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Enhancing the exposure of metal active sites and maximizing metal atom utilization are critical challenges in heterogeneous catalysis. To solve these issues, heterogeneous catalysts are usually activated by chemicals. Herein, potassium chloride (KCl) was used as an activator to prepare cobalt-nitrogen co-doped (Co-N x ) hollow periodic mesoporous organosilica spheres (Co-N x /HPMOs-KCl). Co-N x /HPMOs-KCl showed outstanding catalytic activity for the selective oxidation of ethylbenzene to acetophenone, with a conversion of up to 94.0% for ethylbenzene and a high selectivity of 98.4% towards acetophenone. Additionally, Co-N x /HPMOs-KCl maintained excellent catalytic performance for the oxidation of ethylbenzene after six cycles. The excellent performance of Co-N x /HPMOs-KCl was attributed to the activation of KCl, which increased the specific surface area of the catalyst and thus facilitated the exposure of more metal active sites. After the removal of unstable metal species through further acid treatment, the remaining metal active sites were thus fully exposed and stably embedded in the framework of the hollow periodic mesoporous organosilica spheres (HMPOs). This work presents an efficient catalyst and offers new insights for the improvement of heterogeneous catalysts.

This study reports a fluorescent nanoprobe operated in fluorescence turn-on mode for simultaneously sensing and imaging intracellular GSH and ATP. By using maleimide-derivatives as the ligand, the bimetallic nanoscale metal-organic framework (NMOF) Cu-Mi-UiO-66 has been synthesized for the first time using a straightforward one-step solvothermal approach, serving as a GSH recognition moiety. Subsequently, a Cy5-labeled ATP aptamer was assembled onto Cu-Mi-UiO-66 via strong coordination between phosphate and zirconium, π-π stacking and electrostatic adsorption to develop the dual-responsive fluorescence nanoprobe Cu-Mi-UiO-66/aptamer. Due to the photoinduced electron transfer (PET) effect between maleimide groups and the benzene ring of the ligand and the charge transfer between Cy5 and the Zr(IV)/Cu(II) bimetal center of the NMOF, the Cu-Mi-UiO-66/aptamer exhibits a fluorescence turn-off status. The Michael addition reaction between the thiol group of GSH and the maleimide on the NMOF skeleton results in turning on of the blue fluorescence of Cu-Mi-UiO-66. Meanwhile, upon specific interaction with ATP, the aptamer changes into internal loop structures and detaches from Cu-Mi-UiO-66, resulting in turning on of the red fluorescence of Cy5. The nanoprobe demonstrated an excellent sensing performance with a good linear range (GSH, 5.0-450.0 μM; ATP, 1.0-50.0 μM) and a low detection limit (GSH, 2.17 μM; ATP, 0.635 μM). More importantly, the Cu-Mi-UiO-66/aptamer exhibits good performance for tracing intracellular concentration variations of GSH and ATP in living HepG2 cells under different stimulations. This study highlights the potential of NMOFs for multiplexed analysis and provides a valuable tool for tumor microenvironment research and early cancer diagnosis.

Quantitation of salivary alpha-amylase (sAA) plays a significant role in not only theoretical studies but also clinical practice. This study reports a quantitative point-of-care testing (POCT) system for sAA quantitation anywhere, anytime and by anyone, which consists of customized electrodes and a smartphone-controlled electrochemical analyzer. Organic-inorganic hybrid nanoflowers (NFs) encapsulating α-glucosidase (AG) and glucose dehydrogenase (GDH) have been synthesized and modified onto screen-printed electrodes (SPCEs) to fabricate the customized electrodes. The SPCEs integrated with the smartphone-controlled electrochemical analyzer exhibit good analytical performance for sAA with a low detection limit of 5.02 U mL -1 and a wide dynamic range of 100-2000 U mL -1 using chronoamperometry. The reported POCT system has been successfully demonstrated for quantitation of sAA in clinical saliva samples, and the quantitation results correlated well with those of the Bernfeld method which is extensively used in clinics. More importantly, this study reveals the great potential of sAA as an early warning indicator of abnormal glucose metabolism in obese individuals. Considering the non-invasive saliva sampling process as well as the easy-to-use and cost-effectiveness features of this quantitative POCT system, quantitation of salivary sAA at home by laypersons might become an appealing choice for obese individuals to monitor their glucose metabolism status anytime.

Precision medicine urges the development of theranostics which can efficiently integrate precise diagnosis and effective therapy. In this study, a facile synthesis of Ir/Gd bimetallic oxide nanotheranostics (termed BSA@Gd 2 O 3 /IrO 2 NPs) with good biocompatibility was demonstrated using a biomineralization method where bovine serum albumin (BSA) served as a versatile template. BSA@Gd 2 O 3 /IrO 2 NPs exhibited high longitudinal relaxivity (5.2 mM -1 s -1 ) and X-ray absorption capability (14.5 Hu mM -1 ), illustrating them to be a good contrast agent for magnetic resonance (MR) and computed tomography (CT) dual-modal imaging. Moreover, BSA@Gd 2 O 3 /IrO 2 NPs can act as not only a photothermal conversion agent with ultrahigh efficiency (66.7%) as well as a good photosensitizer, but also an effective catalase to decompose endogenous H 2 O 2 to produce O 2 , thus relieving hypoxia and enhancing the phototherapeutic effect. Both in vitro and in vivo experiments demonstrated the high effectiveness of BSA@Gd 2 O 3 /IrO 2 NPs in MR/CT dual-modal imaging and photothermal and photodynamic synergistic tumor treatments. This work sheds new light on the development of versatile nanotheranostic systems using mild and robust biomineralization methods.

Mixing-induced nanoprecipitation (MINP) is an efficient, controllable, scalable, versatile, and cost-effective technique for the preparation of nanoparticles. In addition to the formulation of drugs, MINP has attracted tremendous interest in other fields. In this review, we highlight recent advances in the preparation of nanoparticles with complex nanostructures via MINP and their emerging applications beyond biomedicine. First, the mechanisms of nanoprecipitation and four mixing approaches for MINP are briefly discussed. Next, three strategies for the preparation of nanoparticles with complex nanostructures including sequential nanoprecipitation, controlling phase separation, and incorporating inorganic nanoparticles, are summarized. Then, emerging applications including the engineering of catalytic nanomaterials, environmentally friendly photovoltaic inks, colloidal surfactants for the preparation of Pickering emulsions, and green templates for the synthesis of nanomaterials, are reviewed. Furthermore, we discuss the structure-function relationships to gain more insight into design principles for the development of functional nanoparticles via MINP. Finally, the remaining issues and future applications are discussed. This review will stimulate the development of nanoparticles with complex nanostructures and their broader applications beyond biomedicine.

Nanotheranostics for fluorescence/magnetic resonance (FL/MR) dual-modal imaging guided photodynamic therapy (PDT) are highly desirable in precision and personalized medicine. In this study, a facile non-covalent electrostatic interaction induced self-assembly strategy is developed to effectively encapsulate gadolinium porphyrin (Gd-TCPP) into homogeneous supramolecular nanoparticles (referred to as Gd-PNPs). Gd-PNPs exhibit the following advantages: (1) excellent FL imaging property, high longitudinal relaxivity (16.157 mM -1 s -1 ), and good singlet oxygen ( 1 O 2 ) production property; (2) excellent long-term colloidal stability, dispersity and biocompatibility; and (3) enhanced in vivo FL/MR imaging guided tumor growth inhibition efficiency for CT 26 tumor-bearing mice. This study provides a new strategy to design and synthesize metalloporphyrin-based nanotheranostics for imaging-guided cancer therapy with enhanced theranostic properties.

Self-propelled micro/nanomotors play a crucial role in the fields of biomedicine, energy and the environment but are limited by low throughput and a tedious fabrication approach. Here, we propose a simple microfluidics-based scheme for fabricating substrate-free graphene oxide (GO)-based micromotors of different shapes and sizes with high throughput. The micromotors are designed to possess a 'Janus'-like porous structure, and half of each micromotor is modified with hierarchical Pt nanoflowers, which can promote the wetting of Pt with an H2O2 solution and result in a high speed of movement. To investigate the applicability of the micromotors, they were employed to rapidly remove an antibiotic, namely, tetracycline, from a solution. It was found that the rapid movement of the micromotors increased the mass transfer of tetracycline and the frequency of collisions between tetracycline molecules and the micromotors, which led to a high removal efficiency. The direction of movement of the micromotors can be conveniently controlled by an external magnetic field. Furthermore, the removal efficiency and removal time as functions of the number of micromotors, the adsorption kinetics and adsorption isotherm, and the removal amount as a function of the pH were investigated. This proved that the micromotors that were constructed exhibit high adsorption capabilities for tetracycline and implied that they hold great promise for the removal of antibiotics with similar structures or other pollutants, including organic compounds, heavy metals and oil droplets.

Obtaining tunable photoluminescence (PL) with improved emission properties is crucial for successfully implementing fluorescent carbon nanodots (fCDs) in all practical applications such as multicolour imaging and multiplexed detection by a single excitation wavelength. In this study, we report a facile hydrothermal approach to adjust the PL peaks of fCDs from blue, green to orange by controlling the surface passivation reaction during the synthesis. This is achieved by tuning the passivating reagents in a step-by-step manner. The as-prepared fCDs with narrow size distribution show improved PL properties with different emission wavelengths. Detailed characterization of fCDs using elemental analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy suggested that the surface chemical composition results in this tunable PL emission. Surface passivation significantly alters the surface status, resulting in fCDs with either stronger surface oxidation or N element doping that ultimately determine their PL properties. Further experiments suggested that the as-prepared orange luminescent fCDs (O-fCDs) were sensitive and specific nanosensing platforms towards Fe(3+) determination in a complex biological environment, emphasizing their potential practical applications in clinical and biological fields.

Charge carrier relaxation dynamics of electronically excited CdSe and CdSe/CdS core/shell nanocrystals (NCs) were studied using femtosecond time-resolved transient absorption spectroscopy, employing both visible and near-infrared (NIR) probe laser pulses. Following 400 nm excitation, the combination of visible and NIR laser probe pulses were used to determine the influence of surface passivation on electronic relaxation dynamics for nanocrystals overcoated with either organic ligands or inorganic semiconductors. In particular, low-energy NIR photons were used to isolate transient absorption signals due to either electron and hole intraband transitions. Four relaxation components were detected for CdSe NCs passivated by organic molecules: (1) picosecond hole relaxation; (2) electron deep trapping; (3) electron surface trapping; and (4) exciton radiative recombination. Based on TA data collected over a broad energy range, electron deep trapping at Se(2-) sites was suppressed for CdSe NCs passivated by inorganic (CdS) semiconducting materials. By comparing the time-dependent transient absorption data of a series of CdSe/CdS NCs with different shell thicknesses, evidence for the transition from Type-I to quasi Type-II NCs was obtained. These data illustrate the sensitivity of femtosecond time-resolved transient absorption measurements carried out over visible and near infrared probe energies for determining the influence of nanocrystal structure on electronic relaxation dynamics.