A hybrid photocatalytic system enables direct glucose utilization for methanogenesis.

Integration of methanogenic archaea with photocatalysts presents a sustainable solution for solar-driven methanogenesis. However, maximizing CH4 conversion efficiency remains challenging due to the intrinsic energy conservation and strictly restricted substrates of methanogenic archaea. Here, we report a solar-driven biotic-abiotic hybrid (biohybrid) system by incorporating cadmium sulfide (CdS) nanoparticles with a rationally designed methanogenic archaeon Methanosarcina acetivorans C2A, in which the glucose synergist protein and glucose kinase, an energy-efficient route for glucose transport and phosphorylation from Zymomonas mobilis, were implemented to facilitate nonnative substrate glucose for methanogenesis. We demonstrate that the photo-excited electrons facilitate membrane-bound electron transport chain, thereby augmenting the Na+ and H+ ion gradients across membrane to enhance adenosine triphosphate (ATP) synthesis. Additionally, this biohybrid system promotes the metabolism of pyruvate to acetyl coenzyme A (AcCoA) and inhibits the flow of AcCoA to the tricarboxylic acid (TCA) cycle, resulting in a 1.26-fold augmentation in CH4 production from glucose-derived carbon. Our results provide a unique strategy for enhancing methanogenesis through rational biohybrid design and reprogramming, which gives a promising avenue for sustainably manufacturing value-added chemicals.

Achiral Solvent Inversed Helical Pathway and Cosolvent Controlled Excited-State "Majority Rule" in Enantiomeric Dansulfonamide Assemblies.

Achiral solvents are commonly utilized to induce the self-assembly of chiral molecules. This study demonstrates that achiral solvents can trigger helicity inversion in the assemblies of dansyl amphiphiles and control the excited-state "majority rule" in assemblies composed of pure enantiomers, through variation of the cosolvent ratio. Specifically, enantiomers of dansyl amphiphiles self-assemble into helical structures with opposite handedness in methanol (MeOH) and acetonitrile (MeCN), together with inversed circular dichroism and circularly polarized luminescence (CPL) signals. When a mixture of MeOH and MeCN is employed, the achiral cosolvents collectively affect the CPL of the assemblies in a way similar to that of "mixed enantiomers". The dominant cosolvent governs the CPL signal. As the cosolvent composition shifts from pure MeCN to MeOH, the CPL signals undergo a significant inversion and amplification, with two maxima observed at ≈20% MeOH and 20% MeCN. This study deepens the comprehension of how achiral solvents modulate helical nanostructures and their excited-state chiroptical properties.

Mechanism of transport and toxicity response of Chlorella sorokiniana to polystyrene nanoplastics.

The toxicity of nanoparticles to freshwater microalgae is of significant importance in maintaining the overall stability of aquatic ecosystems. However, the transport mechanism and toxicity response of microalgae towards nanoplastics (NPs) remain to be further investigated. In this study, we examined the toxicity and internalization mechanisms of polystyrene nanoplastics (PS-NPs) in the microalga Chlorella sorokiniana. The results revealed that the PS-NPs inhibited algal cells' growth and disrupted cell integrity upon contact, leading to cell shrinkage or rupture. Moreover, amino-modified PS-NPs (Nano-PS-NH2) exhibited greater toxicity to C. sorokiniana than carboxyl-modified PS-NPs (Nano-PS-COOH). Furthermore, significant inhibition of PS-NPs internalization was observed when four different endocytosis-related inhibitors were used, indicating that internalized PS-NPs can enter algal cells through endocytic pathways. More importantly, C. sorokiniana exposed to Nano-PS-NH2 responded to the reduction in carbon sources and energy resulting from the suppression of photosynthesis by regulating the metabolism of carbohydrates. These findings elucidate the effects of PS-NPs on C. sorokiniana, including their impact on cell morphology and metabolism, while shedding light on the internalization mechanisms of NPs by C. sorokiniana which deepen our understanding of the toxicity of nanoplastics on algae and provide important theoretical support for solving such aquatic ecological environment problems.

Pathway-Dependent Self-Assembly for Control over Helical Nanostructures and Topochemical Photopolymerization.

Pathway-dependent self-assembly, in which a single building block forms two or more types of self-assembled nanostructures, is an important topic due to its mimic to the complexity in biology and manipulation of diverse supramolecular materials. Here, we report a pathway-dependent self-assembly using chiral glutamide derivatives (L or D-PAG), which form chiral nanotwist and nanotube through a cooperative slow cooling and an isodesmic fast cooling process, respectively. Furthermore, pathway-dependent self-assembly can be harnessed to control over the supramolecular co-assembly of PAG with a luminophore ß-DCS or a photopolymerizable PCDA. Fast cooling leads to the co-assembled PAG/ß-DCS nanotube exhibiting green circularly polarized luminescence (CPL), while slow cooling to nanofiber with blue CPL. Additionally, fast cooling process promotes the photopolymerization of PCDA into a red chiral polymer, whereas slow cooling inhibits the polymerization. This work not only demonstrates the pathway-dependent control over structural characteristics but also highlights the diverse functions emerged from the different assemblies.

Engineering of a Self-Regulatory Bidirectional DNA Assembly Circuit for Amplified MicroRNA Imaging.

The engineering of catalytic hybridization DNA circuits represents versatile ways to orchestrate a complex flux of molecular information at the nanoscale, with potential applications in DNA-encoded biosensing, drug discovery, and therapeutics. However, the diffusive escape of intermediates and unintentional binding interactions remain an unsolved challenge. Herein, we developed a compact, yet efficient, self-regulatory assembly circuit (SAC) for achieving robust microRNA (miRNA) imaging in live cells through DNA-templated guaranteed catalytic hybridization. By integrating the toehold strand with a preblocked palindromic fragment in the stem domain, the proposed miniature SAC system allows the reactant-to-template-controlled proximal hybridization, thus facilitating the bidirectional-sustained assembly and the localization-intensified signal amplification without undesired crosstalk. With condensed components and low reactant complexity, the SAC amplifier realized high-contrast intracellular miRNA imaging. We anticipate that this simple and template-controlled design can enrich the clinical diagnosis and prognosis toolbox.

Pathological characteristics and congenital immunological responses of pigeons-infected with Neospora caninum.

Pigeons are natural intermediate host of Neospora caninum (N. caninum). In comparison to ruminants, N. caninum causes milder clinical symptoms and less financial loss to pigeons. Natural infectious rates and high prevalence of N. caninum in pigeons, and death cases of N. caninum-infected pigeons under experimental conditions have been reported, but the detailed pathological characteristics and congenital immunological responses of pigeons-infected with N. caninum remain not well described. In this study, pigeons were infected intraperitoneally with 107 N. caninum tachyzoites. N. caninum in tissues was detected by qPCR. Pathological changes of tissues were examined by hematoxylin-eosin staining. Blood smears were prepared for counting eosinophils changes in blood. Heterophil extracellular traps (HETs) in vivo and in vitro were quantified by Pico Green. N. caninum-induced HETs structures were observed by immunofluorescence staining. The model of pigeons-infected with N. caninum was successfully established. Lung and duodenum were the main target organs of pigeons-infected with N. caninum. N. caninum caused hemorrhage, edema and inflammatory cell infiltration in liver, pulmonary congestion and hemorrhage, organizational destruction in lung, and shorter villi or even disappear in duodenum. N. caninum also increased the number of eosinophils in blood of pigeons. Moreover, N. caninum-induced HETs release in the congenital immunological system of pigeons were first demonstrated, and the HETs structures were consisted of DNA as the skeleton and modified with citH3 and elastase. N. caninum-induced HETs release was related with NADPH oxidase, TLR 2 and 4, ERK1/2 and p38 MAPK signaling pathways, and glycolysis. In summary, it is the first report on the detailed pathological characteristics and congenital immunological responses of pigeons-infected with N. caninum, which may provide theoretical basis for the prevention and control of Neosporosis in pigeons.

Toxoplasma gondii triggers heterophil extracellular traps via NADPH oxidase, ERK1/2 and P38 signalling pathways, glycolysis and autophagy in chickens.

Toxoplasma gondii is a zoonotic parasite with a global distribution. Heterophil extracellular traps (HETs) are a novel innate immune mechanism of chickens against pathogens, but whether T. gondii can induce HETs release in chickens has not been reported. The effects of T. gondii on heterophils viability were assessed by using Cell Counting Kit-8. T. gondii-induced HETs were observed and analysed by the immunofluorescence method. T. gondii-induced reactive oxygen species (ROS) was determined by the DCFH-DA method. The mechanisms underlying T. gondii-triggered HETs were investigated by inhibitors and fluorescence microplate reader. T. gondii did not significantly affect heterophils viability at a 1:1 ratio within 1 h. It was demonstrated for the first time that T. gondii could induce HETs release in chicken, and the structure of HETs was comprised of DNA, elastase and citrullinated histone 3 (citH3). T. gondii increased ROS production in a dose-dependent manner. Inhibitors of NADPH oxidase, extracellular signal-regulated kinase 1/2 (ERK1/2 ) and P38 signalling pathways, glycolysis and autophagy significantly decreased the release of T. gondii-induced HETs. Taken together, T. gondii can induce HETs release in chickens, and ROS, NADPH oxidase, ERK1/2 and P38 signalling pathways, glycolysis and autophagy participate in the process of HETs release, which provides new insights into the innate immune mechanism of chickens against T. gondii infection.

Solvent-dependent supramolecular assembly behavior of a coumarin-headed amphiphile.

To study the effect of solvent on supramolecular self-assembly behaviors, a chiral courmarin-substituted glutamine amphiphile, L/DG-Cm, was synthesized for investigation. It was found that L/DG-Cm self-assembled into short nanotubes in toluene, while it formed longer nanotubes together with an obvious helix nanobelt structure for L/DG-Cm in DMSO, demonstrating that the nanotubes were formed by nanobelt rolling. The CD and CPL spectra revealed the same chiral property of the L/DG-Cm assemblies formed in toluene and DMSO. Theoretical calculations revealed that LG-Cm was prone to forming similar dimer structures in both DMSO and toluene. However, the distinct hierarchical packing ways in toluene and DMSO led to different nanostructures and chiroptical properties. Based on the temperature-dependent UV-visible and CD spectrometric measurements, LG-Cm was observed to aggregate in different supramolecular self-assembly modes, which was the cooperative (nucleation-elongation) mechanism in toluene and the isodesmic model in DMSO. This work proves that the solvent not only affects the self-assembly morphologies and properties but also determines the self-assembly pathways.

Toxoplasma gondii-induced neutrophil extracellular traps are relevant to glycolysis, TLR2, and TLR4 MAPK signaling pathway in goats.

Toxoplasma gondii (T. gondii) exhibits a significantly high prevalence of infection in goats, leading to adverse consequences such as abortion and stillbirth in ewes, thereby posing a substantial challenge to the goat farming industry. Neutrophil extracellular traps (NETs) have been shown to capture T. gondii in goats; however, the precise mechanisms underlying NET release in goats remain poorly understood. Therefore, the aim of our research was to elucidate the involved mechanism. We assessed the cytotoxicity of T. gondii on neutrophils using CCK-8 assay, visualized the structure of T. gondii-induced goat NETs through immunofluorescence, quantified ROS release during T. gondii-induced NET formation using fluorescence microplate analysis, and employed inhibitors targeting TLR 2, TLR4, NADPH oxidase, ERK1/2, and P38 MAPK signaling pathways as well as glycolysis to dissect the mechanisms underlying T. gondii-induced NET release. Within 1 h, T. gondii did not exhibit significant cytotoxicity towards neutrophils in our findings. The formation of typical NET structures induced by T. gondii involved DNA, citrullinated histone 3 (citH3), and neutrophil elastase (NE). Additionally, T. gondii significantly stimulated the release of NETs in goats. The process was accompanied by the production of reactive oxygen species (ROS) mediated through NADPH oxidase, p38, and ERK1/2 signaling pathways. Inhibition of these pathways resulted in a decrease in NET release. Moreover, inhibition of TLR 2, TLR4, and glycolysis also led to a reduction in T. gondii-induced NET release. Overall, our study demonstrates that T. gondii can induce characteristic NET structures and elucidates the involvement of various mechanisms including TLR2/TLR4 signaling pathway activation, NADPH oxidase activity modulation via ROS production regulation through p38 MAPK and ERK1/2 signaling pathways, and glycolysis regulation during the innate immune response against T. gondii infection in goats.

Ultrasound-Directed Symmetry Breaking and Spin Filtering of Supramolecular Assemblies from only Achiral Building Blocks.

Herein we describe the self-assembly of an achiral molecule into macroscopic helicity as well as the emergent chiral-selective spin-filtering effect. It was found that a benzene-1,3,5-tricarboxamide (BTA) motif with an aminopyridine group in each arm could coordinate with AgI and self-assemble into nanospheres. Upon sonication, symmetry breaking occurred and the nanospheres transferred into helical nanofibers with strong CD signals. Although the sign of the CD signals appeared randomly, it could be controlled by using the as-made chiral assemblies as a seed. Furthermore, it was found that the charge transport of the helical nanofibers was highly selective with a spin-polarization transport of up to 45 %, although the chiral nanofibers are composed exclusively from achiral building blocks. This work demonstrates symmetry breaking under sonication and the chiral-selective spin-filtering effect.

Mutant p53 antagonizes p63/p73-mediated tumor suppression via Notch1.

p53 is the most frequently mutated gene in human cancers and mutant p53 has a gain of function (GOF) that promotes tumor progression and therapeutic resistance. One of the major GOF activities of mutant p53 is to suppress 2 other p53 family proteins, p63 and p73. However, the molecular basis is not fully understood. Here, we examined whether mutant p53 antagonizes p63/p73-mediated tumor suppression in vivo by using mutant p53-R270H knockin and TAp63/p73-deficient mouse models. We found that knockin mutant p53-R270H shortened the life span of p73+/- mice and subjected TAp63+/- or p73+/- mice to T lymphoblastic lymphomas (TLBLs). To unravel the underlying mechanism, we showed that mutant p53 formed a complex with Notch1 intracellular domain (NICD) and antagonized p63/p73-mediated repression of HES1 and ECM1. As a result, HES1 and ECM1 were overexpressed in TAp63+/- ;p53R270H/- and p73+/- ;p53R270H/- TLBLs, suggesting that normal function of HES1 and ECM1 in T cell activation is hyperactivated, leading to lymphomagenesis. Together, our data reveal a previously unappreciated mechanism by which GOF mutant p53 hijacks the p63/p73-regulated transcriptional program via the Notch1 pathway.

Detection of SARS-CoV-2 with Solid-State CRISPR-Cas12a-Assisted Nanopores.

The outbreak of the SARS-CoV-2 caused the disease COVID-19 to spread globally. Specific and sensitive detection of SARS-CoV-2 facilitates early intervention and prevents the disease from spreading. Here, we present a solid-state CRISPR-Cas12a-assisted nanopore (SCAN) sensing strategy for the specific detection of SARS-CoV-2. We introduced a nanopore-sized counting method to measure the cleavage ratio of reporters, which is used as a criterion for positive/negative classification. A kinetic cleavage model was developed and validated to predict the reporter size distributions. The model revealed the trade-offs between sensitivity, turnaround time, and false-positive rate of the SARS-CoV-2 SCAN. With preamplification and a 30 min CRISPR Cas12a assay, we achieved excellent specificity against other common human coronaviruses and a limit of detection of 13.5 copies/µL (22.5 aM) of viral RNA at a confidence level of 95%. These results suggested that the SCAN could provide a rapid, sensitive, and specific analysis of SARS-CoV-2.

Excitation-Dependent Circularly Polarized Luminescence from Helical Assemblies Based on Tartaric Acid-Derived Acylhydrazones.

Here, we combined the merits of emergent excitation-dependent (ExD) emission and circularly polarized luminescence to develop an excitation-dependent circularly polarized luminescence (ExD CPL) material showing unique features. A series of acylhydrazones based on a chiral tartaric skeleton was designed and found to self-assemble into helical nanostructures through non-covalent bonds. The helical assemblies showed ExD CPL due to the cooperation of chirality transfer and excited state intramolecular proton transfer (ESIPT). Remarkably, not only the emission wavelength could be tuned by the excitation wavelength but the handedness of CPL could be modulated in an inverted or ON/OFF manner as well, thus leading to the first example of an ExD inverted or ON/OFF switchable CPL system. Time-dependent density functional theory (TD-DFT) calculations were carried out to explain the inversion of ExD CPL. This work provided a new insight into the unprecedented handedness controllable ExD CPL, which showcased a new paradigm of the advanced CPL materials.

Self-Assembly of Macrocyclic Triangles into Helicity-Opposite Nanotwists by Competitive Planar over Point Chirality.

While helix has elegant biomimetic structures and functionalities, it still remains a big question how the nanoscale helicity evolved from the molecular chiral building blocks across length scales. Herein, macrocyclic triangles composed of achiral edges and chiral vertices were rationally designed, in which the planar chirality emerged due to the restriction of edge rotation by intermolecular stackings and led to a unique chiral self-assembly. In contrast to the solution systems where the chiroptical property is exclusively dominated by the point chiral vertices, the emerged planar chirality was found to control the chiral self-assembly, resulting the nanotwist with the handedness determined by the planar chirality. Our work unveiled the self-assembly behaviors of macrocyclic conformers for the first time and provided a deep understanding on the macrocyclic chirality evolution including the excited-state chirality.

Sub-second heat inactivation of coronavirus using a betacoronavirus model.

Heat treatment denatures viral proteins that comprise the virion, making the virus incapable of infecting a host. Coronavirus (CoV) virions contain single-stranded RNA genomes with a lipid envelope and four proteins, three of which are associated with the lipid envelope and thus are thought to be easily denatured by heat or surfactant-type chemicals. Prior studies have shown that a temperature as low as 75°C with a treatment duration of 15 min can effectively inactivate CoV. The degree of CoV heat inactivation greatly depends on the length of heat treatment time and the temperature applied. With the goal of finding whether sub-second heat exposure of CoV can sufficiently inactivate CoV, we designed and developed a simple fluidic system that can measure sub-second heat inactivation of CoV. The system is composed of a stainless-steel capillary immersed in a temperature-controlled oil bath followed by an ice bath, through which virus solution can flow at various speeds. Flowing virus solution at different speeds, along with temperature control and monitoring system, allows the virus to be exposed to the desired temperature and treatment durations with high accuracy. Using mouse hepatitis virus, a betacoronavirus, as a model CoV system, we identified that 71.8°C for 0.51 s exposure is sufficient to obtain >5 Log10 reduction in viral titer (starting titer: 5 × 107 PFU/ml), and that when exposed to 83.4°C for 1.03 s, the virus was completely inactivated (>6 Log10 reduction).

Inversing supramolecular chirality and boosting circularly polarized luminescence of pyrene moieties via a gel matrix.

Alkyl-substituted l/d-glutamide derivatives (L/D-SG) were designed as gelators to fabricate host gel matrices. Pyrene-appended l/d-glutamide derivatives (Py-LG/Py-DG) were employed as guest luminophores to investigate chiral packing and emission behavior in gel matrices. It was found that Py-LG and Py-DG are prone to form P- and M-chirally packed assemblies in DMSO gels, respectively. However, the chiral packing was inversed, and CPL was boosted after Py-LG/Py-DG was embedded in the L/D-SG gel matrix. M-chiral packing together with left-handed excimer emission ((-)-CPL) was observed in the Py-LG immobilized L-SG gel matrix, while P-chiral packing together with right-handed excimer emission ((+)-CPL) was found in the Py-DG immobilized L-SG gel matrix. It is more interesting to find that the molecular chirality of the matrix gelator did not affect the supramolecular chirality of pyrene assemblies. Either l or a d-matrix gelator can inverse the supramolecular chirality of the pure gel, but did not follow the chirality of the matrix. It was found that the gel matrix converts intralayer pyrene-pyrene (Py-Py) packing in the pure pyrene gel to interlayer Py-Py packing, thus giving an opposite chirality. The study not only deepened our understanding of the supramolecular chirality transfer but also unveiled the effects of an inert gel matrix in regulating the chiroptical properties.

Circularly Polarized Luminescence from Solvent-Free Chiral Organic π-Liquids.

The solvent-free organic π-liquids have been attracting increasing attentions owing to the inherent optoelectronic properties accompanied by the advantages of non-volatility and high processability. Herein, we reported a series of naphthalene derivatives substituted with chiral branched alkyl chains, which are present as liquids (Nap1-3) or solid (Nap4) at room temperature, depending on the substitution positions. Circular dichroism (CD) and circularly polarized luminescence (CPL) were only observed for enantiomeric Nap2 (2,3-substituted) liquid. It is suggested that the chiral aggregation in the π-liquid leads to the CD signal and the chiral excimer resulting in the CPL performance. When achiral anthracene or pyrene was dissolved in Nap2, the π-liquid could serve as chirality and energy transfer media in which both CD and CPL emerged from the achiral anthracene. A CPL dissymmetry factor (|glum |) of anthracene reached to 5.2×10-2 when dissolved in chiral Nap2 liquid, which is nearly two orders of magnitude higher than that of the pure Nap2 π-liquid.

Bamboo-like π-Nanotubes with Tunable Helicity and Circularly Polarized Luminescence.

We report the fabrication of an exotic bamboo-like π-nanotube via the hierarchical self-assembly of a dipeptide-substituted naphthalenediimide gelator with tunable helicity and circularly polarized luminescence (CPL). It was found that in the presence of trifluoroacetic acid (TFA) the gelator molecules self-assembled into a bamboo-like π-nanotube, which is composed of truncated nanocones and CPL active. When defining the diameter ratio of the lower to upper edge of each nanocone as a parameter to express the helicity of different nanotubes, it was found that both the helicity and CPL of these nanotubes can be adjusted by the amount of TFA. Moreover, the helicity of the nanotube can be conveyed to the achiral quantum dots (QDs) and produce a hybrid nanotube/QDs CPL active materials with adjustable dissymmetry factor. This work finds a new type self-assembled bamboo-like π-nanotube and unveils their helicity and CPL control.

Self-assembly of isomeric naphthalene appended glucono derivatives: nanofibers and nanotwists with circularly polarized luminescence emission.

Two isomeric naphthalene appended glucono derivatives substituted at the 1 or 2-naphthyl positions (Nap-1 and Nap-2) were designed and their self-assembly behaviors and optical properties were investigated. Nap-1 and Nap-2 were found to self-assemble into nanofibers and nanotwists, respectively. While the molecular chirality of the glucono moiety could not be effectively transferred to the naphthalene moiety in the Nap-1 system, this was achieved in the Nap-2 assembly. Thus, the Nap-2 assembly showed obvious circular dichroism (CD) and circularly polarized luminescence (CPL) signals. From the XRD patterns and IR spectra of the supramolecular assemblies, it was found that Nap-2 packed in a more orderly fashion than Nap-1, leading to a hierarchical assembly forming nanotwist structures. Moreover, a light-harvesting system based on Nap-2 supramolecular gels and dyes was established, in which an efficient energy transfer was demonstrated from Nap-2 to an acceptor Eosin Y. It was further found that both chirality and energy transfer enhanced the dissymmetry factor of Eosin Y CPL emission.

Applying Marcus theory to describe the carrier transports in organic semiconductors: Limitations and beyond.

Marcus theory has been successfully applied to molecular design for organic semiconductors with the aid of quantum chemistry calculations for the molecular parameters: the intermolecular electronic coupling V and the intramolecular charge reorganization energy λ. The assumption behind this is the localized nature of the electronic state for representing the charge carriers, being holes or electrons. As far as the quantitative description of carrier mobility is concerned, the direct application of Marcus semiclassical theory usually led to underestimation of the experimental data. A number of effects going beyond such a semiclassical description will be introduced here, including the quantum nuclear effect, dynamic disorder, and delocalization effects. The recently developed quantum dynamics simulation at the time-dependent density matrix renormalization group theory is briefly discussed. The latter was shown to be a quickly emerging efficient quantum dynamics method for the complex system.