Calcium Carbonate Nanoparticles Research Articles

A robust superhydrophobic coating of siloxane resin and hydrophobic calcium carbonate nanoparticles for limestone protection

Hydrophobic calcium carbonate (CaCO3) nanoparticles (NPs), modified with dodecanoic acid (DA), are produced and dispersed in solutions of KSE 100, which is a silicic acid ester base product used for the conservation and maintenance of heritage and modern buildings. The dispersions are sprayed on limestone and marble specimens. By adjusting the relative concentrations of DA and NPs, the treated stones obtain superhydrophobic properties. Focusing on limestone it is reported that the treatment has negligible effects on the colour and vapour permeability of the original stone and offers protection against water capillary rise. Several studies are performed to test the durability of the composite (KSE + CaCO3-DA NPs) coating against rain impact, freezing and thawing, salt attack and UV radiation. Moreover, the mechanical, chemical and thermal durability of the coating is studied according to the tape peeling test, contact angles of drops which correspond to a vast range of pH, and heat treatment. The results of the aforementioned tests reveal the very good stability of the composite coating. In sum, it is reported that the wetting properties of the KSE 100 stone strengthener, which is used in building conservation, can be highly improved by adding a small amount of modified CaCO3 NPs. The latter are chemically compatible with calcareous stones.

A review of ternary polymer nanocomposites containing clay and calcium carbonate and their biomedical applications

Abstract Patchy interactions and heterogeneous charge distribution make nanoclay (NC) a promising biomaterial to interact with different biomolecules, polymers, and biological components. Many researchers have studied the polymer/clay nanocomposites in recent years. However, some deficiencies, such as poor impact strength, limit the application of polymer/clay nanocomposites in different fields. As a result, many attempts have been made to resolve this problem. Also, researchers have developed calcium carbonate (CaCO3) nanoparticles as biomedical materials. The nontoxic properties and biocompatibility of both CaCO3 and NC make their nanocomposites ideal for biomedical applications. In this article, a detailed review of the ternary polymer nanocomposites containing NC and CaCO3 is presented. The morphological, thermal, mechanical, and rheological characteristics, in addition to the modeling of behavior and foam properties, are studied in this article. In addition, the potential challenges for ternary nanocomposites and their biomedical applications are discussed.

Efficient Delivery of Recombinant Human Bone Morphogenetic Protein (Rhbmp-2) With Cockle Shell Derived Calcium Carbonate Nanoparticles (CaCO3NPs)

Bone morphogenetic protein-2 (BMP-2) has a significant function in the formation of cartilage and bones. Notably, dosing of only BMP-2 protein intravenously is ineffective. Persistent transportation of the stabilized BMP-2 through a carrier has been seen to be essential for enhancing the osteogenesis im pact of BMP-2. The current research built a new system of drug delivery by utilising cockle shell derived calcium carbonate nanoparticles (CaCO3NPs) and studied the efficacy of the delivery system on the recombinant human bone morphogenetic protein (rhBMP-2). rhBMP-2-CaCO3NPs nanoparticles were synthesised by means of a modest precipitation procedure along with mechanical grinding. Fourier-tran sform infrared spectroscopy, UV–Vis spectrophotometer, scanning electron microscope, X-ray powder diffraction, transmission electron microscope, and zeta potential were u tilised for characterising the conjugated rhBMP-2-CaCO3NPs . Cytotoxicity of rhBMP-2, CaCO3NPs and rhBMP-2-CaCO 3NPs was studied by utilising methylthiazol tetrazolium assay against fibroblast (Rat-1) cells in comparison to rhBMP-2 and CaCO3NPs. The outcomes signified bio-stability of CaCO3NPs and lower toxicity for Rat-1 cells. In summary, CaCO3NPs were prepared by a simp le precipitation process. The ensuing nanoparticles could competently entrap rhBMP-2 and generated stable rhBMP-2-CaCO3NPs. A sustained discharge of rhBMP-2 from t he CaCO3NPs was seen. CaCO3NPs loaded with r hBMP-2 demonstrated reasonable bio-compatibility. The outcomes indicated that CaCO3NPs may have significant ability as carrier of therapeutic proteins within bone tissue en gineering.

Size-dependent therapeutic efficiency of 223Ra-labeled calcium carbonate carriers for internal radionuclide therapy of breast cancer.

The size of drug carriers strongly affects their biodistribution, tissue penetration, and cellular uptake in vivo. As a result, when such carriers are loaded with therapeutic compounds, their size can influence the treatment outcomes. For internal α-radionuclide therapy, the carrier size is particularly important, because short-range α-emitters should be delivered to tumor volumes at a high dose rate without any side effects, i.e. off-target irradiation and toxicity. In this work, we aim to evaluate and compare the therapeutic efficiency of calcium carbonate (CaCO3) microparticles (MPs, >2 μm) and nanoparticles (NPs, <100 nm) labeled with radium-223 (223Ra) for internal α-radionuclide therapy against 4T1 breast cancer. To do this, we comprehensively study the internalization and penetration efficiency of these MPs and NPs, using 2D and 3D cell cultures. For further therapeutic tests, we develop and modify a chelator-free method for radiolabeling of CaCO3 MPs and NPs with 223Ra, improving their radiolabeling efficiency (>97%) and radiochemical stability (>97%). After intratumoral injection of 223Ra-labeled MPs and NPs, we demonstrate their different therapeutic efficiencies against a 4T1 tumor. In particular, 223Ra-labeled NPs show a tumor inhibition of approximately 85%, which is higher compared to 60% for 223Ra-labeled MPs. As a result, we can conclude that 223Ra-labeled NPs have a more suitable biodistribution within 4T1 tumors compared to 223Ra-labeled MPs. Thus, our study reveals that 223Ra-labeled CaCO3 NPs are highly promising for internal α-radionuclide therapy.

Influence of reduced graphene oxide on the morphology, structural, and thermal properties of calcium carbonate nanocomposites

Current highly integrated devices require heat interface materials with excellent heat conductivity. A simple approach was employed to synthesize thermally conductive and outstanding thermal stability nanocomposite. Calcium carbonate nanoparticles (nano CaCO3) reinforced with reduced graphene oxide (rGO) nanoparticles (rGO/CaCO3) are synthesized using a novel process, and the effect of rGO in CaCO3 structure is examined by Field Emission Scanning Electron Microscope, X-ray diffraction, TGA-DTA, and thermal conductivity. The experimental results show that adding rGO resulted in higher crystallinity and thermal stability. As the wt.% of rGO increases from 1 to 5%, the crystallite size was suppressed by 21.06%, 27.39%, 32.48%, 41.5%, and 45.30%, respectively, compared to the pure nano-CaCO3. Additionally, rGO enhances the thermal conductivity by 35.31% and thermal diffusivity to 1.834 mm2/s by adding 5% rGO.

Size and phase preservation of amorphous calcium carbonate nanoparticles in aqueous media using different types of lignin for contrast-enhanced ultrasound imaging

Hypothesis: Calcium carbonate (CaCO3) nanoparticles could have great potential for contrast-enhanced ultrasound imaging (CEUS) due to their gas-generating properties and sensitivity to physiological conditions. However, the use of nano CaCO3 for biomedical applications requires the assistance of stabilizers to control the size and avoid the fast dissolution/recrystallization of the particles when exposed to aqueous conditions.Experiments: Herein, we report the stabilization of nano CaCO3 using lignin, and synthesized core–shell amorphous CaCO3-lignin nanoparticles (LigCC NPs) with a diameter below 100 nm. We have then investigated the echogenicity of the LigCC NPs by monitoring the consequent generation of contrast in vitro for 90 min in linear and non-linear B-mode imaging.Findings: This research explores how lignin type and structure affect stabilization efficiency, lignin structuration around CaCO3 cores, and particle echogenicity. Interestingly, by employing lignin as the stabilizer, it becomes possible to maintain the echogenic properties of CaCO3, whereas the use of lipid coatings prevents the production of signal generation in ultrasound imaging. This work opens new avenue for CEUS imaging of the vascular and extravascular space using CaCO3, as it highlights the potential to generate contrast for extended durations at physiological pH by utilizing the amorphous phase of CaCO3.

Therapeutic Nanovaccines Reshape the Metabolic and Immune Microenvironment for Enhancing Immunotherapy of Primary and Lymphatic Metastatic Tumors

AbstractThe effectiveness of anti‐metastasis therapy is hampered by the highly immunosuppressive microenvironment found in both tumor tissues and lymph nodes. In this work, a therapeutic nanovaccine, CaGlu NPs, is introduced composed of calcium carbonate nanoparticles (CaCO3 NPs) and β‐glucan. Through the synergistic effect of CaCO3 NPs and β‐glucan, CaGlu NPs can induce immunogenic cell death in tumor tissues, repolarize tumor macrophages, reverse the immunosuppressive tumor microenvironment, effectively activate antigen‐specific cytotoxic T lymphocytes, promote dendritic cells maturation, and eventually elicit an effective anti‐tumor immune response in both primary tumors and metastatic lymph nodes. Meanwhile, CaGlu NPs can remodel the metabolic microenvironment in tumors and lymph nodes by decreasing the expression of lactate dehydrogenase A and hypoxia‐inducible factor‐1α, further enhancing the anti‐tumor immune response. CaGlu NPs also inhibit tumor angiogenesis and lymphangiogenesis and induce long‐term immune memory effects. This therapeutic nanovaccine strategy, which simultaneously remodels the metabolic and immunosuppressive microenvironments in tumors and metastatic lymph nodes, showed strong anti‐metastatic effects in vivo. This study presents a promising approach to effectively treat lymph node metastatic tumors using nanomaterial‐assisted immunotherapies and underscores its broad potential for clinical applications.

Nano-modulators with the function of disrupting mitochondrial Ca2+ homeostasis and photothermal conversion for synergistic breast cancer therapy

Breast cancer treatment has been a global puzzle, and apoptosis strategies based on mitochondrial Ca2+ overload have attracted extensive attention. However, various limitations of current Ca2+ nanogenerators make it difficult to maintain effective Ca2+ overload concentrations. Here, we constructed a multimodal Ca2+ nano-modulator that, for the first time, combined photothermal therapy (PTT) and mitochondrial Ca2+ overload strategies to inhibit tumor development. By crosslinking sodium alginate (SA) on the surface of calcium carbonate (CaCO3) nanoparticles encapsulating with Cur and ICG, we prepared a synergistic Ca2+ nano-regulator SA/Cur@CaCO3-ICG (SCCI). In vitro studies have shown that SCCI further enhanced photostability while preserving the optical properties of ICG. After uptake by tumor cells, SCCI can reduce mitochondrial membrane potential and down-regulate ATP production by producing large amounts of Ca2+ at low pH. Near-infrared light radiation (NIR) laser irradiation made the tumor cells heat up sharply, which not only accelerated the decomposition of CaCO3, but also produced large amounts of reactive oxygen species (ROS) followed by cell apoptosis. In vivo studies have revealed that the Ca2+ nano-regulators had excellent targeting, biocompatibility, and anti-tumor effects, which can significantly inhibit the proliferation of tumor cells and play a direct killing effect. These findings indicated that therapeutic strategies based on ionic interference and PTT had great therapeutic potential, providing new insights into antitumor therapy.Graphical

Preparation and properties of water‐borne polyurethane‐sodium lignosulfonate/nano‐calcium carbonate composites

AbstractTo improve the application range of waterborne polyurethane (WPU), in this study, nano calcium carbonate/sodium lignosulfonate (CaCO3/SL) composites were prepared using sodium lignosulfonate (SL) wet‐modified calcium carbonate nanoparticles. Then, a series of waterborne polyurethane (WPU) nanocomposites (WPU‐CaCO3/SL) were prepared by solution mixing. Zeta, FT‐IR, XRD, SEM, and TGA were used to characterize the structure and morphology of CaCO3/SL and WPU‐CaCO3/SL. By conducting an analysis on the impact of various dosages of CaCO3/SL composite on the performance of WPU, the findings revealed that the tensile strength of WPU‐CaCO3/SL nanocomposites, when composed with a 3 wt% CaCO3/SL dosage, exhibited a significant increase of 116% from 6.93 to 14.95 mPa. The water contact angle demonstrated a significant increase from 78.3° to 90.1°. Additionally, the maximum decomposition temperature showed a noticeable rise of approximately 7°C. The WPU exhibit enhanced heat resistance, water resistance and mechanical properties, as well as exceptional ultraviolet (UV) absorption capabilities. This study provides a reference for modifying polymers with inorganic fillers and improving the optical properties of polymeric materials.Highlights Successful modification of nano calcium carbonate using biopolymer SL. Modified CaCO3/SL can be uniformly dispersed in water. Improved thermal stability of WPU composites. WPU composites exhibit excellent mechanical properties and water resistance. Well‐dispersed CaCO3/SL improves ultraviolet radiation resistance of WPU composites.

Morphological Characterization of Calcium Carbonate Nanoparticles Derived from Blood Cockle Shells (Anadara granosa)

Blood cockle shells are a type of shellfish with distinctive bright red color that is commonly found in coastal areas of Asia, a rich source of protein, vitamins, and minerals, including calcium carbonate. Calcium carbonate (CaCO3) is a common mineral supplement that slowly paved its way into nano research to support bone health that also used in the treatment of bone infections due to its inherent properties; reduces inflammation, promotes bone healing, crucial role in the immune system, and slow degradability. The latest invention on CaCO3 from cockle shells, is an alternative mode of drug delivery to circumvent existing antibiotic resistance mechanisms and allow direct drug delivery to the target site, using locally sourced ingredients to reduce long-term high production costs. A top-down approach CaCO3 nanoparticles from blood cockle (Anadara granosa) shells were developed, known as calcium carbonate nanoparticles (CNPs). This research aims to characterize the morphology of CNPs from blood cockle shells via Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM). A homogeneously spherical CNPs. with a mean diameter of 36.5 ± 2.3 nm was observed on TEM, so as FESEM. From AFM, the mean diameter for CNPs was 38.6 ± 3.6 nm The CNPs were spherical in shape, homogenously scattered, less agglomerate, porous with rough surfaces. The size and morphology of the CNPs from blood cockle shells were suitable for transport carrier in situ bone infection, according to the results.

Producing amorphous calcium carbonate using waste Ca-rich solution generated through the bio-leaching of slag

This study presents a new method for treating waste Ca-rich solutions (WCS), from which amorphous calcium carbonate (ACC) nanoparticles, an industrial product in high demand, are produced. The distinctive feature of this method is the use of tannic acid (TA) as a surfactant, employing a CO2 bubbling method under ambient conditions. By modulating the concentration of TA, the morphology and crystallization of the generated CaCO3 nanoparticles can be effectively controlled. Experimental results reveal that with increasing TA dosage, the crystallinity of CaCO3 decreases until an amorphous phase is obtained. The crystallization of ACC in solution was completely inhibited when TA was added at a concentration of more than 1%. Therefore, the proposed method provides a new strategy for the efficient preparation of ACC from WCS.

Bioresponsive and immunotherapeutic nanomaterials to remodel tumor microenvironment for enhanced immune checkpoint blockade

Immune checkpoint blockade (ICB) therapy is a revolutionary approach to treat cancers, but still have limited clinical applications. Accumulating evidence pinpoints the immunosuppressive characteristics of the tumor microenvironment (TME) as one major obstacle. The TME, characterized by acidity, hypoxia and elevated ROS levels, exerts its detrimental effects on infiltrating anti-tumor immune cells. Here, we developed a TME-responsive and immunotherapeutic catalase-loaded calcium carbonate nanoparticles (termed as CAT@CaCO3 NPs) as the simple yet versatile multi-modulator for TME remodeling. CaCO3 NPs can consume protons in the acidic TME to normalize the TME pH. CAT catalyzed the decomposition of ROS and thus generated O2. The released Ca2+ led to Ca2+ overload in the tumor cells which then triggered the release of damage-associated molecular patterns (DAMP) signals to initiate anti-tumor immune responses, including tumor antigen presentation by dendritic cells. Meanwhile, CAT@CaCO3 NPs-induced immunosupportive TME also promoted the polarization of the M2 tumor-associated macrophages to the M1 phenotype, further enhancing tumor antigen presentation. Consequently, T cell-mediated anti-tumor responses were activated, the efficacy of which was further boosted by aPD-1 immune checkpoint blockade. Our study demonstrated that local treatment of CAT@CaCO3 NPs and aPD-1 combination can effectively evoke local and systemic anti-tumor immune responses, inhibiting the growth of treated tumors and distant diseases.

Bio-synthesized calcium carbonate (CaCO3) nanoparticles: Their anti-fungal properties and application as nanofertilizer on Lycopersicon esculentum growth and gas exchange measurements

Bio-synthesized calcium carbonate nanoparticles (CaCO3 NPs) have gained attention because of their cost-effectiveness, minimal toxicity, biological compatibility, cytological compatibility, pH sensitivity, gradual biological degradability and ecological friendliness. As the global population is expected to rise to billions, innovative strategies to enhance crop production are necessary to address poverty challenges. This study assesses the effect of the bioinspired CaCO3 NPs as nanofertilizers on the development, gas exchange and yield parameters of tomatoes (Lycopersicon esculentum) and their antifungal activity. The trial was conducted in a 2×4 completely randomised design (CRD) with four replicates. The treatments consisted of different CaCO3 NPs concentrations (Control = 0 mg/L, 50 mg/L, 150 mg/L and 250 mg/L) on two tomato cultivars (Money-maker and Heinz-1370), and the antifungal activity of the CaCO3 NPs was tested against pathogens that cause diseases in tomato plants. The results demonstrate that CaCO3 NPs exhibit moderate antifungal activity against Cladosporium cladosporioides, Fusarium oxysporum and Penicillium halotolerans at minimum inhibitory concentration (MIC) values of 125, 250 and 500 µg/mL. Results further show that 250 mg/L exhibits the highest number of leaves on Money-maker, while 150 mg/L gave the highest number of leaves at week 8 for Heinz-1370. The application of 150 mg/L yielded the highest number of flowers in both cultivars compared to other treatments. Remarkably, different CaCO3 NP concentrations varied the gas exchange parameters and revealed that at concentrations higher than 150 mg/L, the efficiency of water use during the vegetative and fruiting stages was lowered. The highest fruit weight of the Money-maker was observed at 50 mg/L, whereas Heinz-1370’s fruit weight was higher at 250 mg/L, indicating that the two cultivars are affected differently by the foliar application of CaCO3 NPs. Therefore, the findings of this study suggest that the inclusion of a green synthesis of CaCO3 NPs as a nanofertilizer has the potential to promote tomato growth and yield.

The synergistic treatment of cyclolinopeptide J and calcium carbonate nanoparticles for osteoporosis via BMP/Wnt signaling: In vivo and in vitro

This research focuses on the investigation of cyclolinopeptide J (CLJ), a bioactive peptide naturally present in flaxseed, which loaded in porous calcium carbonate (CA) nanoparticles (JCA) to augment the effectiveness of CLJ on osteogenesis. The JCA was successfully synthesized with a high loading capacity (47.8 %) and encapsulation efficiency (95.6 %). Results showed that CLJ exerted an excellent osteogenic effect at 10 µM in MC3T3-E1 cells. CLJ and CA have been shown to activate osteogenic factors by modulating the Wnt/β-catenin and BMP/Smad signaling pathways. Furthermore, JCA treatment exhibited a remarkable ability to restore the intricate trabecular characteristics of bone in OVX-induced mice. The trabecular bone architecture observed in JCA-treated mice closely resembled that of healthy controls, indicating a substantial amelioration of osteoporotic bone loss. Our findings highlight the synergistic treatment of CLJ and CA in restoring bone integrity and structure and provide compelling evidence for the effectiveness of this novel functional supplement.

Tunable honeycomb-hierarchical multiscale structures of 2D/3D porous PLA/CCN composite films fabricated by the breath figure method

Highly ordered porous structures of PLA composite films can be designed with the addition of calcium carbonate nanoparticles (CCN) in polymeric film formation using the breath figure (BF) technique at controlled humidity. Both 2D and 3D monodispersed honeycomb-like porous structures of the PLA composite films are achieved by the adding CCN at the concentration of up to 1.00 phr, whereas hierarchically multiscale porous structures of the PLA/CCN films are obtained when the CCN concentration in the composites increases to more than 1.00 phr. These structures can be fabricated due to three mechanisms: water absorption and condensation, nano-Pickering emulsion, and capillary flow by self-assembly of the nanoparticles. Moreover, the nano effects of CCN on polymeric film fabrication are maximized by increasing the relative humidity to 90%, resulting in the formation of porous multilayers up to 95–120 μm in thickness. The application of the prepared porous composite films of PLA/CCN in the food and medical industries was illustrated. A model colorimetric sensor is made from PLA/CCN composite films enriched with bromothymol blue. The color of the films quickly changes from yellow to blue within 10 min after coming into contact with histamine, a representative gas generated from spoiled food.

Tetrahedral DNA–mediated biomineralization of calcium carbonate nanoparticles for pH-responsive drug delivery

Tetrahedral DNA–mediated biomineralization of calcium carbonate nanoparticles for pH-responsive drug delivery

Self-fueling ferroptosis-inducing microreactors based on pH-responsive Lipiodol Pickering emulsions enable transarterial ferro-embolization therapy.

Lipiodol chemotherapeutic emulsions remain one of the main choices for the treatment of unresectable hepatocellular carcinoma (HCC) via transarterial chemoembolization (TACE). However, the limited stability of Lipiodol chemotherapeutic emulsions would lead to rapid drug diffusion, which would reduce the therapeutic benefit and cause systemic toxicity of administrated chemotherapeutics. Therefore, the development of enhanced Lipiodol-based formulations is of great significance to enable effective and safe TACE treatment. Herein, a stable water-in-oil Lipiodol Pickering emulsion (LPE) stabilized by pH-dissociable calcium carbonate nanoparticles and hemin is prepared and utilized for efficient encapsulation of lipoxygenase (LOX). The obtained LOX-loaded CaCO3&hemin-stabilized LPE (LHCa-LPE) showing greatly improved emulsion stability could work as a pH-responsive and self-fueling microreactor to convert polyunsaturated fatty acids (PUFAs), a main component of Lipiodol, to cytotoxic lipid radicals through the cascading catalytic reaction driven by LOX and hemin, thus inducing ferroptosis of cancer cells. As a result, such LHCa-LPE upon transcatheter embolization can effectively suppress the progression of orthotopic N1S1 HCC in rats. This study highlights a concise strategy to prepare pH-responsive and stable LPE-based self-fueling microreactors, which could serve as bifunctional embolic and ferroptosis-inducing agents to enable proof-of-concept transarterial ferro-embolization therapy of HCC.

Dual-Wavelength Passively Q-Switched Erbium-Doped Fiber Laser Incorporating Calcium Carbonate Nanoparticles as Saturable Absorber

This study experimentally demonstrates the operation of a dual-wavelength passively Q-switched erbium-doped fiber laser that incorporates CaCO3 nanoparticles as a saturable absorber (SA). The SA was prepared by using the drop-casting method, wherein CaCO3 nanoparticles were embedded in a polyvinyl alcohol (PVA) polymer to form a CaCO3/PVA film SA. The film was integrated into a ring laser cavity with a 976 nm pump to generate Q-switched pulses. The properties of the SA were examined experimentally, and its modulation depth is approximately 47%. As the pump power increased from 180 mW to 270 mW and the pulse repetition rate increased from 12.67 kHz to 21.3 kHz, the corresponding pulse width decreased from 35.27 μs to 18.74 μs. The signal-to-noise ratio was approximately 25 dB, highlighting the laser’s stability. The results indicate that the proposed CaCO3/PVA SA is suitable for realizing portable Q-switched lasers.

Regulation of Ion Homeostasis for Enhanced Tumor Radio-Immunotherapy.

Intra/extracellular ion content affects the growth and metastasis of tumor cells, as well as the efficacy of various antitumor therapies. Herein, a carbonic anhydrase inhibitor (CAI) is loaded onto pH-responsive calcium carbonate (CaCO3 ) nanoparticles and then modify theses nanoparticles with liposomes to obtain biocompatible CaCO3 /CAI@Lipsome (CCL) for enhance tumor radio-immunotherapy. CCL can specially decompose in tumor microenvironment, releasing calcium ion (Ca2+ ) and CAI, as well as increasing the pH value of extracellular fluid. CAI restrains the flow of hydrogen ion (H+ ) inside and outside the tumor cells, resulting in the reversal of tumor acidic microenvironment and the increase of intracellular H+ , both of which can improve the sensitivity of tumor to radiotherapy. Afterward, the increased intracellular H+ together with radiotherapy-causes reactive oxygen species promotes calcium influx, leading to cellular calcium overload. Moreover, the CCL-tailored content of H+ and Ca2+ strengthens radiotherapy-induced immunogenic cell death and dendritic cell maturation, amplifying systemic anti-tumor adaptive immunity. Meanwhile, macrophages in the CCL-treated tumors are polarized from pro-tumor M2 to anti-tumor M1 under X-ray exposure, owing to the neutralization of tumor acidic microenvironment and enhances Ca2+ content. Therefore, multi-directional regulation of the intra/extra tumor cell pH/calcium by simple nano-preparation would provide a powerful way to improve the efficacy of radio-immunotherapy.

Dynamic Growth of Macroscopically Structured Supramolecular Hydrogels through Orchestrated Reaction-Diffusion.

Living organisms are capable of dynamically changing their structures for adaptive functions through sophisticated reaction-diffusion processes. Here we show how active supramolecular hydrogels with programmable lifetimes and macroscopic structures can be created by relying on a simple reaction-diffusion strategy. Two hydrogel precursors (poly(acrylic acid) PAA/CaCl2 and Na2 CO3 ) diffuse from different locations and generate amorphous calcium carbonate (ACC) nanoparticles at the diffusional fronts, leading to the formation of hydrogel structures driven by electrostatic interactions between PAA and ACC nanoparticles. Interestingly, the formed hydrogels are capable of autonomously disintegrating over time because of a delayed influx of electrostatic-interaction inhibitors (NaCl). The hydrogel growth process is well explained by a reaction-diffusion model which offers a theoretical means to program the dynamic growth of structured hydrogels. Furthermore, we demonstrate a conceptual access to dynamic information storage in soft materials using the developed reaction-diffusion strategy. This work may serve as a starting point for the development of life-like materials with adaptive structures and functionalities.