Synthesis and Characterization of New Biodegradable Injectable Thermosensitive Smart Hydrogels for 5-Fluorouracil Delivery

In this paper, injectable, thermosensitive smart hydrogel local drug delivery systems (LDDSs) releasing the model antitumour drug 5-fluorouracil (5-FU) were developed. The systems were based on biodegradable triblock copolymers synthesized via ring opening polymerization (ROP) of ε-caprolactone (CL) in the presence of poly(ethylene glycol) (PEG) and zirconium(IV) acetylacetonate (Zr(acac)₄), as co-initiator and catalyst, respectively. The structure, molecular weight (M_n) and molecular weight distribution (Đ) of the synthesized materials was studied in detail using nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) techniques; the optimal synthesis conditions were determined. The structure corresponded well to the theoretical assumptions. The produced hydrogels demonstrated a sharp sol–gel transition at temperature close to physiological value, forming a stable gel with good mechanical properties at 37 °C. The kinetics and mechanism of in vitro 5-FU release were characterized by zero order, first order, Higuchi and Korsmeyer–Peppas mathematical models. The obtained results indicate good release control; the kinetics were generally defined as first order according to the predominant diffusion mechanism; and the total drug release time was approximately 12 h. The copolymers were considered to be biodegradable and non-toxic; the resulting hydrogels appear to be promising as short-term LDDSs, potentially useful in antitumor therapy.     

Optimization of Synthesis Parameters for Mesoporous Shell Formation on Magnetic Nanocores and Their Application as Nanocarriers for Docetaxel Cancer Drug

In this work, Fe₃O₄@SiO₂ nanoparticles were coated with mesoporous silica shell by S⁻N⁺I⁻ pathway by using anionic surfactant (S⁻) and co-structure directing agent (N⁺). The role of co-structure directing agent (CSDA) is to assist the electrostatic interaction between negatively charged silica layers and the negatively charged surfactant molecules. Prior to the mesoporous shell formation step, magnetic cores were coated with a dense silica layer to prevent iron oxide cores from leaching into the mother system under any acidic circumstances. However, it was found that both dense and mesoporous coating parameters affect the textural properties of the produced mesoporous silica shell (i.e., surface area, pore volume and shell thickness). The synthesized Fe₃O₄@SiO₂@m-SiO₂ (MCMSS) nanoparticles have been characterized by low-angle X-ray diffraction, transmission electron microscopy (TEM), and N₂ adsorption-desorption analysis, and magnetic properties. The synthesized particles had dense and mesoporous silica shells of 8–37 nm and 26–50 nm, respectively. Furthermore, MCMSS possessed surface area of ca. 259–621 m²·g⁻¹, and pore volume of ca. 0.216–0.443 cc·g⁻¹. MCMSS showed docetaxcel cancer drug storage capacity of 25–33 w/w% and possessed control release from their mesochannels which suggest them as proper nanocarriers for docetaxcel molecules.     

Synthesis of magnetite/polyamino-ester dendrimer based on PCL/PEG amphiphilic copolymers via convergent approach for targeted diagnosis and therapy

The aim in this study is to synthesize amphiphilic linear-dendritic-linear block copolymers consisting of a poly ?-caprolactone linear block, poly(amino-ester) dendritic block and m-PEG linear block. G1, G2 and G3 dendrons were produced by sequential acrylation and Micheal addition reactions, using required amounts of acryloyl chloride and diethanolamine respectively to achieve quantitative growth. Amphiphilic dendrons were synthesized from the reaction of hydroxyl group of G1, G2 and G3 with mPEG-adipoyl chloride and their structures were characterized by FT-IR and ¹H NMR spectroscopy. The amphiphilic dendrons can self-assemble and form micelles in water. Their critical micelle concentration (CMC), particle size and zeta potential were determined by fluorescence spectroscopy and dynamic light scattering, respectively. Convergent dendrimers were prepared by self-assembly of the dendrons around oleic acid-stabilized Fe₃O₄ nanoparticles via the ligand exchange method and their morphologies were characterized by transmission electron microscopy (TEM). The in-vitro release behavior of quercetin from dendrimers and hydrolytic degradation of them were investigated at two pHs (7.4 and 5.8).     

Mesoporous H3PW12O40-silica composite: Efficient and reusable solid acid catalyst for the synthesis of diphenolic acid from levulinic acid

Mesoporous H₃PW₁₂O₄₀-silica composite catalysts with controllable H₃PW₁₂O₄₀ loadings (4.0–65.1%) were prepared by a direct sol–gel–hydrothermal technique in the presence of triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymer. Powder X-ray diffraction (XRD) patterns and nitrogen sorption analysis indicate the formation of well-defined mesoporous materials. With H₃PW₁₂O₄₀ loading lower than 20%, the materials exhibit larger BET surface area (604.5–753.0 m² g⁻¹), larger and well-distributed pore size (6.1–8.6 nm), larger pore volume (0.75–1.2 cm³ g⁻¹), and highly dispersed Keggin unit throughout the materials. Raman scattering spectroscopy studies confirm that the primary Keggin structure remained intact after formation of the composites. As a novel kind of reusable solid acid catalyst, as-prepared H₃PW₁₂O₄₀-silica composite was applied for the synthesis of diphenolic acid (DPA) from biomass platform molecule, levulinic acid (LA), under solvent-free condition, and remarkably high catalytic activity and stability were observed.     

Self-assembly behaviors of thermal- and pH- sensitive magnetic nanocarriers for stimuli-triggered release

In the present work, we prepare thermo- and pH-sensitive polymer-based nanoparticles incorporating with magnetic iron oxide as the remote-controlled, stimuli-response nanocarriers. Well-defined, dual functional tri-block copolymer poly[(acrylic acid)-block-(N-isopropylacrylamide)-block-(acrylic acid)], was synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization with S,S′-bis(α,α′-dimethyl-α″-acetic acid)trithiocarbonate (CMP) as a chain transfer agent (CTA). With the aid of using 3-aminopropyltriethoxysilane, the surface-modified iron oxides, Fe₃O₄-NH₂, was then attached on the surface of self-assembled tri-block copolymer micelles via 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride/N-hydroxysuccinamide (EDC/NHS) crosslinking method in order to furnish not only the magnetic resources for remote control but also the structure maintenance for spherical morphology of our nanocarriers. The nanocarrier was characterized by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), and ultraviolet–visible (UV/Vis) spectral analysis. Rhodamine 6G (R6G), as the modeling drugs, was encapsulated into the magnetic nanocarriers by a simple swelling method for fluorescence-labeling and controlled release monitoring. Biocompatibility of the nanocarriers was studied via 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, which revealed that neither the pristine nanocarrier nor the R6G-loaded nanocarriers were cytotoxic to the normal fibroblast cells (L-929 cells). The in vitro stimuli-triggered release measurement showed that the intelligent nanocarriers were highly sensitive to the change of pH value and temperature rising by the high-frequency magnetic field (HFMF) treatment, which provided the significant potential to apply this technology to biomedical therapy by stimuli-responsive controlled release.     

Protein Adsorption onto Modified Porous Silica by Single and Binary Human Serum Protein Solutions

Typical porous silica (SBA-15) has been modified with pore expander agent (1,3,5-trimethylbenzene) and fluoride-species to diminish the length of the channels to obtain materials with different textural properties, varying the Si/Zr molar ratio between 20 and 5. These porous materials were characterized by X-ray Diffraction (XRD), N₂ adsorption/desorption isotherms at −196 °C and X-ray Photoelectron Spectroscopy (XPS), obtaining adsorbent with a surface area between 420–337 m² g⁻¹ and an average pore diameter with a maximum between 20–25 nm. These materials were studied in the adsorption of human blood serum proteins (human serum albumin—HSA and immunoglobulin G—IgG). Generally, the incorporation of small proportions was favorable for proteins adsorption. The adsorption data revealed that the maximum adsorption capacity was reached close to the pI. The batch purification experiments in binary human serum solutions showed that Si sample has considerable adsorption for IgG while HSA adsorption is relatively low, so it is possible its separation.     

Enhanced Fungicidal Efficacy by Co-Delivery of Azoxystrobin and Diniconazole with Cauliflower-Like Metal–Organic Frameworks NH2-Al-MIL-101

Long-term use of a single fungicide increases the resistance risk and causes adverse effects on natural ecosystems. Controlled release formulations of dual fungicides with different modes of action can afford a new dimension for addressing the current issues. Based on adjustable aperture and superhigh surface area, metal–organic frameworks (MOFs) are ideal candidates as pesticide release carriers. This study used Al³⁺ as the metal node and 2-aminoterephthalic acid as the organic chain to prepare aluminum-based metal–organic framework material (NH₂-Al-MIL-101) with “cauliflower-like” structure and high surface area of 2359.0 m²/g. Fungicides of azoxystrobin (AZOX) and diniconazole (Dini) were simultaneously encapsulated into NH₂-Al-MIL-101 with the loading content of 6.71% and 29.72%, respectively. Dual fungicide delivery system of AZOX@Dini@NH₂-Al-MIL-101 demonstrated sustained and pH responsive release profiles. When the maximum cumulative release rate of AZOX and Dini both reached about 90%, the release time was 46 and 136 h, respectively. Furthermore, EC₅₀ values as well as the percentage of inhibition revealed that AZOX@Dini@NH₂-Al-MIL-101 had enhanced germicidal efficacy against rice sheath blight (Rhizoctonia solani), evidenced by the synergistic ratio of 1.83. The present study demonstrates a potential application prospect in sustainable plant protection through co-delivery fungicides with MOFs as a platform.     

Efficient Synthesis of a Maghemite/Gold Hybrid Nanoparticle System as a Magnetic Carrier for the Transport of Platinum-Based Metallotherapeutics

The preparation and thorough characterization of a hybrid magnetic carrier system for the possible transport of activated platinum-based anticancer drugs, as demonstrated for cisplatin (cis-[Pt(NH₃)₂Cl₂], CDDP), are described. The final functionalized mag/Au–LA–CDDP* system consists of maghemite/gold nanoparticles (mag/Au) coated by lipoic acid (HLA; LA stands for deprotonated form of lipoic acid) and functionalized by activated cisplatin in the form of cis-[Pt(NH₃)₂(H₂O)₂]²⁺ (CDDP*). The relevant techniques (XPS, EDS, ICP-MS) proved the incorporation of the platinum-containing species on the surface of the studied hybrid system. HRTEM, TEM and SEM images showed the nanoparticles as spherical with an average size of 12 nm, while their superparamagnetic feature was proven by ⁵⁷Fe Mössbauer spectroscopy. In the case of mag/Au, mag/Au–HLA and mag/Au–LA–CDDP*, weaker magnetic interactions among the Fe³⁺ centers of maghemite, as compared to maghemite nanoparticles (mag), were detected, which can be associated with the non-covalent coating of the maghemite surface by gold. The pH and time-dependent stability of the mag/Au–LA–CDDP* system in different media, represented by acetate (pH 5.0), phosphate (pH 7.0) and carbonate (pH 9.0) buffers and connected with the release of the platinum-containing species, showed the ability of CDDP* to be released from the functionalized nanosystem.     

Tannylated Calcium Carbonate Materials with Antacid,Anti-Inflammatory,and Antioxidant Effects

Calcium carbonate (CaCO₃)-based materials have received notable attention for biomedical applications owing to their safety and beneficial characteristics, such as pH sensitivity, carbon dioxide (CO₂) gas generation, and antacid properties. Herein, to additionally incorporate antioxidant and anti-inflammatory functions, we prepared tannylated CaCO₃ (TA-CaCO₃) materials using a simple reaction between tannic acid (TA), calcium (Ca²⁺), and carbonate (CO₃²⁻) ions. TA-CaCO₃ synthesized at a molar ratio of 1:75 (TA:calcium chloride (CaCl₂)/sodium carbonate (Na₂CO₃)) showed 3–6 μm particles, comprising small nanoparticles in a size range of 17–41 nm. The TA-CaCO₃ materials could efficiently neutralize the acid solution and scavenge free radicals. In addition, these materials could significantly reduce the mRNA levels of pro-inflammatory factors and intracellular reactive oxygen species, and protect chondrocytes from toxic hydrogen peroxide conditions. Thus, in addition to their antacid property, the prepared TA-CaCO₃ materials exert excellent antioxidant and anti-inflammatory effects through the introduction of TA molecules. Therefore, TA-CaCO₃ materials can potentially be used to treat inflammatory cells or diseases.     

Structural aspects of mesoporous AlPO4-5 (AFI) zeotype using microwave radiation and alumatrane precursor

A new route for preparation of mesoporous AlPO₄-5 (AFI) zeotype has been synthesized using alumatrane precursor, prepared from aluminum hydroxide and triisopropanolamine (TIS) by the oxide one pot synthesis (OOPS), via microwave technique using triethylamine (TEA) as a structure-directing agent. The influences of the reaction mixture composition, HF acid, water content and the crystallization temperature and time were investigated. The prepared materials were characterized using X-ray diffraction, SEM and BET. The results showed a mesoporous AlPO₄-5 zeotype having a uniform rod-like structure with surface area around 120–180 m²/g. The high crystallinity with narrow size distribution of crystals was obtained at a high amount of structure-directing agent (the mole ratio of TEA/Al₂O₃ = 3.5). The presence of fluorine ion retarded the nucleation and growth rate, leading to a bigger crystal size. The crystal of the AFI grew preferentially in the c-direction with the reaction time and the water content. The use of lower reaction temperature to obtain good crystalline material can be compensated by a longer reaction time.     

Adsorption and Release of Sulfamethizole from Mesoporous Silica Nanoparticles Functionalised with Triethylenetetramine

Mesoporous silica nanoparticles (MSN) were synthesised and functionalised with triethylenetetramine (MSN-TETA). The samples were fully characterised (transmission electron microscopy, small angle X-ray scattering, Fourier transform infrared spectroscopy, thermogravimetric analysis, zeta potential and nitrogen adsorption/desorption isotherms) and used as carriers for the adsorption of the antimicrobial drug sulphamethizole (SMZ). SMZ loading, quantified by UV–Vis spectroscopy, was higher on MSN-TETA (345.8 mg g⁻¹) compared with bare MSN (215.4 mg g⁻¹) even in the presence of a lower surface area (671 vs. 942 m² g⁻¹). The kinetics of SMZ adsorption on MSN and MSN-TETA followed a pseudo-second-order model. The adsorption isotherm is described better by a Langmuir model rather than a Temkin or Freundlich model. Release kinetics showed a burst release of SMZ from bare MSN samples (k₁ = 136 h⁻¹) in contrast to a slower release found with MSN-TETA (k₁ = 3.04 h⁻¹), suggesting attractive intermolecular interactions slow down SMZ release from MSN-TETA. In summary, the MSN surface area did not influence SMZ adsorption and release. On the contrary, the design of an effective drug delivery system must consider the intermolecular interactions between the adsorbent and the adsorbate.     

Modern concept of acoustic emission (AE) coupled with electrochemical measurements for monitoring the elastomer-coated carbon steel damage in phosphoric acid medium

Elastomer coatings (rubber) are industrially used to protect phosphoric acid storage tanks against corrosion. Rubber constitutes a barrier against the penetration of H₃PO₄ to metallic surface. Coatings damage induces both acid infiltration and steel corrosion. In this concept, acoustic emission (AE) monitoring technique could be used for the detection of coatings damage as well as for steel corrosion under the coating. In the present work AE was coupled to electrochemical measurements (EM) for rubber damage evaluation and steel corrosion on three types of steels (XC48, E20 and A60) at room temperature in concentrated phosphoric acid (30% P₂O₅) contaminated by Cl⁻, F⁻, SO₄²⁻. Electrochemical behaviour of steels was studied and characterized by potentiodynamic curves and polarization resistance measurement. A good correlation between acoustic emission and polarization resistance or corrosion potential measurements was found during stages of coatings damage and steels corrosion. The majority of AE activity recorded during experiments is related to hydrogen bubbles release. The release of hydrogen bubbles gives rise to two populations of signals: one impulsive and another one resonant.     

Aqueous synthesis of high surface area metal oxides

By applying high throughput synthesis and characterization technologies, we have been optimizing common dry or aqueous synthetic routes for the preparation of high surface area metals and oxides, such as precipitation and modified Pechini methods. For wet combustion synthesis, we have been screening a variety of organic acids as dispersants and developed proprietary recipes for individual metals. By resorting to easily decomposable organic acids (as opposed to citric acid in the original Pechini combustion method), such as glyoxylic acid, oxalacetic acid and ketoglutaric acid, it is possible to obtain high surface area materials for many metals after careful optimization of acid/metal ratio and calcination conditions. Examples are Sn, In, Co, Ru, Ni, Fe, Mn, Y, Ce and Rare Earth oxides and their mixtures. After calcination in the temperature range of about 300–400 °C, surface areas >150 m²/g could be obtained for Er, Tm, Co, Ru, and Nb; >200 m²/g for Sn, Fe, Mn, and Y; >300 m²/g for Ce; and >400 m²/g for Ni oxide. Noteworthy are also >140 m²/g for La₂O₃, >80 m²/g for CuO, and 75 m²/g for ZnO. For V, around 40 m²/g was possible for the nearly carbon-free V₂O₅, whereas up to 90 m²/g was obtained for a 90% V–10% carbon composite (by incomplete combustion of the organic acid). Residual carbon helps in stabilizing the porous oxide against sintering. Thus, conventional aqueous routes (precipitation, Pechini) can be competitive to more elaborate and costly methods such as those using organic solvents, sol–gel, supercritical drying or template/hydrothermal synthesis. Combustion synthesis is well suited for the preparation of mixed oxides from mixed metal solutions in aqueous organic acids. Bulk porous Co and CoRu mixed oxides have been screened for liquid phase alcohol oxidations and CoRuCe oxides for CO oxidation and VOC destruction, and doped NiO has been reduced to the metal and tested for various hydrogenations.     

Microporous Carbon and Carbon/Metal Composite Materials Derived from Bio-Benzoxazine-Linked Precursor for CO2 Capture and Energy Storage Applications

There is currently a pursuit of synthetic approaches for designing porous carbon materials with selective CO₂ capture and/or excellent energy storage performance that significantly impacts the environment and the sustainable development of circular economy. In this study we prepared a new bio-based benzoxazine (AP-BZ) in high yield through Mannich condensation of apigenin, a naturally occurring phenol, with 4-bromoaniline and paraformaldehyde. We then prepared a PA-BZ porous organic polymer (POP) through Sonogashira coupling of AP-BZ with 1,3,6,8-tetraethynylpyrene (P-T) in the presence of Pd(PPh₃)₄. In situ Fourier transform infrared spectroscopy and differential scanning calorimetry revealed details of the thermal polymerization of the oxazine rings in the AP-BZ monomer and in the PA-BZ POP. Next, we prepared a microporous carbon/metal composite (PCMC) in three steps: Sonogashira coupling of AP-BZ with P-T in the presence of a zeolitic imidazolate framework (ZIF-67) as a directing hard template, affording a PA-BZ POP/ZIF-67 composite; etching in acetic acid; and pyrolysis of the resulting PA-BZ POP/metal composite at 500 °C. Powder X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller (BET) measurements revealed the properties of the as-prepared PCMC. The PCMC material exhibited outstanding thermal stability (T_d10 = 660 °C and char yield = 75 wt%), a high BET surface area (1110 m² g^–1), high CO₂ adsorption (5.40 mmol g^–1 at 273 K), excellent capacitance (735 F g^–1), and a capacitance retention of up to 95% after 2000 galvanostatic charge–discharge (GCD) cycles; these characteristics were excellent when compared with those of the corresponding microporous carbon (MPC) prepared through pyrolysis of the PA-BZ POP precursors with a ZIF-67 template at 500 °C.     

Design of High-Relaxivity Polyelectrolyte Nanocapsules Based on Citrate Complexes of Gadolinium(III) of Unusual Composition

Through nuclear magnetic relaxation and pH-metry, the details of the complexation of gadolinium(III) ions with citric acid (H₄L) in water and aqueous solutions of cationic polyelectrolytes are established. It is shown that the presence of poly(ethylene imine) (PEI) in solution affects magnetic relaxation behavior of gadolinium(III) complexes with citric acid (Cit) to a greater extent than polydiallyldimethylammonium chloride (PDDC). A large increase in relaxivity (up to 50 mM⁻¹s⁻¹) in the broad pH range (4–8) is revealed for the gadolinium(III)–citric acid–PEI system, which is particularly strong in the case of PEI with the molecular weight of 25 and 60 kDa. In weakly acidic medium (pH 3–7), the presence of PEI results in the formation of two tris-ligand associates [Gd(H₂L)₃]³⁻ and [Gd(H₂L)₂(HL)]⁴⁻, which do not exist in aqueous medium. In weakly alkaline medium (pH 7–10), formation of ternary complexes Gd(III)–Cit–PEI with the Gd(III)–to–Cit ratio of 1:2 is evidenced. Using transmission electron microscopy (TEM) and dynamic light scattering techniques (DLS), the formation of the particles with the size of 50–100 nm possessing narrow molecular-mass distribution (PDI 0.08) is determined in the solution containing associate of PEI with tris-ligand complex [Gd(H₂L)₂(HL)]⁴⁻.     

Preparation of porous rutile titania from ilmenite by mechanical activation and subsequent sulfuric acid leaching

Synthesis of porous titania via mechanical activation of natural ilmenite and subsequent simultaneous dissolution and hydrolysis in dilute solutions of sulfuric acid was investigated by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), N₂ adsorption/desorption measurements, energy-dispersive X-ray spectrometry (EDX) and thermogravimetric analysis (TG). This is a novel template-free approach for synthesis of microporous, mesoporous and micro–mesoporous TiO₂ materials. Effects of sulfuric acid concentration and calcination temperature on physicochemical properties of the TiO₂ materials were examined systematically. The results show that both the factors considerably affected the porosity of the materials. In a 15% acid solution a microporous TiO₂ hydrolysate with BET surface area 109.3 m²/g was prepared. With a 10% H₂SO₄, we obtained a more pure micro/mesopore TiO₂ hydrolysate with BET area of 257.6 m²/g. Calcining the hydrolysate at 500 °C led to the formation of a mesopore TiO₂. The mesoporous TiO₂ generated at 600 °C still has a BET area of 92.1 m²/g. The high thermal stability is probably related to the presence of H₂SO₄ in the channel walls of hydrolysate. The XRD analysis indicated all the TiO₂ materials prepared in this study being rutile. The mechanism for formation of the porous rutile TiO₂ is mainly via in situ hydrolysis and precipitation of the dissolved titanium on the un-reacted ilmenite surface, where H₂SO₄ may play a very important role.     

Effects of the nature of the aluminum source on the acidic properties of some mesostructured materials

Mesostructured aluminosilicates have been synthesized using gels prepared by reacting colloidal silica (Ludox AS) with Al(OH)₃, aluminum isopropoxide (Al(iPrO)₃) or NaAlO₂ in the presence of a surfactant. The hydrothermal transformation at 110°C of these gels produced solids with the hexagonal structure typical of MCM-41-type materials. These crystals have been characterized by X-ray diffraction, thermal analysis (TG/DTA), N₂ sorption and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The type, strength and density of acid sites have been studied using microcalorimetry and infrared (IR) spectroscopy.As a general trend, pore volume and average pore size decreased as the gel SiO₂/Al₂O₃ ratio decreased from 32–8, while the pore wall thickness remained in the 1.0–1.5 nm range. Except for one sample, Al was incorporated in tetrahedral coordination inside the pristine crystals. However, as expected, dealumination occurred upon calcination at 600°C/12 h, yielding materials having both tetrahedral and octahedral Al-species. Fourier transform infrared (FTIR) experiments with pyridine have indicated that these mesostructured aluminosilicates contain both Brönsted and Lewis acid sites and that acidity is strongest in samples prepared with NaAlO₂.Microcalorimetry experiments with ammonia as the probe molecule have shown that Al insertion into the mesoporous silicate framework affects acid site strength and distribution in a manner controlled by synthesis condition. Samples prepared with Al(OH)₃ contain a wide distribution of acid site strengths, indicating the absence of preferred locations of Si-O-Al groups within the pore walls. In contrast, distinct populations of acid sites with strengths in the 130–140 kJ mol⁻¹ range or near 150 kJ mol⁻¹, appear in materials prepared with Al(iPrO)₃ or with NaAlO₂, respectively. Al sites may be located at the surface of the pore wall, where they interact directly with the basic probe molecule. They may also be sandwiched between silica layers within the pore wall (3–4 Si layers thick), giving acid sites with a strength comparable with that of smectites. Finally, they may also be present in the pore (or within the pore walls) as extraframework Al(VI)-species. The nature, size, concentration, ease of hydrolysis and condensation of the aluminum precursors during synthesis control aluminum incorporation, distribution and location within the structure and with it the acidity of the resulting mesoporous aluminosilicate.     

Cyclodextrin Nanosponges Inclusion Compounds Associated with Gold Nanoparticles for Potential Application in the Photothermal Release of Melphalan and Cytoxan

This article describes the synthesis and characterization of β-cyclodextrin-based nano-sponges (NS) inclusion compounds (IC) with the anti-tumor drugs melphalan (MPH) and cytoxan (CYT), and the addition of gold nanoparticles (AuNPs) onto both systems, for the potential release of the drugs by means of laser irradiation. The NS-MPH and NS-CYT inclusion compounds were characterized using scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), UV–Vis, and proton nuclear magnetic resonance (¹H-NMR). Thus, the inclusion of MPH and CYT inside the cavities of NSs was confirmed. The association of AuNPs with the ICs was confirmed by SEM, EDS, TEM, and UV–Vis. Drug release studies using NSs synthesized with different molar ratios of β-cyclodextrin and diphenylcarbonate (1:4 and 1:8) demonstrated that the ability of NSs to entrap and release the drug molecules depends on the crosslinking between the cyclodextrin monomers. Finally, irradiation assays using a continuous laser of 532 nm showed that photothermal drug release of both MPH and CYT from the cavities of NSs via plasmonic heating of AuNPs is possible.     

Spontaneous adsorption of 3,5-bis(3,5-dinitrobenzoylamino) benzoic acid onto carbon

Dendritic molecules contain multifunctional groups that can be used to efficiently control the properties of an electrode surface. We are developing strategies to generate a highly functionalized surface using multifunctional and rigid dendrons immobilized onto different substrates. In the present work, we explore the immobilization of a dendritic molecule: 3,5-bis(3,5-dinitrobenzoylamino) benzoic acid (D-NO₂) onto carbon surfaces showing a simple and rapid way to produce conductive surfaces with electroactive chemical functions. The immobilized D-NO₂ layer has been characterized using atomic force microscopy and cyclic voltammetry. D-NO₂ adsorbs onto carbon surfaces spontaneously by dipping the electrode in dendron solutions. Reduction of this layer generates the hydroxylamine product. The resulting redox-active layer exhibits a well-behaved redox response for the adsorbed nitroso/hydroxylamine couple. The film permeability of the derivatized surface has been analyzed employing the electrochemical response of redox probes: Ru(NH₃)₆³⁺/Ru(NH₃)₆²⁺ and Fe(CN)₆³⁻/Fe(CN)₆⁴⁻. Electrocatalytic oxidation of nicotinamide adenine dinucleotide onto a modified carbon surface was also observed.     

The AEROPILs Generation: Novel Poly(Ionic Liquid)-Based Aerogels for CO2 Capture

CO₂ levels in the atmosphere are increasing exponentially. The current climate change effects motivate an urgent need for new and sustainable materials to capture CO₂. Porous materials are particularly interesting for processes that take place near atmospheric pressure. However, materials design should not only consider the morphology, but also the chemical identity of the CO₂ sorbent to enhance the affinity towards CO₂. Poly(ionic liquid)s (PILs) can enhance CO₂ sorption capacity, but tailoring the porosity is still a challenge. Aerogel’s properties grant production strategies that ensure a porosity control. In this work, we joined both worlds, PILs and aerogels, to produce a sustainable CO₂ sorbent. PIL-chitosan aerogels (AEROPILs) in the form of beads were successfully obtained with high porosity (94.6–97.0%) and surface areas (270–744 m²/g). AEROPILs were applied for the first time as CO₂ sorbents. The combination of PILs with chitosan aerogels generally increased the CO₂ sorption capability of these materials, being the maximum CO₂ capture capacity obtained (0.70 mmol g⁻¹, at 25 °C and 1 bar) for the CHT:P[DADMA]Cl_30% AEROPIL.