. Our synthetic strategy opens the opportunity to access more complex, fully fused, three-dimensional π-conjugated cages.

A Chichibabin's Hydrocarbon-Based Molecular Cage: The Impact of Structural Rigidity on Dynamics, Stability, and Electronic Properties.

A three-dimensional π-conjugated polyradicaloid molecular cage c-Ph14, consisting of three Chichibabin's hydrocarbon motifs connected by two benzene-1,3,5-triyl bridgeheads, was synthesized. Compared with its linear model compound l-Ph4, the prism-like c-Ph14 has a more rigid structure, which shows significant impact on the molecular dynamics, stability, and electronic properties. A higher rotation energy barrier for the quinoidal biphenyl units was determined in c-Ph14 (15.64 kcal/mol) than that of l-Ph4 (11.40 kcal/mol) according to variable-temperature NMR measurements, leading to improved stability, a smaller diradical character, and an increased singlet-triplet energy gap. The pressure-dependent Raman spectroscopic studies on the rigid cage c-Ph14 revealed a quinoidal-to-aromatic transformation along the biphenyl bridges. In addition, the ellipsoidal cavity in the cage allowed selective encapsulation of fullerene C70 over C60, with an associate constant of about 1.43 × 104 M-1. Moreover, c-Ph14 and l-Ph4 exhibited similar redox behavior and their cationic species (c-Ph146+ and l-Ph42+) were obtained by chemical oxidation, and the structures were identified by X-ray crystallographic analysis. The biphenyl unit showed a twisted conformation in l-Ph42+ and remained coplanarity in c-Ph146+. Notably, molecules of c-Ph146+ form a one-dimensional columnar structure via close π-π stacking between the bridgeheads.

[6]Cyclo-para-phenylmethine: An Analog of Benzene Showing Global Aromaticity and Open-Shell Diradical Character.

We report a [6]cyclo-para-phenylmethine ([6]CPPM) macrocycle that shows benzene-like electronic properties. Its mesityl derivative, [6]CPPM-Mes, was isolated in crystalline form. X-ray analysis reveals a C2h symmetry, and the bond lengths of the benzenoid/quinoid rings are averaged via resonance. One averaged 1H NMR peak for the protons on the backbone was observed at room temperature, but it was split into one shielded and one deshielded resonance below 198 K, consistent with its globally aromatic character with a dominant 30π conjugation pathway along the periphery. It exhibits open-shell diradical character with a moderate singlet-triplet energy gap (ΔES-T = -6.23 kcal/mol). Its dication is antiaromatic and open-shell, showing a smaller ΔES-T value (-4.18 kcal/mol). Overall, [6]CPPM behaves like an open-shell aromatic "super-benzene".

[2]Pseudorotaxane-Based Supramolecular Optical Indicator for the Visual Detection of Cellular Cyanide Excretion.

Cyanide is extremely hazardous to living organisms and the environment. Owing to its wide range of applications and high toxicity, the development of functional materials for cyanide detection and sensing is highly desirable. Host-guest complexation between bis(p-phenylene)-34-crown-10 H and N-methylacridinium salt G remarkably decreases the detection limit for cyanide anions compared with that of the guest itself. The [2]pseudorotaxane selectively recognizes the cyanide anion with high optical sensitivity as a result of the nucleophilic addition of the cyanide anion at the 9-position of G. The host-guest complexation is further incorporated into supramolecular materials for the visual detection of cyanide anions, especially the detection of cellular cyanide excretion with a detection limit of 0.6 µm. This supramolecular method provides an extremely distinct strategy for the visual detection of cyanide anions.

Formation of Linear Side-Chain Polypseudorotaxane with Supramolecular Polymer Backbone through Neutral Halogen Bonds and Pillar[5]arene-Based Host-Guest Interactions.

Linear side-chain polypseudorotaxane with supramolecular polymer backbone was assembled by neutral halogen bonds (XB) and pillar[5]arene-based host-guest interactions in solution and in the solid state. The formation of the halogen-bonded supramolecular polymer backbone and side-chain polypseudorotaxane in solution was characterized by 1 H NMR spectroscopy, diffusion ordered NMR spectroscopy and scanning electron microscopy experiments. Furthermore, the solid-state structures of these two highly organized supramolecular architectures were provided by single-crystal X-ray analysis.

Catenane Crosslinked Mechanically Adaptive Polymer Gel.

A new strategy is introduced to prepare an adaptive polymer gel that has a unique adaptability in response to environmental stimuli. This gel is prepared by the thiol-ene "click" reaction between a bisvinyl [2]catenane and a poly(ethylene glycol) derivative containing multiple thiol groups. The catenane crosslinker is responsive to external stimuli due to the existence of intercomponent hydrogen bonding (IHB). The strong IHB restricts the rotation and movement of the crosslinker, giving it a rigid feature; however, the crosslinker becomes flexible when the IHB is destroyed. In consequence, the resulting gel can be reversibly switched between tough and soft states under stimulations.

Construction of Metallacage-Cored Supramolecular Gel by Hierarchical Self-Assembly of Metal Coordination and Pillar[5]arene-Based Host-Guest Recognition.

In this work, a Pd2 L4 metallacage 2•([BF4 ]- )4 with four pillar[5]arene units is first prepared and characterized by 1D multinuclear NMR (1 H, 11 B, and 19 F NMR), 2D 1 H-1 H correlation spectra, 1 H-13 C heteronuclear single quantum coherence, and diffusion-ordered NMR spectroscopy, and electrospray ionization time-of-flight mass spectrometry. By the introduction of a ditopic guest molecule 3 into a chloroform solution of 2•([BF4 ]- )4 , a supramolecular polymer network gel is successfully constructed based on the metal coordination interactions and host-guest recognition between the pillar[5]arene units of 2•([BF4 ]- )4 and neutral ditopic guest molecule 3. The temperature and pH responsivenesses of the supramolecular gel are studied, which are further employed for the controlled release of different cargos. As a demonstration, emodin and methylene blue are trapped in the cavities of the metallacage and in the pores of the supramolecular gel, respectively. Methylene blue is first released along with the gel-sol transition while emodin is then released by the further addition of acid to destroy the metallacage. This study explores the use of metallacage-cored supramolecular network gels for sequential controlled release and contributes to the development of smart and adaptive materials.

Reversible Iodine Capture by Nonporous Pillar[6]arene Crystals.

Here we report that easily obtained per-ethylated pillar[6]arene (EtP6) is a new adsorbent for iodine capture with high chemical and thermal stability. Nonporous EtP6 solids are shown to capture not only volatile iodine in the air but also iodine dissolved in an organic solvent and aqueous solution. Uptake of iodine leads to a structural transformation of EtP6 in the solid state. In the single crystal structure of iodine-doped EtP6 (I2@EtP6), each adsorbed iodine molecule is located between two adjacent EtP6 molecules to form a linear supramolecular polymer. Iodine is released spontaneously from I2@EtP6 solids when they are immersed in cyclohexane. These EtP6 solids can be reused many times without losing iodine capture capacity.

A Porphyrin-Based Discrete Tetragonal Prismatic Cage: Host-Guest Complexation and Its Application in Tuning Liquid-Crystalline Behavior.

The host-guest complexation between a porphyrin-based 3D tetragonal prism (H) and electron-rich pyrene is investigated. This host-guest molecular recognition is further utilized to suppress the liquid-crystalline behavior of a nematic molecule (G) containing cyanobiphenyl mesogens functionalized with a pyrenyl unit. Furthermore, coronene, with an increased number of π-electrons, is used as a competitive guest to recover the liquid-crystalline behavior of G. This supramolecular approach provides a glimpse of the new possibilities to modulate the structures of the mesophases.

Conformation modulated optical activity enhancement in chiral cysteine and au nanorod assemblies.

Assemblies of chiral cysteine (CYS) and Au nanorods (GNRs) are constructed in two typical patterns, end-to-end and side-by-side. Impressively, side-by-side assembled GNRs with CYS show obviously stronger plasmonic circular dichrosim (CD) response compared with the end-to-end assemblies. The corresponding theoretical calculation elucidates the intrinsic relationship among geometric structure, electromagnetic interaction, and induced plasmonic CD of the assemblies. This work will significantly benefit the design and application of plasmonic nanodevices with controllable chiroptical responses.

[Semen expulsion under the ureterocystoscope].

OBJECTIVE: To determine the exact location of the opening of the ejaculatory duct in men and provide some basic anatomical evidence for seminal vesiculoscopy and the treatment of ejaculatory duct obstruction. METHODS: We performed ureterocystoscopy for 21 male patients aged 26 - 47 years with hematuria (n = 12), hematospermia (n = 2), glandular cystitis (n = 6), and anejaculation after radical resection of rectal carcinoma (n = 1), and meanwhile, with the consent of the patients, massaged the prostate and ejaculatory duct and observed the outlet of the expelled fluid. Under the microscope, we described the fluid samples with sperm as the expulsion from the ejaculatory duct. RESULTS: Ureterocystoscopy showed that the exact anatomical sites of the expulsion of prostatic fluid and semen in the patients were the side and lower side of the prostatic utricle opening above the verumontanum and the ventral side of the verumontanum. Quantities of sperm were found in the expulsion fluid of 13 of the patients, and no expulsion, including semen, was seen from the prostatic utricle opening. CONCLUSION: Anatomically, the ejaculatory duct openings of males are located at the two sides of the verumontanum adjacent to the opening of the prostatic utricle, rather than in the prostatic utricle above the verumontanum.

Dynamic Graph Guided Progressive Partial View-Aligned Clustering.

In recent years, there has been a growing focus on multiview data, driven by its rich complementary and consistent information, which has the potential to significantly enhance the performance of downstream tasks. Although many multiview clustering (MVC) methods have achieved promising results by integrating the information of multiple views to learn the consistent representation or consistent graph, these methods typically require complete and entirely accurate correspondences between multiview data, which is challenging to fulfill in practice leading to the problem of partially view-aligned clustering (PVC). To tackle it, we propose a novel method, called dynamic graph guided progressive partial view-aligned clustering (DGPPVC) in this article. To the best of our knowledge, this could be the first work to employ graph convolutional network (GCN) to address the problem of PVC, which explores GCN with dynamic adjacency matrix to reduce unreliable alignments and locate the feature representation with consistent graph structure. In particular, DGPPVC develops an end-to-end framework that encompasses graph construction, feature representation learning, and alignment relationships learning, in which the three parts mutually influence and benefit each other. Moreover, DGPPVC adopts a novel alignment learning strategy that progresses from simplicity to complexity, enabling the step-by-step acquisition of unknown correspondences between different modalities. By giving priority to simple instance pairs, a variant of Jaccard similarities is designed to identify more reliable and complex alignments progressively. During the gradual learning process of alignment relationships, the graph structure matrix is continually and dynamically optimized, thus acquiring a greater variety of graph information between different views. Experiments on several real-world datasets show our promising performance compared with the state-of-the-art methods in partially view-aligned clustering.