Antichirality Emergent in Type-II Weyl Phononic Crystals.

Chiral anomaly as the hallmark feature lies in the heart of the researches for Weyl semimetal. It is rooted in the zeroth Landau level of the system with an applied magnetic field. Chirality or antichirality characterizes the propagation property of the one-way zeroth Landau level mode, and antichirality means an opposite group velocity compared to the case of chirality. Chirality is commonly observed for Weyl semimetals. Interestingly, the type-II Weyl point, with the overtilted dispersion, may flip the chirality to the antichirality, which, however, is yet to be evidenced despite numerous previous experimental efforts. Here, we implement the type-II Weyl point in sonic crystals, and by creating the pseudomagnetic fields with geometric deformation, the chirality flip of zeroth Landau levels is unambiguously demonstrated. Our Letter unveils the novel antichiral transport in the presence of time-reversal symmetry, and paves the way toward the state-of-the-art manipulation of sound waves.

Metabolic characterisation of eight Escherichia coli strains including "Big Six" and acidic responses of selected strains revealed by NMR spectroscopy.

The metabolic diversity of Escherichia coli strains (non-pathogenic E. coli ATCC 25922, and pathogenic E. coli O157:H7, O26:H11, O45:H2, O103:H11, O111, O121:H19, and O145) was tested using nuclear magnetic resonance. Based on two representative two-dimensional 1H-13C spectra, 38 metabolites were identified in E. coli intracellular samples. Principal component analysis indicated that metabolites including lysine, arginine, α-ketoglutaric acid, adenosine, and fumaric acid were responsible for the separation of E. coli ATCC 25922. Relatively large metabolic differences between ATCC 25922 and the pathogenic strains were recoded. The most varied pairwise group (ATCC 25922 vs. O26:H11) was further analysed. The screened metabolites and enrichment pathway tests revealed different amino acid metabolism and higher requirement for energy production in the pathogenic strains. The acidic responses of the selected strains were further tested. The in vitro and in vivo inactivation kinetics, morphological changes, and protein leakage showed higher acid tolerance of E. coli O26:H11. Metabolic analysis of the two strains under acidic stress revealed alternative metabolites and pathways in the two groups. Pathogenic O26:H11 was characterised by higher energy production and amino acid metabolism (lysine and glutamic acid). Real-time PCR tests confirmed that glutamic acid dependent decarboxylase/antiporter system was the major acid resistance mechanism.

Cyclohexyl-Fused, Spirobiindane-Derived, Phosphine-Catalyzed Synthesis of Tricyclic γ-Lactams and Kinetic Resolution of γ-Substituted Allenoates.

A C2-symmetric chiral phosphine catalyst, NUSIOC-Phos, which can be easily derived from cyclohexyl-fused spirobiindane, was introduced. A highly enantioselective domino process involving pyrrolidine-2,3-diones and γ-substituted allenoates catalyzed by NUSIOC-Phos has been disclosed. Diastereospecific tricyclic γ-lactams containing five contiguous stereogenic centers were obtained in high yields and with nearly perfect enantioselectivities. A kinetic resolution process of racemic γ-substituted allenoates was developed for the generation of optically enriched chiral allenoates.

Identification of Cyclic Dipeptides from Escherichia coli as New Antimicrobial Agents against Ralstonia Solanacearum.

Ralstonia solanacearum is a causative agent of bacterial wilt in many important crops throughout the world. How to control bacterial wilt caused by R. solanacearum is a major problem in agriculture. In this study, we aim to isolate the biocontrol agents that have high efficacy in the control of bacterial wilt. Three new bacterial strains with high antimicrobial activity against R. solanacearum GMI1000 were isolated and identified. Our results demonstrated that these bacteria could remarkably inhibit the disease index of host plant infected by R. solanacearum. It was indicated that strain GZ-34 (CCTCC No. M 2016353) showed an excellent protective effect to tomato under greenhouse conditions. Strain GZ-34 was characterized as Escherichia coli based on morphology, biochemistry, and 16S rRNA analysis. We identified that the main antimicrobial compounds produced by E. coli GZ-34 were cyclo(l-Pro-d-Ile) and cyclo(l-Pro-l-Phe) using electrospray ionization mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) analysis. The two active compounds also interfered with the expression levels of some pathogenicity-contributors of R. solanacearum. Furthermore, cyclo(l-Pro-l-Phe) effectively inhibited spore formation of Magnaporthe grisea, which is a vital pathogenesis process of the fungal pathogen, suggesting cyclic dipeptides from E. coli are promising potential antimicrobial agents with broad-spectrum activity to kill pathogens or interfere with their pathogenesis.

Graphene-Oxide-Catalyzed Direct CH-CH-Type Cross-Coupling: The Intrinsic Catalytic Activities of Zigzag Edges.

The development of graphene oxide (GO)-based materials for C-C cross-coupling represents a significant advance in carbocatalysis. Although GO has been used widely in various catalytic reactions, the scope of reactions reported is quite narrow, and the relationships between the type of functional groups present and the specific activity of the GO are not well understood. Herein, we explore CH-CH-type cross-coupling of xanthenes with arenes using GO as real carbocatalysts, and not as stoichiometric reactants. Mechanistic studies involving molecular analogues, as well as trapped intermediates, were carried out to probe the active sites, which were traced to quinone-type functionalities as well as the zigzag edges in GO materials. GO-catalyzed cross-dehydrogenative coupling is operationally simple, shows reusability over multiple cycles, can be conducted in air, and exhibits good functional group tolerance.

Fused Bicyclic Caspase-1 Inhibitors Assembled by Copper-Free Strain-Promoted Alkyne-Azide Cycloaddition (SPAAC).

Challenges exist in the development of potent and selective small-molecule inhibitors against caspase-1. Herein, by making use of the copper-free strain-promoted alkyne-azide cycloaddition (SPAAC) reaction between difluorinated cyclooctynes (DIFOs) and various azide-containing compounds, we showed for the first time that potential caspase-1 inhibitors could be rapidly synthesized. The resulting fused bicyclic compounds structurally resembled the central portion (P2 -P3 ) of Pralnacasan (a well-known small molecule caspase-1 inhibitor), with diversity at the P4 -position of the parental inhibitor conveniently installed from the azide component. Since our SPAAC-assembled inhibitor library was synthesized by using a copper-free bioorthogonal chemistry, the resulting 52-membered library (2 DIFOs×26 azides) was immediately ready for subsequent cell-based screening for rapid identification of potential cell-permeable hits capable of effectively inhibiting endogenous caspase-1 activities. C1FS, a recently reported fluorogenic two-photon probe, which possesses improved live-cell imaging sensitivity against endogenous caspase-1, was used both in vitro and in LPS/ATP-induced macrophages (a well-established caspase-1-activated cell model) to screen against selected compounds from the above-mentioned library, leading to subsequent discovery of a novel caspase-1 inhibitor named b7-b.

Diffusible signal factor family signals provide a fitness advantage to Xanthomonas campestris pv. campestris in interspecies competition.

Diffusible signal factor (DSF) represents a new class of widely conserved quorum sensing signals, which regulates various biological functions through intra- or interspecies signaling. The previous studies identified that there is an antagonistic interaction between Xanthomonas and Bacillus species bacteria in natural ecosystem, but the detailed molecular mechanism of interspecies competition is not clear. This study showed that Xanthomonas campestris pv. campestris (Xcc) interfered with morphological transition and sporulation of Bacillus thuringiensis in mixed cultures, whereas abrogation of the DSF synthase RpfF reduced the interference. DSF inhibited B. thuringiensis cell division and sporulation through modulation of ftsZ, which encodes an important cell division protein in bacterial cells. In addition, RpfF is essential for production of six DSF-family signals in Xcc, which employ the same signaling pathways to regulate biological functions in Xcc and play similar effects on reduction of cell division, sporulation and antibiotic resistance of B. thuringiensis. Furthermore, abrogation of RpfF decreased the competitive capability of Xcc against B. thuringiensis on the surface of Chinese cabbage leaves. Our findings provide new insights into the role of DSF-family signals in interspecies competition and depict molecular mechanisms with which Xcc competes with B. thuringiensis.

Synthesis of Disubstituted 3-Phenylimidazo[1,2-a]pyridines via a 2-Aminopyridine/CBrCl3 α-Bromination Shuttle.

A versatile protocol for the synthesis of disubstituted 3-phenylimidazo[1,2-a]pyridines by coupling 2-aminopyridine with phenylacetophenones, phenylacetones, or ß-tetralone has been developed. Isolated yields of up to 97% were obtained at 80 °C within 5 h. The 2-aminopyridine/CBrCl3 system acts as an α-bromination shuttle by transferring Br from CBrCl3 to the α-carbon of the carbonyl moiety. This triggers a series of steps with double C-N/C-N bond formation to the final product. The distinct advantages of this protocol include the use of commercially available inexpensive substrates, simplicity of a metal-free one-pot synthesis, and ease of scale-up to multigram quantities.

Structure-Dependent cis/trans Isomerization of Tetraphenylethene Derivatives: Consequences for Aggregation-Induced Emission.

The isomerization and optical properties of the cis and trans isomers of tetraphenylethene (TPE) derivatives with aggregation-induced emission (AIEgens) have been sparsely explored. We have now observed the tautomerization-induced isomerization of a hydroxy-substituted derivative, TPETH-OH, under acidic but not under basic conditions. Replacing the proton of the hydroxy group in TPETH-OH with an alkyl group leads to the formation of TPETH-MAL, for which the pure cis and trans isomers were obtained and characterized by HPLC analysis and NMR spectroscopy. Importantly, cis-TPETH-MAL emits yellow fluorescence in DMSO at -20 °C whereas trans-TPETH-MAL shows red fluorescence under the same conditions. Moreover, the geometry of cis- and trans-TPETH-MAL remains unchanged when they undergo thiol-ene reactions to form cis- and trans-TPETH-cRGD, respectively. Collectively, our findings improve our fundamental understanding of the cis/trans isomerization and photophysical properties of TPE derivatives, which will guide further AIEgen design for various applications.

The host plant metabolite glucose is the precursor of diffusible signal factor (DSF) family signals in Xanthomonas campestris.

Plant pathogen Xanthomonas campestris pv. campestris produces cis-11-methyl-2-dodecenoic acid (diffusible signal factor [DSF]) as a cell-cell communication signal to regulate biofilm dispersal and virulence factor production. Previous studies have demonstrated that DSF biosynthesis is dependent on the presence of RpfF, an enoyl-coenzyme A (CoA) hydratase, but the DSF synthetic mechanism and the influence of the host plant on DSF biosynthesis are still not clear. We show here that exogenous addition of host plant juice or ethanol extract to the growth medium of X. campestris pv. campestris could significantly boost DSF family signal production. It was subsequently revealed that X. campestris pv. campestris produces not only DSF but also BDSF (cis-2-dodecenoic acid) and another novel DSF family signal, which was designated DSF-II. BDSF was originally identified in Burkholderia cenocepacia to be involved in regulation of motility, biofilm formation, and virulence in B. cenocepacia. Functional analysis suggested that DSF-II plays a role equal to that of DSF in regulation of biofilm dispersion and virulence factor production in X. campestris pv. campestris. Furthermore, chromatographic separation led to identification of glucose as a specific molecule stimulating DSF family signal biosynthesis in X. campestris pv. campestris. (13)C-labeling experiments demonstrated that glucose acts as a substrate to provide a carbon element for DSF biosynthesis. The results of this study indicate that X. campestris pv. campestris could utilize a common metabolite of the host plant to enhance DSF family signal synthesis and therefore promote virulence.

A Step-by-Step Assembly of a 3D Coordination Polymer in the Solid-State by Desolvation and [2+2] Cycloaddition Reactions.

Two solid-state structural transformations that occur in a stepwise and a controlled manner are described. A combination of desolvation and cycloaddition reactions has been employed to synthesise a 3D coordination polymer (CP) from 1D CP [Cd(bdc)(4-spy)2 (H2 O)]⋅2 H2 O⋅2 DMF (bdc=1,4-benzenedicarboxylate, 4-spy=4-styrylpyridine) presumably via a 2D layered structure, [Cd2 (bdc)2 (4-spy)4 ]. In the absence of single crystals to follow the course of the photocycloaddition reaction, thermogravimetry, XAFS and NOESY NMR experiments were used to propose the formation of layered and pillared layered structures. Further, the present strategy enables us to synthesise new multidimensional architectures that are otherwise inaccessible by the self-assembly process.

A cell-cell communication signal integrates quorum sensing and stress response.

Pseudomonas aeruginosa uses a hierarchical quorum sensing (QS) network consisting of las, pqs and rhl regulatory elements to coordinate the expression of bacterial virulence genes. However, clinical isolates frequently contain loss-of-function mutations in the central las system. This motivated us to search for a mechanism that may functionally substitute las. Here we report identification of a new QS signal, IQS. Disruption of IQS biosynthesis paralyzes the pqs and rhl QS systems and attenuates bacterial virulence. Production of IQS is tightly controlled by las under normal culture conditions but is also activated by phosphate limitation, a common stressor that bacteria encounter during infections. Thus, these results have established an integrated QS system that connects the central las system and phosphate-stress response mechanism to the downstream pqs and rhl regulatory systems. Our discovery highlights the complexity of QS signaling systems and extends the gamut of QS and stress-response mechanisms.

Biosynthesis of mupirocin by Pseudomonas fluorescens NCIMB 10586 involves parallel pathways.

Mupirocin, a clinically important antibiotic produced via a trans-AT Type I polyketide synthase (PKS) in Pseudomonas fluorescens, consists of a mixture of mainly pseudomonic acids A, B, and C. Detailed metabolic profiling of mutant strains produced by systematic inactivation of PKS and tailoring genes, along with re-feeding of isolated metabolites to mutant stains, has allowed the isolation of a large number of novel metabolites, identification of the 10,11-epoxidase, and full characterization of the mupirocin biosynthetic pathway, which proceeds via major (10,11-epoxide) and minor (10,11-alkene) parallel pathways.

The diffusible factor synthase XanB2 is a bifunctional chorismatase that links the shikimate pathway to ubiquinone and xanthomonadins biosynthetic pathways.

The diffusible factor synthase XanB2, originally identified in Xanthomonas campestris pv. campestris (Xcc), is highly conserved across a wide range of bacterial species, but its substrate and catalytic mechanism have not yet been investigated. Here, we show that XanB2 is a unique bifunctional chorismatase that hydrolyses chorismate, the end-product of the shikimate pathway, to produce 3-hydroxybenzoic acid (3-HBA) and 4-HBA. 3-HBA and 4-HBA are respectively associated with the yellow pigment xanthomonadin biosynthesis and antioxidant activity in Xcc. We further demonstrate that XanB2 is a structurally novel enzyme with three putative domains. It catalyses 3-HBA and 4-HBA biosynthesis via a unique mechanism with the C-terminal YjgF-like domain conferring activity for 3-HBA biosynthesis and the N-terminal FGFG motif-containing domain responsible for 4-HBA biosynthesis. Furthermore, we show that Xcc produces coenzyme Q8 (CoQ8) via a new biosynthetic pathway independent of the key chorismate-pyruvate lyase UbiC. XanB2 is the alternative source of 4-HBA for CoQ8 biosynthesis. The similar CoQ8 biosynthetic pathway, xanthomonadin biosynthetic gene cluster and XanB2 homologues are well conserved in the bacterial species within Xanthomonas, Xylella, Xylophilus, Pseudoxanthomonas, Rhodanobacter, Frateuria, Herminiimonas and Variovorax, suggesting that XanB2 may be a conserved metabolic link between the shikimate pathway, ubiquinone and xanthomonadin biosynthetic pathways in diverse bacteria.

Brillouin Klein space and half-turn space in three-dimensional acoustic crystals.

The Bloch band theory and Brillouin zone (BZ) that characterize wave-like behaviors in periodic mediums are two cornerstones of contemporary physics, ranging from condensed matter to topological physics. Recent theoretical breakthrough revealed that, under the projective symmetry algebra enforced by artificial gauge fields, the usual two-dimensional (2D) BZ (orientable Brillouin two-torus) can be fundamentally modified to a non-orientable Brillouin Klein bottle with radically distinct manifold topology. However, the physical consequence of artificial gauge fields on the more general three-dimensional (3D) BZ (orientable Brillouin three-torus) was so far missing. Here, we theoretically discovered and experimentally observed that the fundamental domain and topology of the usual 3D BZ can be reduced to a non-orientable Brillouin Klein space or an orientable Brillouin half-turn space in a 3D acoustic crystal with artificial gauge fields. We experimentally identify peculiar 3D momentum-space non-symmorphic screw rotation and glide reflection symmetries in the measured band structures. Moreover, we experimentally demonstrate a novel stacked weak Klein bottle insulator featuring a nonzero Z2 topological invariant and self-collimated topological surface states at two opposite surfaces related by a nonlocal twist, radically distinct from all previous 3D topological insulators. Our discovery not only fundamentally modifies the fundamental domain and topology of 3D BZ, but also opens the door towards a wealth of previously overlooked momentum-space multidimensional manifold topologies and novel gauge-symmetry-enriched topological physics and robust acoustic wave manipulations beyond the existing paradigms.

Observation of geometry-dependent skin effect in non-Hermitian phononic crystals with exceptional points.

Exceptional points and skin effect, as the two distinct hallmark features unique to the non-Hermitian physics, have each attracted enormous interests. Recent theoretical works reveal that the topologically nontrivial exceptional points can guarantee the non-Hermitian skin effect, which is geometry-dependent, relating these two unique phenomena. However, such novel relation remains to be confirmed by experiments. Here, we realize a non-Hermitian phononic crystal with exceptional points, which exhibits the geometry-dependent skin effect. The exceptional points connected by the bulk Fermi arcs, and the skin effects with the geometry dependence, are evidenced in simulations and experiments. Our work, building an experimental bridge between the exceptional points and skin effect and uncovering the unconventional geometry-dependent skin effect, expands a horizon in non-Hermitian physics.

Oxygen mediated oxidative couplings of flavones in alkaline water.

Catalyzed oxidative C-C bond coupling reactions play an important role in the chemical synthesis of complex natural products of medicinal importance. However, the poor functional group tolerance renders them unfit for the synthesis of naturally occurring polyphenolic flavones. We find that molecular oxygen in alkaline water acts as a hydrogen atom acceptor and oxidant in catalyst-free (without added catalyst) oxidative coupling of luteolin and other flavones. By this facile method, we achieve the synthesis of a small collection of flavone dimers and trimers including naturally occurring dicranolomin, philonotisflavone, dehydrohegoflavone, distichumtriluteolin, and cyclodistichumtriluteolin. Mechanistic studies using both experimental and computational chemistry uncover the underlying reasons for optimal pH, oxygen availability, and counter-cations that define the success of the reaction. We expect our reaction opens up a green and sustainable way to synthesize flavonoid dimers and oligomers using the readily available monomeric flavonoids isolated from biomass and exploiting their use for health care products and treatment of diseases.

A novel multidomain polyketide synthase is essential for zeamine production and the virulence of Dickeya zeae.

Dickeya zeae is the causal agent of the rice foot rot disease, but its mechanism of infection remains largely unknown. In this study, we identified and characterized a novel gene designated as zmsA. The gene encodes a large protein of 2,346 amino acids in length, which consists of multidomains arranged in the order of N-terminus, ß-ketoacyl synthase, acyl transferase, acyl carrier protein, ß-ketoacyl reductase, dehydratase. This multidomain structure and sequence alignment analysis suggest that ZmsA is a member of the polyketide synthase family. Mutation of zmsA abolished antimicrobial activity and attenuated the virulence of D. zeae. To determine the relationship between antimicrobial activity and virulence, active compounds were purified from D. zeae EC1 and were structurally characterized. This led to identification of two polyamino compounds, i.e., zeamine and zeamine II, that were phytotoxins and potent antibiotics. These results have established the essential role of ZmsA in zeamine biosynthesis and presented a new insight on the molecular mechanisms of D. zeae pathogenicity.

Xanthomonas campestris diffusible factor is 3-hydroxybenzoic acid and is associated with xanthomonadin biosynthesis, cell viability, antioxidant activity, and systemic invasion.

Xanthomonas campestris pv. campestris produces a membrane-bound yellow pigment called xanthomonadin. A diffusible factor (DF) has been reported to regulate xanthomonadin biosynthesis. In this study, DF was purified from bacterial culture supernatants using a combination of solvent extraction, flash chromatography, and high-performance liquid chromatography. Mass spectrometry and nuclear magnetic resonance analyses resolved the DF chemical structure as 3-hydroxybenzoic acid (3-HBA), which was further confirmed by synthetic 3-HBA. Significantly, bioassay and in silico analysis suggest that DF production is widely conserved in a range of bacterial species. Analysis of DF derivatives established the hydroxyl group and its position as the key structural features for the role of DF in xanthomonadin biosynthesis. In addition, we showed that DF is also associated with bacterial survival, H2O2 resistance, and systemic invasion. Furthermore, evidence was also presented that DF and diffusible signaling factor have overlapping functions in modulation of bacterial survival, H2O2 resistance, and virulence. Utilization of different mechanisms to modulate similar virulence traits may provide X. campestris pv. campestris with plasticity in response to various environmental cues.

Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols.

We report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C-H bond activation in the presence of stoichiometric CuI, 2,2'-bipyridine and Na(2)CO(3). We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper-thiolate complex [(L)Cu(SR)] (L: nitrogen-based bidentate ligand such as 2,2'-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including ß-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis.