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Mesoporous carbon spheres (MCSs) are widely used in the field of pollutants adsorption, energy storage and various biomedicine applications such as targeted delivery vector, phototherapy sensitizers, bioimaging contrast agents, etc. Current synthetic strategies including soft templating and hard templating methods generally have the limits of using expensive surfactants or lack of control over the pore structures. Therefore, the complex and uncontrollable pore structures limit its further clinical application. Herein, we proposed a new synthetic strategy to control the uniformity of pore channel arrangement in MCSs which can modulate the photonic property and the corresponding light controlled drug release property in intelligent drug delivery. The as obtained MCSs with relative uniform pore channel arrangement and long pore channels are demonstrated to have the best NIR light-induced drug release performance. This work provides not only new synthetic method to modulate pore structure characteristics and biophotonic property of MCSs, but also uniform MCSs as novel delivery platforms with advanced controlled release performance.

Schematic illustration of the preparation of Ni/SAPO-11 and the stabilization of metal species by [Bmim][BF4] and lysine.

Mo dispersion is the key factor promoting the performance of an Mo/ZSM-5 catalyst for the methane dehydroaromatization (MDA) reaction.

Aluminum-containing adjuvants used in vaccine formulations suffer from low cellular immunity, severe aggregation, and accumulation in the brain. Conventional aluminosilicates widely used in the chemical industry focus mainly on acidic sites for catalytic applications, but they are rarely used as adjuvants. Reported here is an innovative "ligand-assisted steric hindrance" strategy to create a high density of six-coordinate VI Al-OH groups with basicity on dendritic mesoporous silica nanoparticles as new nanoadjuvants. Compared to four-coordinate IV Al-modified counterparts, VI Al-OH-rich aluminosilicate nanoadjuvants enhance cellular delivery of antigens and provoke stronger cellular immunity. Moreover, the aluminum accumulation in the brain is more reduced than that with a commercial adjuvant. These results show that coordination chemistry can be used to control the adjuvanticity, providing new understanding in the development of next-generation vaccine adjuvants.

Direct depletion of lactate accumulated in the tumor microenvironment holds promise for cancer therapy, but remains challenging. Here we report a one‐pot synthesis of openwork@ dendritic mesoporous silica nanoparticles (ODMSN) to address this problem. ODMSN self‐assembled through a time‐resolved lamellar growth mechanism feature an openworked core and a dendritic shell, both constructed by silica nanosheets of ~3 nm. With a large pore size, high surface area and pore volume, ODMSN exhibited a high loading capacity (> 0.7 g/g) of lactate oxidase (LOX) and enabled intratumoral lactate depletion by >99.9%, leading to anti‐angiogenesis, down‐regulation of vascular endothelial growth factor and increased tumor hypoxia. The latter event facilitates the activation of a co‐delivered prodrug for enhancing anti‐tumor and anti‐metastasis efficacy. This study provides an innovative nano‐delivery system and demonstrates the first example of direct lactate depletion enabled chemotherapy.

Effective messenger RNA (mRNA) transfection in hard-to-transfect cells delivered by vectors is a long-standing challenge. Now it is hypothesized that the high intracellular glutathione level is associated with suppressed mRNA translation. This theory leads to a new design principle of next-generation mRNA vectors: nanoparticles with glutathione depletion chemistry upregulate mRNA translation and enhance transfection, which is beneficial for mRNA delivery in hard-to-transfect cells in vitro and in vivo.

Nanomaterials functionalized with metal oxide species have aroused broad research interest in biomedical, catalysis and adsorption applications. However, a generalized functionalization approach achieving both high dispersity and high content of metal oxide species is rarely reported. In this study, a novel three-dimensional nanosponge (3D-NS) enabled strategy is developed to tackle this challenge. Instead of directly modifying metal species onto nanoparticles as performed in conventional approaches, the “empty” pores of nanoparticles are creatively converted into a “sponge-like” 3D nanospace by filling up with resoles rich in metal anchors, which efficiently accommodate high content metal species and maintain their highly dispersed state during the fabrication process. This strategy is generic to achieve highly dispersed metal functionalization of different single and binary metal compositions. As a demonstration, highly dispersed copper species derived from this strategy show excellent Fenton-like catalytic activity and enhanced cancer cell inhibition performance. These findings provide new understanding and useful tools for the development of metal functionalized nanomaterials for advanced applications.

Polyethylenimine (PEI) functionalization onto nanoparticles is a widely used strategy for constructing particulate vectors for gene delivery. However, how to control the conformation of PEI chains and the resultant impact on gene transfection efficiency remains largely unexplored. Herein, we report that drying methods dramatically affect the conformation of PEI chains modified on the surface of silica nanoparticles and consequently the plasmid DNA transfection performance. Specifically, lyophilization renders less entangled PEI compared to commonly used vacuum drying as evidenced by an elevated glass transition temperature. The lyophilization induced disentangled conformation is likely associated with the solid-to-gas phase transition drying mechanism, which removes the bound crystal water content and thus reduces hydrogen bonding between amines. Moreover, we find that the stretched PEI chains on the surface of rambutan-like silica nanoparticles promote their binding capacity towards plasmid DNA molecules and thereby enhanced gene delivery and transfection efficiency. Our findings have provided new understanding about amine based polymers modified on nanoparticles, and have significant implications on the design of efficient particulate vectors for gene delivery.

Wonderful black phosphorus (BP) and some BP analogs (BPAs) have been increasingly studied for their biomedical applications owing to their fascinating properties and biodegradability, but opportunities and challenges have always coexisted in their study. Poor stability upon exposure to the natural environment is the major obstacle hampering their in vivo applications. BP/polymer and BPAs/polymer nanocomposites can not only efficiently prevent their oxidation and aggregation but also exhibit "biological activity" due to synergistic effects. In this review, we briefly describe the synthesis methods and stability strategies of BP/polymer and BPAs/polymer. Then, advances pertaining to their exciting therapeutic applications in various fields are systematically introduced, such as cancer therapy (phototherapy, drug delivery, and synergistic immunotherapy), bone regeneration, and neurogenesis. Some challenges for future clinical trials and possible directions for further study are finally discussed.

Fractal objects such as snowflakes and trees are ubiquitous in nature. However, fractal nanoparticles with uniform morphology and controllable structures are difficult to make. Herein, using a fractal-in-a-sphere strategy, we report the confined self-assembly of fractal silica nanoparticles with tunable fractal generations and uniform sizes. One advantage of controllable fractal generations has been demonstrated in enzyme delivery for parasite oocyst control. The fractal silica nanoparticles exhibited better oocysticidal performance compared with nanoparticles of other structures due to combined effects of enhanced adhesion, penetration across the oocyst wall, and high local enzyme concentrations. This study paves the way for the fabrication of fractal silica nanoparticles with fine structures and versatile applications.

Asymmetric mesoporous silica nanoparticles (AMSNs) with one side featuring a spiky nanotopography, while the other side is smooth and solid, were synthesized via an ethylenediamine (EDA)-directed silica-polymer cooperative assembly approach. By simply varying the EDA amount (x), AMSNs-x samples with adjustable spiky surface coverage were obtained. It is demonstrated that a spiky coverage higher than 50% improved the hemocompatibility of AMSN-x, possibly due to the reduced contact area of the smooth side exposed to the red blood cell (RBC) membrane. Moreover, AMSNs-175 and AMSNs-200 with high spiky coverage enhanced their plasmid DNA (pDNA) loading and binding capability, as well as cellular uptake into HEK-293T cells, thus resulting in high transfection performance. The good hemocompatibility and high performance in pDNA delivery of AMSNs-x with high spiky coverage allow them to serve as promising nonviral vectors for potential applications in gene therapies and DNA vaccines.

Iron oxide nanoparticles (IONPs) have emerging anticancer applications via polarizing tumor-associated macrophages from tumor-promoting phenotype (M2) to tumor-suppressing phenotype (M1). However, the underlying mechanism and structure-function relationship remain unclear. We report magnetite IONPs are more effective compared to hematite in M1 polarization and tumor suppression. Moreover, magnetite IONPs specifically rely on interferon regulatory factor 5 signaling pathway for M1 polarization and down-regulate M2-assoicated arginase-1. This study provides new understandings and paves the way for designing advanced iron-based anticancer technologies.

Biopesticides, such as spinosad, are a new‐generation of ecofriendly pesticides in livestock industry. However, spinosad suffers from short duration of effectiveness and low potency in field conditions. Herein we report the development of a new nanospinosad design with dual adhesion and protection functions. Silica nanoparticles with spiky nanotopography loaded with spinosad possess rough surfaces. When applied topically, this nanospinosad formulation exhibited enhanced adhesion to both cattle hair and pest surface. The dual adhesion property led to significantly higher pest mortality toward tick (Rhipicephalus microplus, an ectoparasite) than a nanospinosad formulation using nanoparticles with smooth surface and a benchmark commercial product. The adhesion performance was further quantitatively measured using rainfastness test. Moreover, solar radiation test revealed that the nanospinosad exhibited >10 times higher photostability over the commercial product. This work paves the way toward the development of high performance nanobiopesticides for sustainable agricultural applications.

Series Al-SBA-16 supports with different crystal sizes were fabricated by adding different inorganic salts to the synthesis system and used as the catalyst support for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS). The supports and the corresponding catalysts were well analyzed in depth to investigate their structure–property relationship. NiMo/AS-Mn catalyst with the smallest crystal sizes, the largest BET surface areas, and the highest total acid and Bronsted acid content displayed the highest kHDS of 4,6-DMDBT and DBT. HYD was the preferential route for the DBT HDS over NiMo/AS-Mn, while ISO was the preferential pathway for 4,6-DMDBT HDS. Moreover, the DBT and 4,6-DMDBT HDS reaction networks over NiMo/AS-Mn were proposed.

ZSM-5/SBA-16 (ZS) composite materials with different morphologies were synthesized successfully. The series supports were utilized to prepare NiMo/ZS for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions. Series ZS supports and NiMo/ZS were well characterized to investigate their structure–property relationship. The NiMo/ZS catalyst (NiMo/ZS-3) with uniform morphology and well-ordered pore channels showed the maximum kHDS and TOF values of DBT and 4,6-DMDBT HDS. The kHDS value (13.9 × 10–4 mol g–1 h–1) of DBT over NiMo/ZS-3 was more than 2 times greater than that over the reference NiMo/ZS-M catalyst (5.5 × 10–4 mol g–1 h–1), 3 times greater than that over the NiMo/SBA-16 catalyst (4.4 × 10–4 mol g–1 h–1), and almost 4 times greater than that over the NiMo/ZSM-5 catalyst (3.5 × 10–4 mol g–1 h–1). Furthermore, the kHDS value (8.4 × 10–4 mol g–1 h–1) of 4,6-DMDBT over NiMo/ZS-3 was more than 3 times greater than that over the reference NiMo/ZS-M catalys...

Plasmid DNA molecules with unique loop structures have widespread bioapplications, in many cases relying heavily on delivery vehicles to introduce them into cells and achieve their functions. Herein, we demonstrate that control over delicate nanotopography of silica nanoparticles as plasmid DNA vectors has significant impact on the transfection efficacy. For silica nanoparticles with rambutan-, raspberry-, and flower-like morphologies composed of spike-, hemisphere-, and bowl-type subunit nanotopographies, respectively, the rambutan-like nanoparticles with spiky surfaces demonstrate the highest plasmid DNA binding capability and transfection efficacy of 88%, higher than those reported for silica-based nanovectors. Moreover, it is shown that the surface spikes of rambutan nanoparticles provide a continuous open space to bind DNA chains via multivalent interactions and protect the gene molecules sheltered in the spiky layer against nuclease degradation, exhibiting no significant transfection decay. This unique protection feature is in great contrast to a commercial transfection agent with similar transfection performance but poor protection capability against enzymatic cleavage. Our study provides new understandings in the rational design of nonviral vectors for efficient gene delivery.

Dendritic mesoporous silica nanospheres (DMSNs) with center–radial pore structure were successfully fabricated via an anion-assisted method. Al-modified DMSNs-supported NiMo catalysts were prepared and used for hydrodesulfurization (HDS) of dibenzothiophene (DBT). The DMSNs supports and corresponding supported NiMo catalysts were characterized by SEM, TEM, N2 adsorption/desorption, electron tomography (ET), 27Al NMR, NH3-TPD, UV–Vis spectroscopy, XPS, H2-TPR, Raman spectroscopy, and Pyridine-FTIR spectra. The average pore diameter of DMSNs is around 26.4 nm, which is helpful for eliminating the diffusion resistance of S-containing compounds. The center–radial pore structure of DMSNs, confirmed by ET measurement, is beneficial for enhancing the accessibility of active sites in the pore channels. The incorporation of aluminum into the framework of DMSNs can improve the acidity and modulate the metal–support interaction. Consequently, NiMo/Al-DMSNs catalysts exhibited higher HDS conversions (97.9%) for DBT than commercial NiMo/γ-Al2O3 catalyst. The superior catalytic activity of NiMo/Al-DMSNs results from a perfect combination of large center–radial pore channels, increased acidity, suitable metal–support interaction, and good dispersion/accessibility of active metals.

The catalytic performance of nanomotors is highly dependent on their interaction with substrates, for which the motion dynamics of the nanomotors needs to be carefully manipulated via materials design. Herein, we report a facile one-step self-assembly strategy for hundred-gram scale synthesis of shuttlecock-shaped silica nanoparticles as advanced catalytic nanomotors. These asymmetric nanoparticles have a streamline conical morphology with ultra-large opening in one side. The shuttlecock-mimetic morphology endows the nanoparticles with minimized drag force during fluid motion and consequently high diffusibility, while the large open cavity ensures efficient encapsulation of lipase (a model enzyme) to provide propulsive force. These unique features collectively result in superior diffusibility, leading to significantly improved catalytic performance compared with conventional large pore mesoporous silica nanoparticles with a spherical morphology. This research provides a new conceptual design and synthetic strategy to develop high-performance nanomotors.

Multifunctional core-shell-structured dendritic mesoporous silica nanoparticles with a fullerene-doped silica core, a dendritic silica shell and large pores have been prepared. The combination of photodynamic therapy and antibody therapeutics significantly inhibits the cancer cell growth by effectively reducing the level of anti-apoptotic proteins.

Nanostructured MgO has been identified as a promising material for As(III) removal, however its application is hindered by one engineering drawback (nanoparticles cannot be directly used in wastewater treatment) and its performance is limited by two unanswered scientific questions: (1) which composition is the optimized one for As(III) sorption, MgO, Mg(OH)2 or a mixed composition? (2) If the sorption of As(III) relies on the formation of Mg(OH)2 after hydration of MgO, why does nanostructured Mg(OH)2 have generally low As(III) sorption performance? To address the challenges, we report the synthesis of Mg(OH)2–MgO@rGO nanocomposites with tunable compositions for arsenic sequestration for the first time. It is demonstrated that the nanocomposite with an optimized composition of Mg(OH)2–MgO has an exceptionally higher As(III) sorption capacity than pure Mg(OH)2 or MgO composition, reaching a maximum arsenite sorption capacity of 681.3 mg g−1 (equal to 866.0 mg g −1 As(III)/MgO). It is revealed that only the adsorbent with a balanced composition and reduced crystallinity generates interconnected Mg(OH)2 nanosheets in situ during the sorption process, providing abundant and accessible sites for As(III) sorption with enhanced sorption capacity. The rGO in the nanocomposite has multiple functions, including (1) reducing the size and crystallinity of Mg(OH)2–MgO, (2) favoring the formation of interconnected Mg(OH)2 nanosheets and (3) facilitating the oxidation of As(III) partially into As(V), all beneficial for enhanced arsenic sorption capacity. The Mg(OH)2–MgO@rGO nanocomposite has been applied to treat As(III) contaminated water in a household water treatment device with excellent performance. Our findings have provided new understanding in the rational design of highly efficient nanocomposite adsorbents for arsenite removal applications.

Designed Janus silica nanoparticles can stimulate stronger phagocytosis and exhibit higher cargo transport across an in vitro epithelial monolayer model mimicking the human intestinal epithelium., A bottom-up self-assembly approach is developed for the synthesis of ABC type heterotrimeric nanoparticles, which can be converted into secondary Janus-type silica derivatives. Compared to spherical ones, Janus silica nanoparticles stimulate stronger phagocytosis and transcytosis through intestinal epithelial microfold cells and exhibit higher cargo transport across an in vitro epithelial monolayer model mimicking the human intestinal epithelium.

Fractal silica nanoparticles (FSN) have just emerged as a new type of nanoporous materials with high branching self-similarity and sharp tips. FSN are synthesized in ethanol-water mixed solvent at a reaction temperature well above the flash point, thus large-scale and safe synthesis of FSN remains challenging. In this work, two strategies were combined for scalable, safe and cost-effective synthesis of FSN. Firstly, by decreasing ethanol/water volume ratio, the yield of FSN per unit volume of synthesis solution was increased and the production cost was reduced. Secondly, by introducing ethylene glycol (EG) as a cosolvent, the flash point of the reaction solution of FSN was increased above the reaction temperature. Using these strategies and a synthesis temperature of 30 °C, kilogram-scale synthesis of FSN (506 g in one batch) was achieved, paving the way for the practical application of FSN.

Therapeutic targeting of the immune system, including chimeric antigen receptor-T cell therapy, immune checkpoint blockade therapy, neoantigen vaccines, and small molecule modulators emerges as one of the most effective therapeutic modalities for treating various cancers in human patients. However, clinical efficacies of these immunotherapeutics are generally modest and only a minority of cancer patients benefit from immunotherapy. Further, broad adverse effects, lack of reliable biomarkers, tumour relapses, drug resistance, and metastasis have become increasingly recognized concerns, which may restrain their clinical utility. Unlike most other anticancer strategies, nanomaterial-based therapeutics parade unique and distinct biological features to achieve precision targeting, local drug release, and enhancing therapeutic efficacy. As long-term and sustained release of immunotherapeutics are necessary for enhancing anticancer immunity, nanotechnology ensures accumulation of immunotherapuetics, controlled release, and precision delivery of immune drugs. Combination of these two therapeutic modalities would provide synergistic efficacy for effectively treating various cancers in human patients. To the best of our knowledge, the concept of combination therapy employing nanomaterials and immunotherapy has been overlooked. In this article, we discuss possible mechanisms underlying nano-immunotherapy and unique opportunities of nanotechnology in synergizing cancer treatment.

Anisotropic Janus nanoparticles have been widely investigated in recent years on both the nanoparticles preparation strategies and the advanced applications. Janus nanoparticles possess biphasic geometry of distinct compositions or asymmetric morphologies that bring distinct novel properties. Janus nanoparticles have been widely used in various applications such as catalysts, nanomotors, and nanomedicine. In biomedical fields, the special spatially separated surface chemistry of Janus nanoparticles provides efficient targeting and delivery capability, which can be used to design next generation delivery vectors. Moreover, the unique asymmetric morphology of Janus nano-particles exhibits unusual behaviours when internalized by cells. Janus nanoparticles can be developed as new probes to investigate the nanoparticle-cell interaction during the critical cellular delivery processes. This review focuses on recent progress of the design and synthesis of novel Janus nanoparticles and their unusual performance in cellular delivery related applications. The advantages and new opportunities of Janus nanoparticles as cellular delivery vectors are discussed.

ABSTRUCT Dendritic mesoporous organosilica nanoparticles (DMONs) have attracted increasing attention owing to the variety of appealing properties offered by the hybrid organic-inorganic framework and the central-radial pore structure. To date, two synthetic routes have been developed for the preparation of DMONs, including aqueous phase and water/oil bi-phasic systems. However, the impact of synthetic routes on the compositional and structural properties of the resultant nanomaterials remains largely unexplored. In the present work, we aim to gain insight on these two synthetic routes and have observed an unexpected reversed “double-edged sword” effect of reaction time on the compositional and structural properties of DMONs for two synthetic routes. For the aqueous phase route, prolonged reaction time is beneficial for improving the organosilica content, but leads to the loss of porous structure. In contrast, for the water/oil biphasic route, prolonging the reaction time causes the reduction of organic content in the products, but facilitates the formation of well-defined dendritic mesoporous structure. A “rate determine step” based mechanism has been proposed to explain these observations. Moreover, DMONs prepared from aqueous route possess higher organic content than those prepared from the biphasic route, which has resulted in a significantly higher hydro-stability. Our work unravels that synthetic routes largely determine the compositional and structural properties of DMONs, for which the reaction time needs to pay particular attention to achieve maximized organic content and well-preserved pore structure for optimal performance in desired applications.

In this paper, a highly active three-dimensional Zr modified TUD-1 mesoporous material was successfully synthesized by using TEA as a template and TEAOH as an auxiliary template via sol–gel method. The synthesized materials were characterized by XRD, SEM, TEM, BET and UV–vis DRS. The characterization results indicated that zirconium was incorporated into the framework of TUD-1. TEM images of ZrT-100 showed a clearly worm-like structure, indicating that the TUD-1 silica framework or mesoporous conformation was still kept even after the incorporation of Zr. Additionally, the as-synthesized material had large pore size, high surface area and high pore volume. The hydrodesulfurization(HDS) performances of the supported catalysts were evaluated in a high pressure micro-reactor using FCC diesel from PetroChina Hohhot petrochemical company as feedstock, furthermore, it was found that NiMo/Al 2 O 3 -ZrT-100 with a relatively high Si/Zr ratio among the series catalysts of NiMo/Al 2 O 3 -ZrT-m showed the highest HDS efficiency, which was as high as 99.3%. Moreover, the best operating conditions of NiMo/Al 2 O 3 -ZrT-100 catalyst were achieved, which are the temperature of 350–360 °C, the pressure of 6 MPa, the WHSV of 1.0–1.2 h −1 , and the H 2 to oil ratio of 600 ml ml −1 .

Aluminum-modified 3D mesoporous TUD-1 materials (denoted as Al-TUD-1, abbreviated as AT) were successfully synthesized by a sol–gel method using TEA and TEAOH as the co-template. Several analytical techniques such as XRD, N2 physisorption, TEM, NH3-TPD, H2-TPR and UV-vis DRS were used to characterize the typical physico-chemical properties of Al2O3–AT composite supports and their corresponding catalysts. The characterization results indicated that most of the aluminum species was partially incorporated into the framework of the TUD-1 silicate network, and the as-synthesized material had a uniform pore size distribution, high surface area and high pore volume. The catalytic performances of hydrotreating were evaluated by using PetroChina Hohhot petrochemical company FCC diesel as the feedstock. Among the series catalysts of NiMo/Al2O3–AT-m, the catalyst with 30 m% AT in the support exhibited the highest HDS conversion, which was as high as 97.42%. Moreover, the influence factors in the synthetic process of the Al modified TUD-1 such as Si/Al ratio, heat treatment time and heat temperature were systematically studied and the corresponding supported NiMo series catalysts showed good hydrotreating performances. The catalyst with the Si/Al ratio of 50 in AT, heat treatment time of 18 h and heat treatment temperature of 180 °C exhibited the highest HDS (97.56%) and HDN (99.63%) efficiencies, respectively.

Post-synthesis methods are a promising technology and have received much attention. In this paper, a series of post-synthesis aluminum modified TUD-1 (PAT) materials with different Al contents were successfully prepared by using aluminum isopropoxide to be Al sources, then the as-synthesized materials were adopted as support additives mixed with commercial γ-Al2O3 to prepare hydrodesulfurization (HDS) catalysts for FCC diesel. The supports and catalysts were analyzed using N2 adsorption-desorption, XRD, SEM, Py-IR, ICP, 27Al MAS NMR, UV-vis, H2-TPR and HRTEM techniques. The results of Py-IR and 27Al MAS NMR indicated that the addition of Al species could bring Lewis (L) and Bronsted (B) sites into Si-TUD-1, and that the material of PAT-3 had the highest total acidity sites and Bronsted acid sites among the series PAT composites. The HRTEM technique showed that, compared to the traditional catalyst NiMo/γ-Al2O3, the sulfided catalyst NiMo/APAT-3 had a relatively short length (3.2 nm) and suitable stacking number (2.5) of MoS2 slabs. The HDS efficiencies of all the catalysts were tested in a fixed bed micro-reactor with FCC diesel as feedstock. The catalytic results confirmed that the catalyst NiMo/APAT-3 possessed the highest HDS efficiency (97.0%), due to synergistic effects of advantageous properties such as higher acidity, moderate MSI, and relatively short length of the MoS2 slabs.