Substantial Confinement of Crystal Growth of Organic Crystalline Materials in Metal-Organic Membrane Microshells.

This study proposes a robust microshell encapsulation system in which a metal-organic membrane (MOM), consisting of phytic acids (PAs) and metal ions, intrinsically prevents the molecular crystal growth of organic crystalline materials (OCMs). To develop this system, OCM-containing oil-in-water (O/W) Pickering emulsions were enveloped with the MOM, in which anionic pulp cellulose nanofiber (PCNF) primers electrostatically captured zinc ions at the O/W interface and chelated with PA, thus producing the MOM with a controlled shell thickness at the micron scale. We ascertained that the MOM formation fills and covers ∼75% of the surface pore size of PCNF films, which enhances the interfacial modulus by 2 orders of magnitude compared to that when treated with bare PCNFs. Through a feasibility test using a series of common OCMs, including ethylhexyl triazone, avobenzone, and ceramide, we demonstrated the excellent ability of our MOM microshell system to stably encapsulate OCMs while retaining their original molecular structures over time. These findings indicate that our MOM-reinforced microshell technology can be applied as a platform to substantially confine the crystal growth of various types of OCMs.

Shear-Responsive Sol-Gel Transition of Phase Change Material Emulsions for an Injectable Thermal Insulation Platform.

Phase change materials (PCMs) have attracted significant attention as promising insulating materials. However, they often suffer from the simple yet critical problem of leakage in practical applications. Therefore, in this study, an injectable PCM emulsion insulation platform is developed. For this, n-hexadecane, as a PCM, emulsion droplets are armored with a metal-organic membrane (MOM) through the coordination of zinc ions and phytic acid. The MOM layer not only provides a rigid interfacial modulus but also allows the emulsion to exhibit viscoelastic behavior by shear stress-induced interdrop association. This MOM-enveloped PCM emulsion (PCMEMOM ) exhibited typical sol-gel transition behavior in response to applied shear stress, indicating the injectable characteristic of the PCMEMOM . After observing the rheological hysteresis and thermal stability of the PCMEMOM under repetitive heating and cooling cycles, the thermal insulation performance of PCMEMOM is quantitatively and visually demonstrated. These findings suggest an efficient method to exploit high-performance insulation systems.

Biofunctional Inorganic Layered Double Hydroxide Nanohybrid Enhances Immunotherapeutic Effect on Atopic Dermatitis Treatment.

Atopic dermatitis (AD) is a widespread, recurrent, and chronic inflammatory skin condition that imposes a major burden on patients. Conventional treatments, such as corticosteroids, are associated with various side effects, underscoring the need for innovative therapeutic approaches. In this study, the possibility of using indole-3-acetic acid-loaded layered double hydroxides (IAA-LDHs) is evaluated as a novel treatment for AD. IAA is an auxin-class plant hormone with antioxidant and anti-inflammatory effects. Following the synthesis of IAA-LDH nanohybrids, their ability to induce M2-like macrophage polarization in macrophages obtained from mouse bone marrow is assessed. The antioxidant activity of IAA-LDH is quantified by assessing the decrease in intracellular reactive oxygen species levels. The anti-inflammatory and anti-atopic characteristics of IAA-LDH are evaluated in a mouse model of AD by examining the cutaneous tissues, immunological organs, and cells. The findings suggest that IAA-LDH has great therapeutic potential as a candidate for AD treatment based on its in vitro and in vivo modulation of AD immunology, enhancement of macrophage polarization, and antioxidant activity. This inorganic drug delivery technology represents a promising new avenue for the development of safe and effective AD treatments.

Cabozantinib-Loaded PLGA Nanoparticles: A Potential Adjuvant Strategy for Surgically Resected High-Risk Non-Metastatic Renal Cell Carcinoma.

Patients with high-risk non-metastatic renal cell carcinoma (RCC) are at risk of metastatic relapse following nephrectomy. Cabozantinib (CZ), a potent multitarget tyrosine kinase inhibitor, interferes with angiogenesis and immunosuppression associated with surgery-induced metastasis. Here, we explored the therapeutic potential of CZ-loaded poly(lactic-co-glycolic acid) (PLGA) nanoparticles (CZ-PLGA-NPs) as an adjuvant strategy for targeting post-nephrectomy metastasis. A clinically relevant subline recapitulating post-nephrectomy lung metastasis of high-risk human RCC, namely Renca-SRLu5-Luc, was established through in vivo serial selection of luciferase-expressing murine RCC Renca-Luc cells. CZ was encapsulated into PLGA-NPs via the conventional single emulsion technique. The multifaceted preclinical antimetastatic efficacy of CZ-PLGA-NPs was assessed in Renca-SRLu5-Luc cells. CZ-PLGA-NPs with a smooth surface displayed desirable physicochemical properties, good CZ encapsulation efficiency, as well as controlled and sustained CZ release. CZ-PLGA-NPs exhibited remarkable dose-dependent toxicity against Renca-SRLu5-Luc cells by inducing G2/M cell cycle arrest and apoptosis. CZ-PLGA-NPs attenuated in vitro colony formation, migration, and invasion by abrogating AKT and ERK1/2 activation. An intravenous injection of CZ-PLGA-NPs markedly reduced lung metastatic burden and prolonged lifespan with favorable safety in the Renca-SRLu5-Luc experimental lung metastasis model. The novel CZ-PLGA-NPs system with multifaceted antimetastatic effects and alleviating off-target toxicity potential is a promising adjunctive agent for patients with surgically resected high-risk RCC.

Development of a UV Index Sensor-Based Portable Measurement Device with the EUVB Ratio of Natural Light.

Ultraviolet (UV) rays are electromagnetic waves that account for about 5% of solar light, and when overexposed, they pose malevolent effects on human skin and health. However, with recent reports on the beneficial effects of some wavelength bands of UV rays, people's interest in UV information has increased. This has resulted in requiring not just simple information, such as the amount of UV or UV index (UVI), but detailed UV information that directly affects health, such as EUVB (erythemally weighted UVB). However, calculating EUVB, which can be done by applying the erythemal weighted function on the intensity value in wavelength, requires specialized optical measurement devices, which cannot be easily accessed by the general public; furthermore, public institutions' UV information services do not offer EUVB information for individuals. Therefore, the present study proposes a UVI sensor-based portable measurement device, with which the general public can have easy access to UV-related information. The proposed device comprises a UVI sensor that can measure the intensity of erythemal UV radiation, a Bluetooth Low Energy (BLE) module that supports communication, and a micro controller unit (MCU) for key operations. In addition, it applies the ratio of EUVB by month/time, resulting from the actual analysis of natural light to calculate the EUVB and provides the amount of UVI and EUVB to check if they meet conditions required for outdoor activities through the device and smartphone applications. The applicability of the proposed device was verified by the measurement performance comparison test with the standard device, a spectrometer (CAS 140 CT), which showed an average error of 0.045 for UVI and 0.0014 W/m². The proposed device's offering of UV-related information such as UVI and EUVB to the user is expected to prevent potential damage due to exposure to UV and to support healthy outdoor activities.

Highly Crystalline Mesoporous Phosphotungstic Acid: A High-Performance Electrode Material for Energy-Storage Applications.

Heteropoly acids (HPAs) are unique materials with interesting properties, including high acidity and proton conductivity. However, their low specific surface area and high solubility in polar solvents make them unattractive for catalytic or energy applications. This obstacle can be overcome by creating nanoporosity within the HPA. We synthesized mesoporous phosphotungstic acid (mPTA) with a spherical morphology through the self-assembly of phosphotungstic acid (PTA) with a polymeric surfactant as stabilized by KCl and hydrothermal treatment. The mPTA nanostructures had a surface area of 93 m2 g-1 and a pore size of 4 nm. Their high thermal stability (ca. 450 °C) and lack of solubility in ethylene carbonate/diethyl carbonate (EC/DEC) electrolyte are beneficial for lithium-ion batteries (LIBs). Optimized mPTA showed a reversible capacity of 872 mAh g-1 at 0.1 A g-1 even after 100 cycles for LIBs, as attributed to a super-reduced state of HPA and the storage of Li ions within the mesochannels of mPTA.

Cell-Penetrating Peptide-Patchy Deformable Polymeric Nanovehicles with Enhanced Cellular Uptake and Transdermal Delivery.

We herein propose a polymeric nanovehicle system that has the ability to remarkably improve cellular uptake and transdermal delivery. Cell-penetrating peptide-patchy deformable polymeric nanovehicles were fabricated by tailored coassembly of amphiphilic poly(ethylene oxide)- block-poly(ε-caprolactone) (PEO- b-PCL), mannosylerythritol lipid (MEL), and YGRKKRRQRRR-cysteamine (TAT)-linked MEL. Using X-ray diffraction, differential scanning calorimetry, and nuclear magnetic resonance analyses, we revealed that the incorporation of MEL having an asymmetric alkyl chain configuration was responsible for the deformable phase property of the vehicles. We also discovered that the nanovehicles were mutually attracted, exhibiting a gel-like fluid characteristic due to the dipole-dipole interaction between the hydroxyl group of MEL and the methoxy group of PEO- b-PCL. Coassembly of TAT-linked MEL with the deformable nanovehicles significantly enhanced cellular uptake due to macropinocytosis and caveolae-/lipid raft-mediated endocytosis. Furthermore, the in vivo skin penetration test revealed that our TAT-patchy deformable nanovehicles remarkably improved transdermal delivery efficiency.

Mesoporous carbon nitrides: synthesis, functionalization, and applications.

Mesoporous carbon nitrides (MCNs) with large surface areas and uniform pore diameters are unique semiconducting materials and exhibit highly versatile structural and excellent physicochemical properties, which promote their application in diverse fields such as metal free catalysis, photocatalytic water splitting, energy storage and conversion, gas adsorption, separation, and even sensing. These fascinating MCN materials can be obtained through the polymerization of different aromatic and/or aliphatic carbons and high nitrogen containing molecular precursors via hard and/or soft templating approaches. One of the unique characteristics of these materials is that they exhibit both semiconducting and basic properties, which make them excellent platforms for the photoelectrochemical conversion and sensing of molecules such as CO2, and the selective sensing of toxic organic acids. The semiconducting features of these materials are finely controlled by varying the nitrogen content or local electronic structure of the MCNs. The incorporation of different functionalities including metal nanoparticles or organic molecules is further achieved in various ways to develop new electronic, semiconducting, catalytic, and energy harvesting materials. Dual functionalities including acidic and basic groups are also introduced in the wall structure of MCNs through simple UV-light irradiation, which offers enzyme-like properties in a single MCN system. In this review article, we summarize and highlight the existing literature covering every aspect of MCNs including their templating synthesis, modification and functionalization, and potential applications of these MCN materials with an overview of the key and relevant results. A special emphasis is given on the catalytic applications of MCNs including hydrogenation, oxidation, photocatalysis, and CO2 activation.

Correction: Mesoporous carbon nitrides: synthesis, functionalization, and applications.

Correction for 'Mesoporous carbon nitrides: synthesis, functionalization, and applications' by Kripal S. Lakhi et al., Chem. Soc. Rev., 2017, DOI: .

Highly Crystalline Mesoporous C60 with Ordered Pores: A Class of Nanomaterials for Energy Applications.

Highly ordered mesoporous C60 with a well-ordered porous structure and a high crystallinity is prepared through the nanohard templating method using a saturated solution of C60 in 1-chloronaphthalene (51 mg mL-1 ) as a C60 precursor and SBA-15 as a hard template. The high solubility of C60 in 1-chloronaphthalene helps not only to encapsulate a huge amount of the C60 into the mesopores of the template but also supports the oligomerization of C60 and the formation of crystalline walls made of C60 . The obtained mesoporous C60 exhibits a rod-shaped morphology, a high specific surface area (680 m2 g-1 ), tuneable pores, and a highly crystalline wall structure. This exciting ordered mesoporous C60 offers high supercapacitive performance and a high selectivity to H2 O2 production and methanol tolerance for ORR. This simple strategy could be adopted to make a series of mesoporous fullerenes with different structures and carbon atoms as a new class of energy materials.

Energy Efficient Synthesis of Ordered Mesoporous Carbon Nitrides with a High Nitrogen Content and Enhanced CO2 Capture Capacity.

Highly ordered mesoporous carbon nitrides (MCN) with 3D structure and a high nitrogen content are successfully prepared for the first time using "uncalcined" mesoporous silica template, KIT-6 and 3-amino-1,2,4-triazole as a single molecular carbon and nitrogen precursor. The prepared MCN with C and N stoichiometry of C3 N5 shows unique CN framework and exhibits the CO2 capture capacity of 5.63 mmol g-1 at 273 K and 30 bar, which is higher than that of MCN with 2D structure and C3 N4 stoichiometry.

Highly Ordered Nitrogen-Rich Mesoporous Carbon Nitrides and Their Superior Performance for Sensing and Photocatalytic Hydrogen Generation.

Mesoporous carbon nitrides (MCN) are fascinating materials with unique semiconducting and basic properties that are useful in many applications including photocatalysis and sensing. Most syntheses of MCN focus on creating theoretically predicted C3 N4 stoichiometry with a band gap of 2.7 eV using a nano-hard templating approach with triazine-based precursors. However, the performance of the MCN in semiconducting applications is limited to the MCN framework with a small band gap, which would be linked with the addition of more N in the CN framework, but this remains a huge challenge. Here, we report a precursor with high nitrogen content, 3-amino-1,2,4-triazole, that enables the formation of new and well-ordered 3D MCN with C3 N5 stoichiometry (MCN-8), which has not been predicted so far, and a low-band-gap energy (2.2 eV). This novel class of material without addition of any dopants shows not only a superior photocatalytic water-splitting performance with a total of 801 µmol of H2 under visible-light irradiation for 3 h but also excellent sensing properties for toxic acids.

Particulate Coacervation of Associative Polymer Brushes-Grafted Nanoparticles To Produce Structurally Stable Pickering Emulsions.

This study introduces a new type of associative nanoparticle (ANP) that provides controlled chain-to-chain attraction with an associative polymer rheology modifier (APRM) to produce highly stable Pickering emulsions. The ANPs were synthesized by grafting hydrophobically modified hygroscopic zwitterionic poly(2-methacryloyloxyethyl phosphorylcholine-co-stearyl methacrylate) brushes onto 20 nm sized silica NPs via surface-mediated living radical polymerization. The ANP-stabilized Pickering emulsions show significant viscosity enhancement in the presence of the APRM. This indicates that the ANPs act as particulate concentration agents at the interface owing to their hydrophobic association with the APRM in the aqueous phase, which leads to the generation of an ANP-mediated complex colloidal film. Consequently, the described ANP-reinforced Pickering emulsion system exhibits improved resistance to pH and salinity changes. This coacervation approach is advantageous because the complex colloidal layer at the interface provides the emulsion drops with a mechanically robust barrier, thus guaranteeing the improved Pickering emulsion stability against harsh environmental factors.

Biodegradable Inorganic Nanovector: Passive versus Active Tumor Targeting in siRNA Transportation.

The biodegradable inorganic nanovector based on a layered double hydroxide (LDH) holds great promise for gene and drug delivery systems. However, in vivo targeted delivery of genes through LDH still remains a key challenge in the development of RNA interference therapeutics. Here, we describe in vivo and in vitro delivery system for Survivin siRNA (siSurvivin) assembled with passive LDH with a particle size of 100 nm or active LDH conjugated with a cancer overexpressing receptor targeting ligand, folic acid (LDHFA), conferring them an ability to target the tumor by either EPR-based clathrin-mediated or folate receptor-mediated endocytosis. When not only transfected into KB cells but also injected into xenograft mice, LDHFA/siSurvivin induced potent gene silencing at mRNA and protein levels in vitro, and consequently achieved a 3.0-fold higher suppression of tumor volume than LDH/siSurvivin in vivo. This anti-tumor effect was attributed to a selectively 1.2-fold higher accumulation of siSurvivin in tumor tissue compared with other organs. Targeting to the tumor with inorganic nanovector can guide and accelerate an evolution of next-generation theranosis system.

Mesoporous BN and BCN nanocages with high surface area and spherical morphology.

Novel mesoporous BN and BCN materials with cage type porous structure and spherical morphology have been synthesized using carbon nanocages with 3D porous structure as a template via an elemental substitution method at a low synthesis temperature. The obtained materials exhibit a large specific pore volume with uniform pore size distribution and the specific surface area ranging from 945 to 1023 m(2) g(-1).

Multi-Compartmentalized Cellulose Macrobead Catalysts for In Situ Organic Reaction in Aqueous Media.

This study reports a promising approach to fabricate bacterial cellulose (BC)-based macrobead catalysts with improved catalytic activities and recyclability for organic reactions in aqueous media. To this end, the consecutive extrusion and gelation of BC precursor fluids is conducted using a combined micronozzle device to compartmentalize the resulting BC macrobeads in a programmed manner. The use of BCs laden with Au and Pd nanoparticles (NPs), and Fe3 O4 NPs led to the production of catalytically and magnetically compartmentalized BC macrobeads, respectively. Through the model reduction reaction of 4-nitrophenol to 4-aminophenol using NaBH4 , it is finally demonstrated that the BC macrobead catalysts not only enhance catalytic activities while exhibiting high reaction yields (>99%) in aqueous media, but also repeatedly retrieve the products with ease in response to the applied magnetic field, enabling the establishment of a useful green catalyst platform.

Trench Formation under the Tunable Nanogap: Its Depth Depends on Maximum Strain and Periodicity.

Metallic nanogaps have been studied for many years in the context of a significant amount of field enhancements. Nanogaps of macroscopic lengths for long-wave applications have attracted much interest, and recently one dimensional tunable nanogaps have been demonstrated using flexible PET substrates. For nanogaps on flexible substrates with applied tensile strain, large stress is expected in the vicinity of the gap, and it has been confirmed that several hundred nanometer-deep trenches form beneath the position of the nanogap because of this stress singularity. Here, we studied trench formation under nanogap structures using COMSOL Multiphysics 6.1. We constructed a 2D nanogap unit cell, consisting of gold film with a crack on a PDMS substrate containing a trench beneath the crack. Then, we calculated the von Mises stress at the bottom of the trench for various depths and spatial periods. Based on it, we derived the dependence of the trench depth on the strain and periodicity for various yield strengths. It was revealed that as the maximum tensile strain increases, the trench deepens and then diverges. Moreover, longer periods lead to larger depths for the given maximum strain and larger gap widths. These results could be applied to roughly estimate achievable gap widths and trench depths for stretchable zerogap devices.

Nanoparticle-Based Chimeric Antigen Receptor Therapy for Cancer Immunotherapy.

Adoptive cell therapy with chimeric antigen receptor (CAR)-engineered T cells (CAR-Ts) has emerged as an innovative immunotherapy for hematological cancer treatment. However, the limited effect on solid tumors, complex processes, and excessive manufacturing costs remain as limitations of CAR-T therapy. Nanotechnology provides an alternative to the conventional CAR-T therapy. Owing to their unique physicochemical properties, nanoparticles can not only serve as a delivery platform for drugs but also target specific cells. Nanoparticle-based CAR therapy can be applied not only to T cells but also to CAR-natural killer and CAR-macrophage, compensating for some of their limitations. This review focuses on the introduction of nanoparticle-based advanced CAR immune cell therapy and future perspectives on immune cell reprogramming.

Strain versus Tunable Terahertz Nanogap Width: A Simple Formula and a Trench below.

A flexible zerogap metallic structure is periodically formed, healing metal cracks on a flexible substrate. Zerogap is continuously tunable from nearly zero to one hundred nanometers by applying compressive strains on the flexible substrate. However, there have been few studies on how the gap width is related to the strain and periodicity, nor the mechanism of tunability itself. Here, based on atomic force microscopy (AFM) measurements, we found that 200 nm-deep nano-trenches are periodically generated on the polymer substrate below the zerogap owing to the strain singularities extant between the first and the second metallic deposition layers. Terahertz and visible transmission properties are consistent with this picture whereby the outer-bending polyethylene terephthalate (PET) substrate controls the gap size linearly with the inverse of the radius of the curvature.

Reprogramming the tumor microenvironment with biotechnology.

The tumor microenvironment (TME) is a unique environment that is developed by the tumor and controlled by tumor-induced interactions with host cells during tumor progression. The TME includes immune cells, which can be classified into two types: tumor- antagonizing and tumor-promoting immune cells. Increasing the tumor treatment responses is associated with the tumor immune microenvironment. Targeting the TME has become a popular topic in research, which includes polarizing macrophage phenotype 2 into macrophage phenotype 1 using Toll-like receptor agonists with cytokines, anti-CD47, and anti-SIPRα. Moreover, inhibiting regulatory T cells through blockades and depletion restricts immunosuppressive cells in the TME. Reprogramming T cell infiltration and T cell exhaustion improves tumor infiltrating lymphocytes, such as CD8+ or CD4+ T cells. Targeting metabolic pathways, including glucose, lipid, and amino acid metabolisms, can suppress tumor growth by restricting the absorption of nutrients and adenosine triphosphate energy into tumor cells. In conclusion, these TME reprogramming strategies exhibit more effective responses using combination treatments, biomaterials, and nanoparticles. This review highlights how biomaterials and immunotherapy can reprogram TME and improve the immune activity.