Exploring the Effects of the Photochromic Response and Crystallization on the Local Structure of Noncrystalline Niobium Oxide.

Niobium oxide (Nb2O5) is a versatile semiconductor material with photochromic properties. This study investigates the local structure of noncrystalline, short-range-ordered niobium oxide synthesized via a sol-gel method. X-ray atomic pair distribution function analysis unravels the structural arrangements within the noncrystalline materials at a local scale. In the following, in situ scattering and diffraction experiments elucidate the heat-induced structure transformation of the amorphous material into crystalline TT-Nb2O5 at 550 °C. In addition, the effect of photocatalytic conditions on the structure of the material was investigated by exposing the short-range-ordered and crystalline materials to ultraviolet light, resulting in a reversible color change from white to dark brown or blue. This photochromic response is due to the reversible elongation of the nearest Nb-O neighbors, as shown by local structure analysis based on in situ PDF analyses. Optical band gap calculations based on the ultraviolet-visible spectra collected for both the short-range-ordered and crystalline materials show that the band gap values reduced for the darkened materials return to their initial state after bleaching. Furthermore, electron energy loss spectroscopy reveals the reduction of Nb5+ to Nb4+ centers as a persistent effect. The study establishes a correlation between the band gap and the structure of niobium oxide, providing insights into the structure-performance relation at the atomic level.

Spectroscopic visualization of reversible hydrogen spillover between palladium and metal-organic frameworks toward catalytic semihydrogenation.

Hydrogen spillover widely occurs in a variety of hydrogen-involved chemical and physical processes. Recently, metal-organic frameworks have been extensively explored for their integration with noble metals toward various hydrogen-related applications, however, the hydrogen spillover in metal/MOF composite structures remains largely elusive given the challenges of collecting direct evidence due to system complexity. Here we show an elaborate strategy of modular signal amplification to decouple the behavior of hydrogen spillover in each functional regime, enabling spectroscopic visualization for interfacial dynamic processes. Remarkably, we successfully depict a full picture for dynamic replenishment of surface hydrogen atoms under interfacial hydrogen spillover by quick-scanning extended X-ray absorption fine structure, in situ surface-enhanced Raman spectroscopy and ab initio molecular dynamics calculation. With interfacial hydrogen spillover, Pd/ZIF-8 catalyst shows unique alkyne semihydrogenation activity and selectivity for alkynes molecules. The methodology demonstrated in this study also provides a basis for further exploration of interfacial species migration.

Biogenic Copper Selenide Nanoparticles for Near-Infrared Photothermal Therapy Application.

Near-infrared (NIR) photothermal therapy (PTT) is attractive for cancer treatment but is currently restricted by limited availability and insufficient NIR-II photoactivity of photothermal agents, for which artificial nanomaterials are usually used. Here, we report the first use of biogenic nanomaterials for PTT application. A fine-controlled extracellular biosynthesis of copper selenide nanoparticles (bio-Cu2-xSe) by Shewanella oneidensis MR-1 was realized. The resulting bio-Cu2-xSe, with fine sizes (∼35.5 nm) and high product purity, exhibited 76.9% photothermal conversion efficiency under 1064 nm laser irradiation, outperforming almost all the existing counterparts. The protein capping also imparted good biocompatibility to bio-Cu2-xSe to favor a safe PTT application. The in vivo PTT with injected bio-Cu2-xSe in mice (without extraction nor further modification) showed 87% tumor ablation without impairing the normal organisms. Our work not only opens a green route to synthesize the NIR-II photothermal nanomaterial but may also lay a basis for the development of bacteria-nanomaterial hybrid therapy technologies.

Recent developments in lead-free bismuth-based halide perovskite nanomaterials for heterogeneous photocatalysis under visible light.

Halide perovskite materials, especially lead-based perovskites, have been widely used for optoelectronic and catalytic applications. However, the high toxicity of the lead element is a major concern that directs the research work toward lead-free halide perovskites, which could utilize bismuth as a promising candidate. Until now, the replacement of lead by bismuth in perovskites has been well studied by designing bismuth-based halide perovskite (BHP) nanomaterials with versatile physical-chemical properties, which are emerging in various application fields, especially heterogeneous photocatalysis. In this mini-review, we present a brief overview of recent progress in BHP nanomaterials for photocatalysis under visible light. The synthesis and physical-chemical properties of BHP nanomaterials have been comprehensively summarized, including zero-dimensional, two-dimensional nanostructures and hetero-architectures. Later, we introduce the photocatalytic applications of these novel BHP nanomaterials with visible-light response, improved charge separation/transport and unique catalytic sites. Due to advanced nano-morphologies, a well-designed electronic structure and an engineered surface chemical micro-environment, BHP nanomaterials demonstrate enhanced photocatalytic performance for hydrogen generation, CO2 reduction, organic synthesis and pollutant removal. Finally, the challenges and future research directions of BHP nanomaterials for photocatalysis are discussed.

Precisely Tailoring Heterometallic Polyoxotitanium Clusters for the Efficient and Selective Photocatalytic Oxidation of Hydrocarbons.

Photocatalysis is a promising yet challenging approach for the selective oxidation of hydrocarbons to valuable oxygenated chemicals with O2 under mild conditions. In this work, we report an atomically precise material model to address this challenge. The key to our solution is the rational incorporation of Fe species into polyoxotitanium cluster to form a heterometallic Ti4 Fe1 cocrystal. This newly designed cocrystal cluster, which well governs the energy and charge transfer as evidenced by spectroscopic characterizations and theoretical calculations, enables the synergistic process involving C(sp3 )-H bond activation by photogenerated holes and further reactions by singlet oxygen (1 O2 ). Remarkably, the cocrystal Ti4 Fe1 cluster achieves efficient and selective oxidation of hydrocarbons (C5 to C16 ) into aldehydes and ketones with a conversion rate up to 12 860 µmol g-1 h-1 , 5 times higher than that of Fe-doped Ti3 Fe1 cluster. This work provides insights into photocatalyst design at atomic level enabling synergistic catalysis.

Mineralization of tribromophenol under anoxic/oxic conditions in the presence of copper(II) doped green rust: Importance of sequential reduction-oxidation process.

The groundwater environment often undergoes the transition from anoxic to oxic due to natural processes or human activities, but the influence of this transition on the fate of groundwater contaminates are not entirely understood. In this work, the degradation of tribromophenol (TBP) in the presence of environmentally relevant iron (oxyhydr)oxides (green rust, GR) and trace metal ions Cu(II) under anoxic/oxic-alternating conditions was investigated. Under anoxic conditions, GR-Cu(II) reduced TBP to 4-BP completely within 7 h while GR only had an adsorption effect on TBP. Under oxic conditions, GR-Cu(II) could generate •OH via dioxygen activation, which resulted in the oxidative transformation of TBP. Sixty-five percentage of TBP mineralization was achieved via a sequential reduction-oxidation process, which was not achieved through single reduction or oxidation process. The produced Cu(I) in GR-Cu(II) enhanced not only the reductive dehalogenation under anoxic conditions, but also the O2 activation under oxic conditions. Thus, the fate of TBP in anoxic/oxic-alternating groundwater environment is greatly influenced by the presence of GR-Cu(II). The sequential reduction-oxidation degradation of TBP by GR-Cu(II) is promising for future remediation of TBP-contaminated groundwater.

Hydroxyl groups bridge the electron transfer from Fe(II) to carbon tetrachloride.

Reductive dechlorination of chlorinated organic pollutants (COPs) by Fe(II) occurs in natural environments and engineered systems. Fe(II) ions undergo hydroxylation in aqueous solutions to form Ferrous Hydroxyl Complex (FHC), which plays an essential role in Fe(II)-mediated reductive dechlorination. However, how hydroxyl groups of FHC bridge the electron transfer from Fe(II) to COPs is still not fully understood. This work shows that the rate of reductive dechlorination of carbon tetrachloride (CT) by FHC increased with increasing OH- dosage. XRD data shows the increase of OH- dosage transform FHC from Fe2(OH)3Cl to Fe(OH)2, which leads to increased reductive strength of FHC. More non-hydrogen bonded hydroxyl groups coordinate with Fe(II) in FHC with increasing the OH- dosage, which stabilizes the octahedral structure of Fe(II) as shown by Mössbauer data. Electrochemical analysis reveals that the increase of OH- dosage enhances the reductive activity of FHC, which is also confirmed by the decreased HOMO-LUMO gap. It was found that FHC dechlorinated CT to methane, which was attributed to the stabilization of trichlorocarbene anion(˸CCl3-) by [surface-O-Fe(II)-OH]+. This work deepens our understanding on the bridge effect of hydroxyl groups on the electron transfer from Fe(II) to COPs, and provides a theoretical foundation for the reductive dechlorination of COPs in both natural environments and engineered systems.

Sunlight-Driven Highly Selective Catalytic Oxidation of 5-Hydroxymethylfurfural Towards Tunable Products.

Owing to the easy over-oxidation, it is a promising yet challenging task to explore renewable carbon resources to control the sunlight-driven selective catalytic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF), producing important chemical feedstocks, namely, less-oxidized 2,5-diformylfuran (DFF) and 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). Herein, we have developed a photocatalyst by anchoring a Ru complex on CdS quantum dots, which achieves selective oxidation of HMF toward DFF or HMFCA with high conversion (>81 %) and selectivity (>90 %), based on the controllable generation of two oxygen radicals under different atmospheres. Such selective conversion can also work well outside the laboratory by using natural sunlight. In particular, the selective production of HMFCA through photocatalytic HMF oxidation is achieved for the first time. More importantly, our photocatalyst is applicable for the selective oxidation of other compounds with hydroxyl and aldehyde groups.

From 1D to 3D Graphitic Carbon Nitride (Melon): A Bottom-Up Route via Crystalline Microporous Templates.

Herein, we present a novel bottom-up preparation route for heptazine-based polymers (melon), also known as graphitic carbon nitride. The growth characteristics of isolated 1D melon strings in microporous templates are presented and studied in detail. Removal of the microporous silicate template via etching is accompanied by the self-assembly of a 1D melon to stacked 3D structures. The advantages and limitations of the bottom-up approach are shown by using microporous templates with different pore sizes (ETS-10, ZSM-5, and zeolite Y). In accordance with the molecular size of the heptazine units (0.67 nm), a 1D melon can be deposited in ETS-10 with a pore width of about 0.78 nm, whereas its formation in the smaller 0.47 nm pores of ZSM-5 is sterically impeded. The self-assembly of isolated 1D melon to stacked 3D structures offers a novel experimental perspective to the controversial debate on the polymerization degree in 2D sheets of graphitic carbon nitride as micropore sizes below 1 nm confine the condensation degree of heptazine to isolated 1D strands at a molecular level. The growth characteristics and structural features were investigated by X-ray diffraction, N2 physisorption, scanning transmission electron microscopy/energy-dispersive X-ray analysis, 13C CP-NMR spectroscopy, and attenuated total reflection-infrared spectroscopy.

Monitoring the Structure Evolution of Titanium Oxide Photocatalysts: From the Molecular Form via the Amorphous State to the Crystalline Phase.

Amorphous Tix Oy with high surface area has attracted significant interest as photocatalyst with higher activity in ultraviolet (UV) light-induced water splitting applications compared to commercial nanocrystalline TiO2 . Under photocatalytic operation conditions, the structure of the molecular titanium alkoxide precursor rearranges upon hydrolysis and leads to higher connectivity of the structure-building units. Structurally ordered domains with sizes smaller than 7 Šform larger aggregates. The experimental scattering data can be explained best with a structure model consisting of an anatase-like core and a distorted shell. Upon exposure to UV light, the white Tix Oy suspension turns dark corresponding to the reduction of Ti4+ to Ti3+ as confirmed by electron energy loss spectroscopy (EELS). Heat-induced crystallisation was followed by in situ temperature-dependent total scattering experiments. First, ordering in the Ti-O environment takes place upon to 350 °C. Above this temperature, the distorted anatase core starts to grow but the structure obtained at 400 °C is still not fully ordered.

A Family of Nonribosomal Peptides Modulate Collective Behavior in Pseudovibrio Bacteria Isolated from Marine Sponges*.

Although swarming motility and biofilms are opposed collective behaviors, both contribute to bacterial survival and host colonization. Pseudovibrio bacteria have attracted attention because they are part of the microbiome of healthy marine sponges. Two-thirds of Pseudovibrio genomes contain a member of a nonribosomal peptide synthetase-polyketide synthase gene cluster family, which is also found sporadically in Pseudomonas pathogens of insects and plants. After developing reverse genetics for Pseudovibrio, we isolated heptapeptides with an ureido linkage and related nonadepsipeptides we termed pseudovibriamides A and B, respectively. A combination of genetics and imaging mass spectrometry experiments showed heptapetides were excreted, promoting motility and reducing biofilm formation. In contrast to lipopeptides widely known to affect motility/biofilms, pseudovibriamides are not surfactants. Our results expand current knowledge on metabolites mediating bacterial collective behavior.

In situ total scattering experiments of nucleation and crystallisation of tantalum-based oxides: from highly dilute solutions via cluster formation to nanoparticles.

The exact formation mechanism of tantalum oxides (and in general, metal/mixed metal oxides) from alkoxide precursors is still not fully understood, particularly when forming cluster-like or amorphous materials. The structural evolution of Ta-based oxides was studied in detail using X-ray total scattering experiments along with subsequent pair distribution function (PDF) analyses. Starting from a tantalum alkoxide precursor (Ta2(OEt)10), the formation of hydrolysed TaxOyHz clusters in highly diluted aqueous solution was analysed. From the PDF data, the connectivity and arrangement of TaxOy octahedra in the cluster could be deduced as well as the approximate size of the clusters (<1 nm). Construction of cluster models allowed for identification of common structural motifs in the TaxOyHz clusters, ruling out the formation of chain- or ring-like clusters. More likely, bulky clusters with a high number of corner-sharing octahedra are formed. After separation of the amorphous solid from the liquid, temperature-induced crystallisation processes were monitored via in situ total scattering experiments. Between room temperature and 600 °C, only small rearrangements of the amorphous structure are observed. At about 610 °C, amorphous TaxOyHz transforms directly into crystalline orthorhombic L-Ta2O5 without formation of any crystalline intermediate structures.

A knowledge-based intensity-modulated radiation therapy treatment planning technique for locally advanced nasopharyngeal carcinoma radiotherapy.

BACKGROUND: To investigate the feasibility of a knowledge-based automated intensity-modulated radiation therapy (IMRT) planning technique for locally advanced nasopharyngeal carcinoma (NPC) radiotherapy. METHODS: One hundred forty NPC patients treated with definitive radiation therapy with the step-and-shoot IMRT techniques were retrospectively selected and separated into a knowledge library (n = 115) and a test library (n = 25). For each patient in the knowledge library, the overlap volume histogram (OVH), target volume histogram (TVH) and dose objectives were extracted from the manually generated plan. 5-fold cross validation was performed to divide the patients in the knowledge library into 5 groups before validating one group by using the other 4 groups to train each neural network (NN) machine learning models. For patients in the test library, their OVH and TVH were then used by the trained models to predict a corresponding set of mean dose objectives, which were subsequently used to generate automated plans (APs) in Pinnacle planning system via an in-house developed automated scripting system. All APs were obtained after a single step of optimization. Manual plans (MPs) for the test patients were generated by an experienced medical physicist strictly following the established clinical protocols. The qualities of the APs and MPs were evaluated by an attending radiation oncologist. The dosimetric parameters for planning target volume (PTV) coverage and the organs-at-risk (OAR) sparing were also quantitatively measured and compared using Mann-Whitney U test and Bonferroni correction. RESULTS: APs and MPs had the same rating for more than 80% of the patients (19 out of 25) in the test group. Both AP and MP achieved PTV coverage criteria for no less than 80% of the patients. For each OAR, the number of APs achieving its criterion was similar to that in the MPs. The AP approach improved planning efficiency by greatly reducing the planning duration to about 17% of the MP (9.85 ± 1.13 min vs. 57.10 ± 6.35 min). CONCLUSION: A robust and effective knowledge-based IMRT treatment planning technique for locally advanced NPC is developed. Patient specific dose objectives can be predicted by trained NN models based on the individual's OVH and clinical TVH goals. The automated planning scripts can use these dose objectives to efficiently generate APs with largely shortened planning time. These APs had comparable dosimetric qualities when compared to our clinic's manual plans.

Controllable Synthesis and Crystallization of Nanoporous TiO2 Deep-Submicrospheres and Nanospheres via an Organic Acid-Mediated Sol-Gel Process.

Although considerable progress has been achieved in the preparation of uniform hydrous TiO2 spheres (HTS) through the sol-gel process, there is plenty of room left in tailoring the size and morphology of HTS on the deep-submicron scale or even nanoscale since the diameters of the so far reported HTS are mostly on the (sub)micron scale (0.3-1.2 µm). Here, we develop a novel titanium tetraisopropoxide (TTIP)-organic acid (OA)-acetonitrile (ACN)-methanol (MeOH)-H2O system, which facilitates the control of nanoporous HTS to the range of 50-300 nm. The synthetic parameters including OA, (co-)solvent, concentration of precursor, and reaction temperature are comprehensively optimized, aiming at reproducible preparation and precise size control. Among the various OAs, n-valeric acid presents the best capability in controlling the spherical morphology and size uniformity. The synthesized amorphous HTS containing numerous micropores and mesopores show excellent hydrothermal stability and offer suitable self-template for the subsequent synthesis of mesoporous anatase TiO2 spheres (MAT) with a large surface area of 99.1 m2/g. The obtained TiO2 deep-submicrospheres and nanospheres with tunable sizes show great potential in various research fields.

Rapid and label-free urine test based on surface-enhanced Raman spectroscopy for the non-invasive detection of colorectal cancer at different stages.

The concept of being able to urinate in a cup and screen for colorectal cancer (CRC) is fascinating to the public at large. Here, a simple and label-free urine test based on surface-enhanced Raman spectroscopy (SERS) was employed for CRC detection. Significant spectral differences among normal, stages I-II, and stages III-IV CRC urines were observed. Using discriminant function analysis, the diagnostic sensitivities of 95.8%, 80.9%, and 84.3% for classification of normal, stages I-II, and stages III-IV CRC were achieved in training model, indicating the great promise of urine SERS as a rapid, convenient and noninvasive method for CRC staging detection.

A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C-H Bond Activation.

Direct selective oxidation of hydrocarbons to oxygenates by O2 is challenging. Catalysts are limited by the low activity and narrow application scope, and the main focus is on active C-H bonds at benzylic positions. In this work, stable, lead-free, Cs3 Bi2 Br9 halide perovskites are integrated within the pore channels of mesoporous SBA-15 silica and demonstrate their photocatalytic potentials for C-H bond activation. The composite photocatalysts can effectively oxidize hydrocarbons (C5 to C16 including aromatic and aliphatic alkanes) with a conversion rate up to 32900 µmol gcat -1 h-1 and excellent selectivity (>99 %) towards aldehydes and ketones under visible-light irradiation. Isotopic labeling, in situ spectroscopic studies, and DFT calculations reveal that well-dispersed small perovskite nanoparticles (2-5 nm) possess enhanced electron-hole separation and a close contact with hydrocarbons that facilitates C(sp3 )-H bond activation by photoinduced charges.

Boosting Photocatalytic Hydrogen Production by Modulating Recombination Modes and Proton Adsorption Energy.

Solar-driven production of renewable energy (e.g., H2) has been investigated for decades. To date, the applications are limited by low efficiency due to rapid charge recombination (both radiative and nonradiative modes) and slow reaction rates. Tremendous efforts have been focused on reducing the radiative recombination and enhancing the interfacial charge transfer by engineering the geometric and electronic structure of the photocatalysts. However, fine-tuning of nonradiative recombination processes and optimization of target reaction paths still lack effective control. Here we show that minimizing the nonradiative relaxation and the adsorption energy of photogenerated surface-adsorbed hydrogen atoms are essential to achieve a longer lifetime of the charge carriers and a faster reaction rate, respectively. Such control results in a 16-fold enhancement in photocatalytic H2 evolution and a 15-fold increase in photocurrent of the crystalline g-C3N4 compared to that of the amorphous g-C3N4.

Lead-Free Cs3 Bi2 Br9 Perovskite as Photocatalyst for Ring-Opening Reactions of Epoxides.

Herein, an innovative approach was developed by using stable, lead-free halide perovskite for solar-driven organic synthesis. The ring-opening reaction of epoxides was chosen as a model system for the synthesis of value-added ß-alkoxy alcohols, which require energy-intensive process conditions and corrosive, strong acids for conventional synthesis. The developed concept included the in situ preparation of Cs3 Bi2 Br9 and its simultaneous application as photocatalyst for epoxide alcoholysis under visible-light irradiation in air at 293 K, with exceptional high activity and selectivity ≥86 % for ß-alkoxy alcohols and thia-compounds. The Cs3 Bi2 Br9 photocatalyst exhibited good stability and recyclability. In contrast, the lead-based perovskite showed a conversion rate of only 1 %. The origin of the unexpected catalytic behavior was attributed to the combination of the photocatalytic process and the presence of suitable Lewis-acidic centers on the surface of the bismuth halide perovskite photocatalyst.

Solid Base Bi24 O31 Br10 (OH)δ with Active Lattice Oxygen for the Efficient Photo-Oxidation of Primary Alcohols to Aldehydes.

The selective oxidation of primary alcohols to aldehydes by O2 instead of stoichiometric oxidants (for example, MnVII , CrVI , and OsIV ) is an important but challenging process. Most heterogeneous catalytic systems (thermal and photocatalysis) require noble metals or harsh reaction conditions. Here we show that the Bi24 O31 Br10 (OH)δ photocatalyst is very efficient in the selective oxidation of a series of aliphatic (carbon chain from C1 to C10 ) and aromatic alcohols to their corresponding aldehydes/ketones under visible-light irradiation in air at room temperature, which would be challenging for conventional thermal and light-driven processes. High quantum efficiencies (71 % and 55 % under 410 and 450 nm irradiation) are reached in a representative reaction, the oxidation of isopropanol. We propose that the outstanding performance of the Bi24 O31 Br10 (OH)δ photocatalyst is associated with basic surface sites and active lattice oxygen that boost the dehydrogenation step in the photo-oxidation of alcohols.

Identification and Directed Development of Non-Organic Catalysts with Apparent Pan-Enzymatic Mimicry into Nanozymes for Efficient Prodrug Conversion.

Nanozymes, nanoparticles that mimic the natural activity of enzymes, are intriguing academically and are important in the context of the Origin of Life. However, current nanozymes offer mimicry of a narrow range of mammalian enzymes, near-exclusively performing redox reactions. We present an unexpected discovery of non-proteinaceous enzymes based on metals, metal oxides, 1D/2D-materials, and non-metallic nanomaterials. The specific novelty of these findings lies in the identification of nanozymes with apparent mimicry of diverse mammalian enzymes, including unique pan-glycosidases. Further novelty lies in the identification of the substrate scope for the lead candidates, specifically in the context of bioconversion of glucuronides, that is, human metabolites and privileged prodrugs in the field of enzyme-prodrug therapies. Lastly, nanozymes are employed for conversion of glucuronide prodrugs into marketed anti-inflammatory and antibacterial agents, as well as "nanozyme prodrug therapy" to mediate antibacterial measures.