Meaningful nomograms based on systemic immune inflammation index predicted survival in metastatic pancreatic cancer patients receiving chemotherapy.

OBJECTIVE: The purpose of the study is to construct meaningful nomogram models according to the independent prognostic factor for metastatic pancreatic cancer receiving chemotherapy. METHODS: This study is retrospective and consecutively included 143 patients from January 2013 to June 2021. The receiver operating characteristic (ROC) curve with the area under the curve (AUC) is utilized to determine the optimal cut-off value. The Kaplan-Meier survival analysis, univariate and multivariable Cox regression analysis are exploited to identify the correlation of inflammatory biomarkers and clinicopathological features with survival. R software are run to construct nomograms based on independent risk factors to visualize survival. Nomogram model is examined using calibration curve and decision curve analysis (DCA). RESULTS: The best cut-off values of 966.71, 0.257, and 2.54 for the systemic immunological inflammation index (SII), monocyte-to-lymphocyte ratio (MLR), and neutrophil-to-lymphocyte ratio (NLR) were obtained by ROC analysis. Cox proportional-hazards model revealed that baseline SII, history of drinking and metastasis sites were independent prognostic indices for survival. We established prognostic nomograms for primary endpoints of this study. The nomograms' predictive potential and clinical efficacy have been evaluated by calibration curves and DCA. CONCLUSION: We constructed nomograms based on independent prognostic factors, these models have promising applications in clinical practice to assist clinicians in personalizing the management of patients.

Small but bright: origin of the enhanced luminescence of ultrasmall ZnGa2O4:Cr3+ in mesoporous silica nanoparticles.

Chromium(III)-doped zinc gallate (CZGO) is one of the representative persistent luminescent phosphors emitting in the near-infrared (NIR) region. The emission wavelength it covers falls in the tissue-transparent window, making CZGO a promising optical probe for various biomedical applications. The PersL mechanism dictates that such a phenomenon is only profound in large crystals, so the preparation of CZGO with sizes small enough for biological applications while maintaining its luminescence remains a challenging task. Recent attempts to use mesoporous silica nanoparticles (MSN) as a template for growing nanosized CZGO have been successful. MSN is also a well-studied drug carrier, and incorporating CZGO in MSN further expands its potential in imaging-guided therapeutics. Despite the interest, it is unclear of how the addition of MSN would affect the luminescence properties of CZGO. In this work, we observed that forming a CZGO@MSN nanocomposite could enhance the luminescence intensity and extend the PersL lifetime of CZGO. X-ray absorption fine structure (XAFS) analysis was conducted to investigate the local structure of Zn2+, and an interaction between Zn2+ in CZGO and the MSN matrix was identified.

ScnML models single-cell transcriptome to predict spinal cord neuronal cell status.

Injuries to the spinal cord nervous system often result in permanent loss of sensory, motor, and autonomic functions. Accurately identifying the cellular state of spinal cord nerves is extremely important and could facilitate the development of new therapeutic and rehabilitative strategies. Existing experimental techniques for identifying the development of spinal cord nerves are both labor-intensive and costly. In this study, we developed a machine learning predictor, ScnML, for predicting subpopulations of spinal cord nerve cells as well as identifying marker genes. The prediction performance of ScnML was evaluated on the training dataset with an accuracy of 94.33%. Based on XGBoost, ScnML on the test dataset achieved 94.08% 94.24%, 94.26%, and 94.24% accuracies with precision, recall, and F1-measure scores, respectively. Importantly, ScnML identified new significant genes through model interpretation and biological landscape analysis. ScnML can be a powerful tool for predicting the status of spinal cord neuronal cells, revealing potential specific biomarkers quickly and efficiently, and providing crucial insights for precision medicine and rehabilitation recovery.

Efficient and durable seawater electrolysis with a V2O3-protected catalyst.

The ocean, a vast hydrogen reservoir, holds potential for sustainable energy and water development. Developing high-performance electrocatalysts for hydrogen production under harsh seawater conditions is challenging. Here, we propose incorporating a protective V2O3 layer to modulate the microcatalytic environment and create in situ dual-active sites consisting of low-loaded Pt and Ni3N. This catalyst demonstrates an ultralow overpotential of 80 mV at 500 mA cm-2, a mass activity 30.86 times higher than Pt-C and maintains at least 500 hours in seawater. Moreover, the assembled anion exchange membrane water electrolyzers (AEMWE) demonstrate superior activity and durability even under demanding industrial conditions. In situ localized pH analysis elucidates the microcatalytic environmental regulation mechanism of the V2O3 layer. Its role as a Lewis acid layer enables the sequestration of excess OH- ions, mitigate Cl- corrosion, and alkaline earth salt precipitation. Our catalyst protection strategy by using V2O3 presents a promising and cost-effective approach for large-scale sustainable green hydrogen production.

Axially Modified Square-Pyramidal CoN4-F1 Sites Enabling High-Performance Zn-Air Batteries.

Cobalt-nitrogen-carbon (Co-N-C) catalysts with a CoN4 structure exhibit great potential for oxygen reduction reaction (ORR), but the imperfect adsorption energy toward oxygen species greatly limits their reduction efficiency and practical application potential. Here, F-coordinated Co-N-C catalysts with square-pyramidal CoN4-F1 configuration are successfully synthesized using F atoms to regulate the axial coordination of Co centers via hydrothermal and chemical vapor deposition methods. During the synthesis process, the geometry structure of the Co atom converts from six-coordinated Co-F6 to square-pyramidal CoN4-F1 in the coordinatively unsaturated state, which provides an open binding site for the O2. The introduction of axial F atoms into the CoN4 plane alters the local atomic environment around Co, significantly improving the ORR activity and Zn-air batteries performance. In situ spectroscopy proves that CoN4-F1 sites strongly combine with the OOH* intermediate and facilitate the splitting of O-O bond, making OOH* readily decompose into O* and OH* via a dissociative pathway. Theoretical calculations confirm that the axial F atom effectively reduces the electronic density of the Co centers and facilitates the desorption of the OH* intermediate, efficiently accelerating the overall ORR kinetics. This work advances a feasible synthesis mechanism of axial ligands and provides a route to construct efficient high-coordination catalysts.

Development and validation of an insulated isothermal polymerase chain reaction assay for the rapid detection of Mycoplasma synoviae.

Mycoplasma synoviae, which causes the disease known as chicken synovitis, causes serious immunosuppression. We developed a rapid insulated isothermal polymerase chain reaction (iiPCR) assay for on-site detection of M. synoviae using a primer and probe set targeting the variable lipoprotein and haemagglutinin (vlhA) gene. In addition, the specificity, sensitivity, repeatability, and clinical detection of this method were evaluated. Our iiPCR assay detected M. synoviae clinical isolates and samples successfully and produced negative results on Mycoplasma galliscepticum, avian viral arthritis, Escherichia coli, Salmonella, Staphylococcus aureus and Corynebacterium, indicating that the PCR reactions were specific. Additionally, our iiPCR assay detected the prepared positive standard plasmid diluted 10 times (1.00 × 10-1 - 1.00 × 10-10) as a template. The undiluted positive plasmid was positive and double distilled water was negative indicating that the PCR reactions were sensitive, respectively. Finally, the vlhA positive standard plasmid with dilution multiple of 1.00 × 10-4 - 1.00 × 10-6 was repeatedly detected three times to evaluate the repeatability of the iiPCR method established in this experiment showing that the iiPCR of M. synoviae is repeatable. The established iiPCR was also used to detect 50 chicken joint enlargement samples. The thermostatic detection PCR established in this experiment was comparable to a reference real-time PCR (qPCR).

Synergistic Lewis and Brønsted Acid Sites Promote OH* Formation and Enhance Formate Selectivity: Towards High-efficiency Glycerol Valorization.

As a sustainable valorization route, electrochemical glycerol oxidation reaction (GOR) involves in formation of key OH* and selective adsorption/cleavage of C-C(O) intermediates with multi-step electron transfer, thus suffering from high potential and poor formate selectivity for most non-noble-metal-based electrocatalysts. So, it remains challenging to understand the structure-property relationship as well as construct synergistic sites to realize high-activity and high-selectivity GOR. Herein, we successfully achieve dual-high performance with low potentials and superior formate selectivity for GOR by forming synergistic Lewis and Brønsted acid sites in Ni-alloyed Co-based spinel. The optimized NiCo oxide solid-acid electrocatalyst exhibits low reaction potential (1.219 V@10 mA/cm2) and high formate selectivity (94.0 %) toward GOR. In situ electrochemical impedance spectroscopy and pH-dependence measurements show that the Lewis acid centers could accelerate OH* production, while the Brønsted acid centers are proved to facilitate high-selectivity formation of formate. Theoretical calculations reveal that NiCo alloyed oxide shows appropriate d-band center, thus balancing adsorption/desorption of C-O intermediates. This study provides new insights into rationally designing solid-acid electrocatalysts for biomass electro-upcycling.

The complete plastomes of thirteen Libanotis (Apiaceae, Apioideae) plants: comparative and phylogenetic analyses provide insights into the plastome evolution and taxonomy of Libanotis.

BACKGROUND: The genus Libanotis Haller ex Zinn, nom. cons., a contentious member of Apiaceae, encompasses numerous economically and medicinally significant plants, comprising approximately 30 species distributed across Eurasia. Despite many previous taxonomic insights into it, phylogenetic studies of the genus are still lacking. And the establishment of a robust phylogenetic framework remains elusive, impeding advancements and revisions in the taxonomic system for this genus. Plastomes with greater variability in their genetic characteristics hold promise for building a more robust Libanotis phylogeny. RESULTS: During our research, we sequenced, assembled, and annotated complete plastomes for twelve Libanotis species belong to three sections and two closely related taxa. We conducted a comprehensive comparative analysis through totally thirteen Libanotis plastomes for the genus, including an additional plastome that had been published. Our results suggested that Libanotis plastome was highly conserved between different subclades, while the coding regions were more conserved than the non-coding regions, and the IR regions were more conserved than the single copy regions. Nevertheless, eight mutation hotspot regions were identified among plastomes, which can be considered as candidate DNA barcodes for accurate species identification in Libanotis. The phylogenetic analyses generated a robustly framework for Libanotis and revealed that Libanotis was not a monophyletic group and their all three sections were polygenetic. Libanotis schrenkiana was sister to L. sibirica, type species of this genus, but the remainders scattered within Selineae. CONCLUSION: The plastomes of Libanotis exhibited a high degree of conservation and was effective in enhancing the support and resolution of phylogenetic analyses within this genus. Based on evidence from both phylogeny and morphology, we propose the recognition of "Libanotis sensu stricto" and provide taxonomic recommendations for other taxa that previously belonged to Libanotis. In conclusion, our study not only revealed the phylogenetic position and plastid evolution of Libanotis, but also provided new insights into the phylogeny of the family Apiaceae and phylogenetic relationships within the tribe Selineae.

Construction of oxime-functionalized PCN-222 based on the directed molecular structure design for recovering uranium from wastewater.

The directed construction of productive adsorbents is essential to avoid damaging human health from the harmful radioactive and toxic U(VI)-containing wastewater. Herein, a sort of Zr-based metal organic framework (MOF) called PCN-222 was synthesized and oxime functionalized based on directed molecular structure design to synthesize an efficient adsorbent with antimicrobial activity, named PCN-222-OM, for recovering U(VI) from wastewater. PCN-222-OM unfolded splendid adsorption capacity (403.4 mg·g-1) at pH = 6.0 because of abundant holey structure and mighty chelation for oxime groups with U(VI) ions. PCN-222-OM also exhibited outstanding selectivity and reusability during the adsorption. The XPS spectra authenticated the -NH and oxime groups which revealed a momentous function. Concurrently, PCN-222-OM also possessed good antimicrobial activity, antibiofouling activity, and environmental safety; adequately decreased detrimental repercussions about bacteria and Halamphora on adsorption capacity; and met non-toxic and non-hazardous requirements for the application. The splendid antimicrobial activity and antibiofouling activity perhaps arose from the Zr6(µ3-O)4(µ3-OH)4(H2O)4(OH)4 clusters and rich functional groups within PCN-222-OM. Originally proposed PCN-222-OM was one potentially propitious material to recover U(VI) in wastewater on account of outstanding adsorption capacity, antimicrobial activity, antibiofouling activity, and environmental safety, meanwhile providing a newfangled conception on the construction of peculiar efficient adsorbent.

In-Plane Topological-Defect-Enriched Graphene as an Efficient Metal-Free Catalyst for pH-Universal H2 O2 Electrosynthesis.

Developing efficient metal-free catalysts to directly synthesize hydrogen peroxide (H2 O2 ) through a 2-electron (2e) oxygen reduction reaction (ORR) is crucial for substituting the traditional energy-intensive anthraquinone process. Here, in-plane topological defects enriched graphene with pentagon-S and pyrrolic-N coordination (SNC) is synthesized via the process of hydrothermal and nitridation. In SNC, pentagon-S and pyrrolic-N originating from thiourea precursor are covalently grafted onto the basal plane of the graphene framework, building unsymmetrical dumbbell-like S─C─N motifs, which effectively modulates atomic and electronic structures of graphene. The SNC catalyst delivers ultrahigh H2 O2 productivity of 8.1, 7.3, and 3.9 mol gcatalyst -1  h-1 in alkaline, neutral, and acidic electrolytes, respectively, together with long-term operational stability in pH-universal electrolytes, outperforming most reported carbon catalysts. Theoretical calculations further unveil that defective S─C─N motifs efficiently optimize the binding strength to OOH* intermediate and substantially diminish the kinetic barrier for reducing O2 to H2 O2 , thereby promoting the intrinsic activity of 2e-ORR.

Positive Synergy between the Helical Poly(phenylacetylene) Backbones and the Helical L-Proline Oligopeptide Pendants for Enhanced Enantioseparation Properties.

A series of optically active helical poly(phenylacetylene)s (PPA-Pro1, PPA-Pro3, PPA-Pro6, PPA-Pro9, and PPA-Pro12) bearing different chain lengths of L-proline oligopeptide in the side chains were obtained by polymerizing the corresponding novel phenylacetylene monomers. The monomer adopted a trans-rich helix structure when the L-proline oligopeptide chain length was longer, according to the optical activities and 2D-NMR analysis. The helical structure could be maintained and significantly influenced the polymers' helical conformation by introducing the L-proline oligopeptide to the pendants. By the way, the morphology of PPA-Pro3 was observed by atomic force microscope (AFM) on highly oriented pyrolytic graphite (HOPG), and the information on the helix direction, pitch, and chain arrangement was obtained. Also, the chiral separation properties of these polymer-based chiral stationary phases (CSPs) were investigated using high-performance liquid chromatography (HPLC). The poly(phenylacetylene)s showed enhanced enantioseparation properties toward various racemates depending on the longer chain length of the L-proline oligopeptide in the pendants and the positive synergy between the helical backbone and helical side chains. Particularly, PPA-Pro9 showed comparable or even superior enantioseparation properties for racemates 2 and 9 to four commercial columns (Daicel Chiralpak or Chiralcel AD, AS, OD, and OT), indicating that these poly(phenylacetylene)-based CSPs have potential practical values. This work presented here provides inspiration for the further development of CSPs based on a new paradigm.

A convenient functionalization strategy of polyimide covalent organic frameworks for uranium-containing wastewater treatment and uranium recovery.

The purpose of this research was to design and synthesize an adsorbent based on polyimide covalent organic frameworks (PICOFs) for uranium-containing wastewater treatment and uranium recovery. A modified solvothermal method was innovatively proposed to synthesize PICOFs with high specific surface area (1998.5 m2 g-1) and regular pore structure. Additionally, a convenient functionalization strategy of PICOFs was designed through polydopamine (PDA) and a well-dispersed polymer (MPC-co-AO) containing multiple functional groups, forming stable composite (PMCA-TPPICOFs) in which the hydrogen bonding and cation-π interactions between PDA and MPC-co-AO played a key role. The obtained PMCA-TPPICOFs as an adsorbent exhibited strong selectivity for uranyl ions (maximum adsorption capacity was 538 mg g-1). In simulated wastewater with low uranium concentrations, the removal rate reached 98.3%, and the concentration of treated simulated wastewater met discharge standards. Moreover, PMCA-TPPICOFs was suitable for fixed-bed column adsorption because of its favorable structure. According to the research about adsorption mechanism, the adsorption primarily relied on electrostatic interaction and complexation. In summary, PMCA-TPPICOFs exhibited good potential for uranium-containing wastewater treatment, expanding the application of PICOFs. And the proposed functionalization strategy and modified solvothermal method may promote research in the fields of material functionalization and COFs synthesis. ENVIRONMENTAL IMPLICATION: Uranium is a raw material for nuclear energy applications, which is toxic and radioactive. If uranium is discharged with wastewater, it would not only pose a threat to the environmental protection and life safety, but also cause the loss of precious nuclear raw materials. Although adsorption was considered to be an effective way to remove uranium, many of the developed adsorbents were difficult to apply due to the harsh wastewater environment and complex preparation processes. This study reported a novel adsorbent and a new functionalization strategy, which was expected to solve the problem of uranium recovery in wastewater.

Fabrication of Schiff-base crosslinked films modified dialdehyde starch with excellent UV-blocking and antibacterial properties for fruit preservation.

Starch-based films have received considerable attention, owing to their commendable biocompatible and biodegradable properties; however, their poor ultraviolet (UV)-blocking and antibacterial performances limit their application in fruit preservation. Herein, bio-based bifunctional benzoxazine (Bi-BOZ) compounds with different carbon chain lengths were synthesized, and the influence of chain lengths on the antibacterial effect was explored. Benzoxazine with 1,12-dodecanediamine as the amine source (BOZ-DDA) exhibited excellent antibacterial and antibiofilm activities, with minimum inhibitory concentrations of 21.7 ± 2.2 and 23.3 ± 2.6 µg/mL against Escherichia coli and Staphylococcus aureus, respectively, mainly because the electrostatic attraction and hydrophobic effect of BOZ-DDA, effectively disrupted the bacterial integrity. DS/DDA films with hydrophobic, antibacterial, and UV-resistant abilities were prepared by the Schiff-base reaction between BOZ-DDA and dialdehyde starch (DS). The interactions between the films increased with BOZ-DDA content, enhanced mechanical and barrier properties. DS/DDA films exhibited acid-responsive antibacterial activity attributed to the acid hydrolysis of Schiff bases, released of BOZ-DDA from the films, and the protonation of BOZ-DDA. DS/DDA films exhibited commendable antibacterial and anti-ultraviolet characteristics compared to commercially available films, allowing them to prevent the degradation of mangoes and grapes. As sustainable antibacterial materials, the multifunctional DS/DDA films manifest promising prospects in fruit preservation packaging applications.

Amorphous 1-D nanowires of calcium phosphate/pyrophosphate: A demonstration of oriented self-growth of amorphous minerals.

Amorphous inorganic solids are traditionally isotropic, thus, it is believed that they only grow in a non-preferential way without the assistance of regulators, leading to the morphologies of nanospheres or irregular aggregates of nanoparticles. However, in the presence of (ortho)phosphate (Pi) and pyrophosphate ions (PPi) which have synergistic roles in biomineralization, the highly elongated amorphous nanowires (denoted ACPPNs) form in a regulator-free aqueous solution (without templates, additives, organics, etc). Based on thorough characterization and tracking of the formation process (e.g., Cryo-TEM, spherical aberration correction high resolution TEM, solid state NMR, high energy resolution monochromated STEM-EELS), the microstructure and its preferential growth behavior are elucidated. In ACPPNs, amorphous calcium orthophosphate and amorphous calcium pyrophosphate are distributed at separated but close sites. The ACPPNs grow via either the preferential attachment of ∼2 nm nanoclusters in a 1-dimension way, or the transformation of bigger nanoparticles, indicating an inherent driving force-governed process. We propose that the anisotropy of ACPPNs microstructure, which is corroborated experimentally, causes their oriented growth. This study proves that, unlike the conventional view, amorphous minerals can form via oriented growth without external regulation, demonstrating a novel insight into the structures and growth behaviors of amorphous minerals.

Efficient and well-controlled ring opening polymerization of biobased ethylene brassylate by α-diimine FeCl3 catalysts via a coordination-insertion mechanism.

A highly efficient late-transition metal based catalytic system of α-diimine FeCl3 for well-controlled ring opening polymerization of a cheap and biobased macrolactone, ethylene brassylate (EB), is described herein. Proceeding via a coordination-insertion mechanism, such a catalytic system is capable of demonstrating unprecedented higher activities than previously reported organocatalysts or main-group metal based catalysts. Moreover, benefiting from the bulky nature of the α-diimine ligands, transesterification side reactions can be greatly suppressed, allowing the polymerization to proceed in a well-controlled living manner, as revealed from detailed kinetic studies. Additionally, such a catalytic system was also workable for ring opening copolymerization of EB and ε-caprolactone (ε-CL), giving the desired random copolymers with various compositions.

Misoriented high-entropy iridium ruthenium oxide for acidic water splitting.

Designing an efficient catalyst for acidic oxygen evolution reaction (OER) is of critical importance in manipulating proton exchange membrane water electrolyzer (PEMWE) for hydrogen production. Here, we report a fast, nonequilibrium strategy to synthesize quinary high-entropy ruthenium iridium-based oxide (M-RuIrFeCoNiO2) with abundant grain boundaries (GB), which exhibits a low overpotential of 189 millivolts at 10 milliamperes per square centimeter for OER in 0.5 M H2SO4. Microstructural analyses, density functional calculations, and isotope-labeled differential electrochemical mass spectroscopy measurements collectively reveal that the integration of foreign metal elements and GB is responsible for the enhancement of activity and stability of RuO2 toward OER. A PEMWE using M-RuIrFeCoNiO2 catalyst can steadily operate at a large current density of 1 ampere per square centimeter for over 500 hours. This work demonstrates a pathway to design high-performance OER electrocatalysts by integrating the advantages of various components and GB, which breaks the limits of thermodynamic solubility for different metal elements.

Tuning Binding Strength of Multiple Intermediates towards Efficient pH-universal Electrocatalytic Hydrogen Evolution by Mo8 O26 -NbNx Oy Heterocatalysts.

Developing efficient and robust hydrogen evolution reaction (HER) catalysts for scalable and sustainable hydrogen production through electrochemical water splitting is strategic and challenging. Herein, heterogeneous Mo8 O26 -NbNx Oy supported on N-doped graphene (defined as Mo8 O26 -NbNx Oy /NG) is synthesized by controllable hydrothermal reaction and nitridation process. The O-exposed Mo8 O26 clusters covalently confined on NbNx Oy nanodomains provide a distinctive interface configuration and appropriate electronic structure, where fully exposed multiple active sites give excellent HER performance beyond commercial Pt/C catalyst in pH-universal electrolytes. Theoretical studies reveal that the Mo8 O26 -NbNx Oy interface with electronic reconstruction affords near-optimal hydrogen adsorption energy and enhanced initial H2 O adsorption. Furthermore, the terminal O atoms in Mo8 O26 clusters cooperate with Nb atoms to promote the initial H2 O adsorption, and subsequently reduce the H2 O dissociation energy, accelerating the entire HER kinetics.

Xenobiotic Bi3+ Coordination by Cysteine-Rich Metallothionein-3 Reveals a Cooperatively Formed Thiolate-Sharing Bi2S5 Cluster.

The field of designing artificial metalloproteins has yet to effectively tackle the incorporation of multimetal clusters, which is a key component of natural metalloproteins, such as metallothioneins (MTs) and calmodulin. MT is a physiological, essential, cysteine-rich metalloprotein that binds to a variety of metals but is only known to form metal-thiolate clusters with Cd2+, Zn2+, and Cu+. Bismuth is a xenobiotic metal and a component of metallodrugs used to treat gastric ulcers and cancer, as well as an emerging metal used in industrial practices. Electrospray ionization mass spectrometry, UV-visible spectroscopy, and extended X-ray absorption fine structure spectroscopy were used to probe the Bi3+ binding site structures in apo-MT3 (brain-located MT) at pH 7.4 and 2 and provide the complete set of binding affinities. We discovered the highly cooperative formation of a novel Bi3+ species, Bi2MT3, under physiological conditions, where each Bi3+ ion is coordinated by three cysteinyl thiolates, with one of the thiolates bridging between the two Bi3+ ions. This cluster structure was associated with a strong visible region absorption band, which was disrupted by the addition of Zn2+ and reversibly disrupted by acidification and increased temperature. This is the first reported presence of bridging cysteines for a xenobiotic metal in MT3 and the Bi2MT structure is the first Bi cluster found in a metalloprotein.

Preparation and Properties of Natural Polysaccharide-Based Drug Delivery Nanoparticles.

In recent years, natural polysaccharides have been widely used in the preparation of drug delivery systems. In this paper, novel polysaccharide-based nanoparticles were prepared by layer-by-layer assembly technology using silica as a template. The layers of nanoparticles were constructed based on the electrostatic interaction between a new pectin named NPGP and chitosan (CS). The targeting ability of nanoparticles was formed by grafting the RGD peptide, a tri-peptide motif containing arginine, glycine, and aspartic acid with high affinity to integrin receptors. The layer-by-layer assembly nanoparticles (RGD-(NPGP/CS)3NPGP) exhibited a high encapsulation efficiency (83.23 ± 6.12%), loading capacity (76.51 ± 1.24%), and pH-sensitive release property for doxorubicin. The RGD-(NPGP/CS)3NPGP nanoparticles showed better targeting to HCT-116 cells, the integrin αvß3 high expression human colonic epithelial tumor cell line with higher uptake efficiency than MCF7 cells, the human breast carcinoma cell line with normal integrin expression. In vitro antitumor activity tests showed that the doxorubicin-loaded nanoparticles could effectively inhibit the proliferation of the HCT-116 cells. In conclusion, RGD-(NPGP/CS)3NPGP nanoparticles have potential as novel anticancer drug carriers because of their good targeting and drug-carrying activity.

Ru-P pair sites boost charge transport in hematite photoanodes for exceeding 1% efficient solar water splitting.

Fast transport of charge carriers in semiconductor photoelectrodes are a major determinant of the solar-to-hydrogen efficiency for photoelectrochemical (PEC) water slitting. While doping metal ions as single atoms/clusters in photoelectrodes has been popularly used to regulate their charge transport, PEC performances are often low due to the limited charge mobility and severe charge recombination. Here, we disperse Ru and P diatomic sites onto hematite (DASs Ru-P:Fe2O3) to construct an efficient photoelectrode inspired by the concept of correlated single-atom engineering. The resultant photoanode shows superior photocurrent densities of 4.55 and 6.5 mA cm-2 at 1.23 and 1.50 VRHE, a low-onset potential of 0.58 VRHE, and a high applied bias photon-to-current conversion efficiency of 1.00% under one sun illumination, which are much better than the pristine Fe2O3. A detailed dynamic analysis reveals that a remarkable synergetic ineraction of the reduced recombination by a low Ru doping concentration with substitution of Fe site as well as the construction of Ru-P bonds in the material increases the carrier separation and fast charge transportation dynamics. A systematic simulation study further proves the superiority of the Ru-P bonds compared to the Ru-O bonds, which allows more long-lived carriers to participate in the water oxidation reaction. This work offers an effective strategy for enhancing charge carrier transportation dynamics by constructing pair sites into semiconductors, which may be extended to other photoelectrodes for solar water splitting.