Geometric Matching for Cross-Modal Retrieval.

Despite its significant progress, cross-modal retrieval still suffers from one-to-many matching cases, where the multiplicity of semantic instances in another modality could be acquired by a given query. However, existing approaches usually map heterogeneous data into the learned space as deterministic point vectors. In spite of their remarkable performance in matching the most similar instance, such deterministic point embedding suffers from the insufficient representation of rich semantics in one-to-many correspondence. To address the limitations, we intuitively extend a deterministic point into a closed geometry and develop geometric representation learning methods for cross-modal retrieval. Thus, a set of points inside such a geometry could be semantically related to many candidates, and we could effectively capture the semantic uncertainty. We then introduce two types of geometric matching for one-to-many correspondence, i.e., point-to-rectangle matching (dubbed P2RM) and rectangle-to-rectangle matching (termed R2RM). The former treats all retrieved candidates as rectangles with zero volume (equivalent to points) and the query as a box, while the latter encodes all heterogeneous data into rectangles. Therefore, we could evaluate semantic similarity among heterogeneous data by the Euclidean distance from a point to a rectangle or the volume of intersection between two rectangles. Additionally, both strategies could be easily employed for off-the-self approaches and further improve the retrieval performance of baselines. Under various evaluation metrics, extensive experiments and ablation studies on several commonly used datasets, two for image-text matching and two for video-text retrieval, demonstrate our effectiveness and superiority.

Identification of ferroptosis-related molecular subtypes and a methylation-related ferroptosis gene prognostic signature in cervical squamous cell carcinoma.

PURPOSE: We aimed to investigate the molecular characteristics of cervical squamous cell carcinoma (CESC) by analyzing ferroptosis-related gene (FRG) expression data to predict prognosis. METHODS: Gene expression and clinicopathological data of patients with CESC were collected from the Cancer Genome Atlas and the Genotype-Tissue Expression databases. Using Cox regression analysis, we identified 21 FRGs associated with prognosis. Cluster analysis categorized patients into subgroups based on these genes and compared their clinicopathological, biological, and immune infiltration features. FRG methylation levels were examined, and a risk model based on such FRG methylation levels was constructed using LASSO and Cox regression analyses. The model's predictive capacity was validated, and the relationships between the risk score and immune infiltration, tumor microenvironment, and drug sensitivity were explored. FRG methylation in CESC tissues was validated by immunohistochemistry. RESULTS: We identified 21 FRGs associated with CESC prognosis. Patients were stratified into two subtypes based on these genes, they showed differences in prognosis, immune cell types, and immune checkpoint expression. A three-gene risk score (including AQP3, MGST1, and TFRC) was generated, and the low-risk group showed better overall survival. The high-risk and low-risk groups differed in terms of immune infiltration, gene mutations, and drug sensitivity. Experimental validation confirmed the upregulation of AQP3 and TFRC, whereas MGST1 expression was not significantly altered in CESC tissues compared with that in normal cervical tissues. CONCLUSION: This study highlights the potential role of FRG methylation in predicting CESC prognosis and provides a personalized assessment of immune responses in patients with CESC.

pH-dependent self-assembly mechanism of a single repetitive domain from a spider silk protein.

Spider silk is self-assembled from full-length silk proteins, and some silk protein fragments can also form silk-like fibers in vitro. However, the mechanism underlying the silk fiber formation is not understood well. In this study, we investigated the fiber formation of a single repetitive domain (RP) from a minor ampullate silk protein (MiSp). Our findings revealed that pH and salt concentration affect not only the stability of MiSp-RP but also its self-assembly into fibers and aggregates. Using nuclear magnetic resonance (NMR) spectroscopy, we solved the three-dimensional (3D) structure of MiSp RP in aqueous solution. On the basis of the structure and mutagenesis, we revealed that charge-dipole interactions are responsible for the pH- and salt-dependent properties of MiSp-RP. Our results indicate that fiber formation is regulated by a delicate balance between intermolecular and intramolecular interactions, rather than by the protein stability alone. These findings have implications for the design of silk proteins for mass production of spider silk.

Oxidative Roles of Polystyrene-Based Nanoplastics in Inducing Manganese Oxide Formation under Light Illumination.

Every year, large quantities of plastics are produced and used for diverse applications, growing concerns about the waste management of plastics and their release into the environment. Plastic debris can break down into millions of pieces that adversely affect natural organisms. In particular, the photolysis of micro/nanoplastics can generate reactive oxygen species (ROS). However, their oxidative roles in initiating redox chemical reactions with heavy and transition metals have received little attention. In this study, we investigated whether the photolysis of polystyrene (PS) nanoplastics can induce the oxidation of Mn2+(aq) to Mn oxide solids. We found that PS nanoplastics not only produced peroxyl radicals (ROO•) and superoxide radicals (O2•-) by photolysis, which both play a role in unexpected Mn oxidation, but also served as a substrate for facilitating the heterogeneous nucleation and growth of Mn oxide solids and controlling the formation rate and crystalline phases of Mn oxide solids. These findings help us to elucidate the oxidative roles of nanoplastics in the oxidation of redox-active metal ions. The production of ROS from nanoplastics in the presence of light can endanger marine life and human health, and affect the mobility of the nanoplastics in the environment via redox reactions, which in turn may negatively impact their environmental remediation.

Photochemical reactions of dissolved organic matter and bromide ions facilitate abiotic formation of manganese oxide solids.

Manganese (Mn) oxide solids are ubiquitous in nature, acting as both electron donors and acceptors in diverse redox reactions in the environment. Reactions of Mn(III/IV) oxides with dissolved natural organic matter (DOM) are commonly described as reductive dissolutions that generate Mn2+(aq). In this study, we investigated the role of photochemical reactions of DOM in Mn2+(aq) oxidation and the resulting formation of Mn oxide solids. During the photolysis of DOM, reactive intermediates can be generated, including excited triplet state DOM (3DOM*), hydroxyl radicals (•OH), superoxide radicals (O2•-), hydrogen peroxide, and singlet oxygen. Among these, we found that O2•- radicals were mainly responsible for Mn oxidation. The solution pH controlled the formation of Mn oxide solids by affecting both Mn2+ oxidation by O2•- during photolysis of DOM and reductive dissolutions of Mn oxide solids by DOM. Further, with the addition of bromide ions (Br-), reactions between 3DOM* and Br-, together with reactions between •OH and Br-, can form reactive bromide radicals. The formed Br radicals also promoted Mn oxide formation. In DOM with more aromatic functional groups, more Mn2+ was oxidized to Mn oxide solids. This enhanced oxidation could be the result of promoted pathways from charge-transfer state DOM (DOM•+/•-) to O2•-. These new observations advance our understanding of natural Mn2+ oxidation and Mn(III/IV) oxide formation and highlight the underappreciated oxidative roles of DOM in the oxidation of metal ions in surface water illuminated by sunlight.

Process-Specific Effects of Sulfate on CaCO3 Formation in Environmentally Relevant Systems.

Additives, such as ions, small molecules, and macromolecules, have been found to regulate the formation of CaCO3 and control its morphologies and properties. However, a single additive usually affects dominantly one process in CaCO3's formation and is seldom found to significantly affect multiple CaCO3 formation processes. Here, we used in situ grazing incidence X-ray techniques to observe the heterogeneous formation of CaCO3 and found that a series of formation processes (i.e., nucleation, growth, and Ostwald ripening) were modulated by sulfate. In the nucleation process, increased interfacial free energy and bulk free energy cooperatively increased the nucleation barrier and decreased nucleation rates. In the growth process, sulfate reduced the electrostatic repulsion between CaCO3 precursors and nuclei, promoting CaCO3 growth. This influence on the growth counteracted the inhibition effect in the nucleation process, causing a nearly 100% increase in the volume of heterogeneously formed CaCO3. Meanwhile, adsorbed sulfate on CaCO3 nuclei may poison the surface of smaller CaCO3 nuclei, inhibiting Ostwald ripening. These revealed sulfate's active roles in controlling CaCO3 formation advance our understanding of sulfate-incorporated biomineralization and scaling phenomena in natural and engineered aquatic environments.

Does Tert-Butyl Alcohol Really Terminate the Oxidative Activity of •OH in Inorganic Redox Chemistry?

The hydroxyl radical, •OH, is one of the most reactive free radicals and plays significant roles in the oxidative degradation of organic pollutants and the electron transfer of inorganic ions in natural and engineered environmental processes. To quantitatively determine the contribution of •OH to oxidative reactions, a specific scavenger, such as tert-butyl alcohol (TBA), is usually added to eliminate •OH effects. Although TBA is commonly assumed to transform •OH into oxidatively inert products, this study demonstrates that utilizing TBA as an •OH scavenger generates the secondary peroxyl radical (ROO•), influencing the oxidation of transition metals, such as Mn. Although ROO• is less reactive than •OH, it has an extended half-life and a longer diffusion distance that enables more redox reactions, such as the oxidation of Mn2+(aq) to MnIV oxide solids. In addition to promoting Mn2+(aq) oxidation kinetics, TBA can also affect the crystalline phases, oxidation states, and morphologies of Mn oxide solids. Thus, the oxidative roles of •OH in aqueous redox reactions cannot be examined simply by adding TBA: the effects of secondary ROO• must also be considered. This study urges a closer look at the potential formation of secondary radicals during scavenged oxidative reactions in environmental systems.

Parity-Induced Thermalization Gap in Disordered Ring Lattices.

The gaps separating two different states widely exist in various physical systems: from the electrons in periodic lattices to the analogs in photonic, phononic, plasmonic systems, and even quasicrystals. Recently, a thermalization gap, an inaccessible range of photon statistics, was proposed for light in disordered structures [Nat. Phys. 11, 930 (2015)NPAHAX1745-247310.1038/nphys3482], which is intrinsically induced by the disorder-immune chiral symmetry and can be reflected by the photon statistics. The lattice topology was further identified as a decisive role in determining the photon statistics when the chiral symmetry is satisfied. Being very distinct from one-dimensional lattices, the photon statistics in ring lattices are dictated by its parity, i.e., odd or even sited. Here, we for the first time experimentally observe a parity-induced thermalization gap in strongly disordered ring photonic structures. In a limited scale, though the light tends to be localized, we are still able to find clear evidence of the parity-dependent disorder-immune chiral symmetry and the resulting thermalization gap by measuring photon statistics, while strong disorder-induced Anderson localization overwhelms such a phenomenon in larger-scale structures. Our results shed new light on the relation among symmetry, disorder, and localization, and may inspire new resources and artificial devices for information processing and quantum control on a photonic chip.

Non-classical photon correlation in a two-dimensional photonic lattice.

Quantum interference and quantum correlation, as two main features of quantum optics, play an essential role in quantum information applications, such as multi-particle quantum walk and boson sampling. While many experimental demonstrations have been done in one-dimensional waveguide arrays, it remains unexplored in higher dimensions due to tight requirement of manipulating and detecting photons in large-scale. Here, we experimentally observe non-classical correlation of two identical photons in a fully coupled two-dimensional structure, i.e. photonic lattice manufactured by three-dimensional femtosecond laser writing. Photon interference consists of 36 Hong-Ou-Mandel interference and 9 bunching. The overlap between measured and simulated distribution is up to 0.890 ± 0.001. Clear photon correlation is observed in the two-dimensional photonic lattice. Combining with controllably engineered disorder, our results open new perspectives towards large-scale implementation of quantum simulation on integrated photonic chips.

Highly active Pd-In/mesoporous alumina catalyst for nitrate reduction.

The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd-In/Al2O3 with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO2-buffered water and under continuous H2 as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd-In ratio of 4, with a first-order rate constant (k(obs) = 0.241 L min(-1) g(cata)(-1)) that was 1.3× higher than that of conventional Pd-In/Al2O3 (5 wt% Pd; 0.19 L min(-1) g(cata)(-1)). The Pd-In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate.

Structural characterization of minor ampullate spidroin domains and their distinct roles in fibroin solubility and fiber formation.

Spider silk is protein fibers with extraordinary mechanical properties. Up to now, it is still poorly understood how silk proteins are kept in a soluble form before spinning into fibers and how the protein molecules are aligned orderly to form fibers. Minor ampullate spidroin is one of the seven types of silk proteins, which consists of four types of domains: N-terminal domain, C-terminal domain (CTD), repetitive domain (RP) and linker domain (LK). Here we report the tertiary structure of CTD and secondary structures of RP and LK in aqueous solution, and their roles in protein stability, solubility and fiber formation. The stability and solubility of individual domains are dramatically different and can be explained by their distinct structures. For the tri-domain miniature fibroin, RP-LK-CTD(Mi), the three domains have no or weak interactions with one another at low protein concentrations (<1 mg/ml). The CTD in RP-LK-CTD(Mi) is very stable and soluble, but it cannot stabilize the entire protein against chemical and thermal denaturation while it can keep the entire tri-domain in a highly water-soluble state. In the presence of shear force, protein aggregation is greatly accelerated and the aggregation rate is determined by the stability of folded domains and solubility of the disordered domains. Only the tri-domain RP-LK-CTD(Mi) could form silk-like fibers, indicating that all three domains play distinct roles in fiber formation: LK as a nucleation site for assembly of protein molecules, RP for assistance of the assembly and CTD for regulating alignment of the assembled molecules.