A "Dual-Key-and-Lock" MRI Contrast Agent with T1-T2 Switchable Function for Accurate Diagnosis of Tumors.

Extremely small iron oxide nanoparticle (ESIONP)-based stimuli-responsive switchable MRI contrast agents (CAs) show great promise for accurate detection of tumors due to their outstanding advantages of high specificity and low background signal. However, currently developed ESIONP-based switchable CAs often suffer single-biomarker-induced responses, which lack absolute specificity to pathological tissues, potentially diminishing diagnostic accuracy. In this study, weak acidity and hypoxia, two of the most remarkable characteristics of tumors, are introduced as dual biomarker stimuli to construct an ESIONP-based switchable MRI CA (DKL-CA), with its signal switch controlled by a "dual-key-and-lock" strategy. Only when DKL-CA is exposed to a coexisting weakly acidic and hypoxic environment can monodispersed ESIONPs form nanoclusters, thereby realizing a switch from the T1 to T2 contrast. Moreover, DKL-CA exhibits favorable biosafety and the capacity for precise tumor diagnosis in tumor-bearing mice. Overall, DKL-CA paves the way for designing highly accurate ESIONP-based MRI CAs for tumor diagnosis.

Advanced stimuli-responsive membranes for smart separation.

Membranes have been extensively studied and applied in various fields owing to their high energy efficiency and small environmental impact. Further conferring membranes with stimuli responsiveness can allow them to dynamically tune their pore structure and/or surface properties for efficient separation performance. This review summarizes and discusses important developments and achievements in stimuli-responsive membranes. The most commonly utilized stimuli, including light, pH, temperature, ions, and electric and magnetic fields, are discussed in detail. Special attention is given to stimuli-responsive control of membrane pore structure (pore size and porosity/connectivity) and surface properties (wettability, surface topology, and surface charge), from the perspective of determining the appropriate membrane properties and microstructures. This review also focuses on strategies to prepare stimuli-responsive membranes, including blending, casting, polymerization, self-assembly, and electrospinning. Smart applications for separations are also reviewed as well as a discussion of remaining challenges and future prospects in this exciting field. This review offers critical insights for the membrane and broader materials science communities regarding the on-demand and dynamic control of membrane structures and properties. We hope that this review will inspire the design of novel stimuli-responsive membranes to promote sustainable development and make progress toward commercialization.

Modified nano-SiO2/PU hydrophobic composite film prepared through in-situ coupling by KH550 for oil-water separation.

In this study, hydrophobic polymer composite films based on polyurethane (PU) were prepared for oil-water separation. Hydrophilic fumed silica (nano-SiO2) was introduced as reinforcing filler, and silane coupling agent (KH550) was used to crosslink PU with nano-SiO2 in situ for enhancing the nano-SiO2 dispersion in the films. The microscopic morphology, crystalline structure, and hydrophobic properties of the films were characterized by using scanning electron microscopy, X-ray diffraction, FTIR spectroscopy, water contact angle, and water absorption tests. The results showed that the hydrophobicity of the nano-SiO2/PU composite films increased with the addition of nano-SiO2. KH550 not only significantly promoted the crosslink action between PU and nano-SiO2 but also enhanced the dispersion of nano-SiO2 in the composite films. Moreover, the pore structure of the prepared films was changed with the addition of nano-SiO2 and KH550, which greatly improved the hydrophobicity. The test results for oil-water separation performance showed that the prepared composite films can efficiently separate the oil from oil-water mixtures with good repeatability.

Fabrication of two-phase Ca2+-doped LaVO4:Eu3+ structures: morphology modification, tunable optical performance and detection of Fe3+ ions with high sensitivity.

Two-phase Ca2+-doped LaVO4:Eu3+ nanocrystals were prepared through a hydrothermal method with the help of SOD CITR and EDTA surfactants. The phase and morphology of the products were characterized by XRD and TEM, and the fluorescence performances were also recorded. The results indicated that Ca2+ ions were doped into the LaVO4:Eu3+ host lattice, impeding the aggregation of the nanocrystals and enhancing the luminescence intensity. The morphology transformation process and luminescence enhancement were systematacially investigated. The fluorescence intensity of the two selected samples could be completely quenched by Fe3+ ions without the disturbance of other ions, with the mechanism being due to the adsorption of Fe3+ ions onto the grains and a subsequent energy transfer from Eu3+ to Fe3+. Therefore, the present two Ca2+-doped LaVO4:Eu3+ samples can be applied as appropriate candidates for detecting Fe3+ ions with agility and sensitivity in aqueous solution.

Facile in situ synthesis of silver nanocomposites based on cellulosic paper for photocatalytic applications.

In this work, various photocatalysts were synthesized with an impregnation-precipitation process to in situ decorate Ag-based nanoparticles (NPs, including Ag3PO4, AgCl, Ag2O, and Ag2CO3) on the cellulosic paper. The structure and properties of the Ag-based composites were characterized by scanning electron microscopy, X-ray diffraction, transmitting electron microscopy, UV-vis diffuse reflectance spectra, and photocatalysis testing. The results showed that cellulosic paper is an efficient carrier which is feasible to grasp NPs due to the cellulosic nanofiber-network microstructure. Among the obtained samples, Ag2CO3 and AgCl NPs on cellulosic paper displayed high photocatalytic activity for the degradation of methyl orange under ultraviolet and visible light. However, photo lability of Ag2CO3 limits its recyclable. AgCl showed a better reutilization with the assistance of a surface plasmon resonance effect by Ag NPs that were grown in situ on the AgCl NPs, which formed Ag@AgCl nanocomposite structure. The photocatalytic activity of the AgCl/cellulosic paper decreased only slightly after three runs of photodegradation of methyl orange. The possible mechanism for photocatalysis was proposed. This work may provide a new method for the design of silver-based NPs/cellulosic paper nanocomposite photoreactors with favorable photocatalytic activities for industrial applications.

Synthesis of Polyurethane Hydrogel and Polyurethane Thermoplastic Elastomer Composite Based Separation Membranes.

A series of polyurethane hydrogel and polyurethane thermoplastic elastomer composite based separation membranes were successfully prepared via wet phase inversion method. The morphology, chemical structure, phase transition temperature and crystallinity of the polyurethane (PU) membranes were characterized by SEM, FTIR, DSC, and XRD, respectively. The SEM observation showed that the PU membranes exhibited irregular porous structure on the surface and path of the hole was flexural and asymmetrical in cross-section. The FTIR analysis demonstrated that thermalsensitive groups and pH-sensitive components (-N(CH3)-) were incorporated into the PU network. The DSC experiment and XRD experiment showed that the regular arrangement of PU network was destroyed partly due to the introduction of polyurethane thermoplastic elastomer. The equilibrium swelling ratio (ESR) and water flux (J) for PU membranes clearly decreased and increased with functional groups and sophisticated structure of PU membranes, respectively. In addition, the permeation experiments indicated that the permeation percentage (P) of the glycine was strongly affected by the external temperature and pH value.

Preparation and performance of poly(4-vinylpyridine)-b-polysulfone-b-poly(4-vinylpyridine) triblock copolymer/polysulfone blend membrane for separation of palladium (II) from electroplating wastewaters.

In order to separate palladium (II) from electroplating wastewaters, poly(4-vinylpyridine)-b-polysulfone-b-poly(4-vinylpyridine) (P4VP-PSF-P4VP) / polysulfone blend membranes were fabricated by combining non-solvent induced phase separation, surface segregation and self-assembly of block copolymer. Amphiphilic P4VP-PSF-P4VP was used as the membrane base material, which was synthesized by introducing the functional monomer of 4-vinylpyridine (4-VP), and polysulfone as the additive. Effects of blend ratio and 4-VP content on membrane performance, such as structure, hydrophilicity, pure water flux and adsorption capacity towards Pd (II), were investigated. The membranes exhibited dense surface structure and low roughness due to surface segregation and self-assembly of P4VP-PSF-P4VP. The presence of 4-VP increased hydrophilicity and water flux of membrane, and it also provided good adsorption capacity towards Pd (II) (up to 103.1 ±â€¯5.15 mg/g). Further, the membrane was used to separate Pd (II) from simulated wastewaters during filtration. It showed good rejection ability and high selectivity towards Pd (II) in co-existence of Cu (II) and Ni (II), and selectivity coefficients of Pd/Cu and Pd/Ni are 41.9 ±â€¯1.88 and 97.8 ±â€¯4.32, respectively. In filtration process of actual electroplating wastewater, the membrane also exhibited excellent rejection performance (Pd (II) rejection reached up to 96.8 ±â€¯2.71%). Perhaps it is suitable for future practice applications.

In-situ preparation of silver salts/collagen fiber hybrid composites and their photocatalytic and antibacterial activities.

To promote the utilization of collagen fiber, silver salts/collagen fiber hybrid composites with photocatalytic and antibacterial activities were successfully prepared in this study via the in-situ organic-inorganic process. The surface morphology, chemical composition and structure were discussed. Scanning electron microscopy (SEM) observation showed that the silver salts/collagen fiber hybrid composites were successfully prepared with silver salt particles (300-500 nm) distributing evenly on the surface of collagen fiber. X-ray diffraction (XRD) patterns and Fourier transform infrared spectroscopy (FTIR) analysis provided strong evidence for the successful coating of silver salts on the surface of collagen fiber and the hybrid mechanism was subsequently discussed. The photocatalytic activity was evaluated by degrading methyl orange (MO) under ultraviolet (UV) light and visible light, respectively. The results indicated that AgCl/Collagen Fiber showed the most efficient photocatalytic activity under UV and visible light irradiation. Furthermore, the introduction of Ag+ endowed the photocatalysts with antibacterial performance, which was investigated by measuring the width of the bacteriostatic belts. The results indicated the antibacterial activity of the composites, proving that the photocatalysts were durable and reusable.

Preparation of a surface-grafted imprinted ceramic membrane for selective separation of molybdate anion from water solutions.

A surface-grafted imprinted ceramic membrane (IIP-PVI/CM) for recognizing molybdate (Mo(VI)) anion was prepared by surface-initiated graft-polymerization. Firstly, raw alumina ceramic membrane (CM) was deposited with SiO2 active layer by situ hydrolysis deposition method. Subsequently, γ-methacryloxy propyl trimethoxyl silane (MPS) was used as a coupling agent to introduce double bonds onto the SiO2 layer (MPS-CM). Then, 1-vinylimidazole (VI) was employed as a functional monomer to graft-polymerization onto the MPS-CM (PVI-CM). During the graft-polymerization, the influence factors of grafting degree of PVI were investigated in detail. Under optimum conditions (monomer concentration 20wt%, temperature 70°C, initiator amount 1.1wt% and reaction time 8h), the grafting degree of 20.39g/100g was obtained. Further, Mo(VI) anion was used as a template to imprint in the PVI-CM by employing 1,6-dibromohexane as a cross-linking agent, and then Mo(VI) was removed, obtaining the IIP-PVI/CM with many imprinted cavities for Mo(VI). Thereafter, static adsorption and dynamic separation properties of IIP-PVI/CM for Mo(VI) were studied. Results indicate that IIP-PVI/CM shows a specific selectivity for Mo(VI) with the adsorption capacity of 0.69mmol/100g, and the selectivity coefficient of IIP-PVI/CM is 7.48 for molybdate to tungstate anions. During the dynamic separation, IIP-PVI/CM has also good selectivity for separation of Mo(VI) and W(VI) anions.

Application of the hybrid complexation-ultrafiltration process for metal ion removal from aqueous solutions.

Complexation-ultrafiltration process was investigated for mercury and cadmium removal from aqueous solutions by using poly(acrylic acid) sodium salt (PAASS) as a complexing agent. The kinetics of complexation reactions of PAASS with the metal ions were studied under a large excess PAASS and pH 5.5. It takes 25 and 50 min for mercury and cadmium to get the complexation equilibrium, respectively, and the reaction kinetics can be described by a pseudo-first-order equation. Effects of various operating parameters such as loading ratios, pH values, etc. on metal rejection coefficients (R) were investigated. In the process of concentration, membrane fluxes decline slowly and R values are about 1. The concentrated retentates were used further for the decomplexation. The decomplexation ratio of mercury-PAASS complex is about 30%, whereas that of cadmium-PAASS complex reaches 93.5%. After the decomplexation, diafiltration experiments were carried out at pH 2.5. Cadmium can be diafiltrated satisfactorily from the retentate, but for mercury it is the contrary. Selective separation of the both metal ions was studied from a binary solution at pH 5. When mercury, cadmium and PAASS concentrations are 30, 30 and 40 mg L(-1), respectively, mercury is retained by ultrafiltration while almost all cadmium passes through the membrane.