Green synthesis trends and potential applications of bimetallic nanoparticles towards the sustainable development goals 2030.

The world faces threats that the United Nations has classified into 17 categories with different objectives as solutions for each challenge that are enclosed in the Sustainable Development Goals (SDGs). These actions involved the widespread use of science and technology as pathways to ensure their implementation. In this regard, sustainability science seeks the research community's contribution to addressing sustainable development challenges. Specifically, nanotechnology has been recognized as a key tool to provide disruptive and effective strategies to reach the SDGs. This review proposes the application of bimetallic nanoparticle substances capable of providing possible solutions to achieve target SDG 3: good health and well-being, SDG 6: clean water and sanitation, and SDG 12: responsible consumption and production. Furthermore, the term green nanotechnology is introduced in each section to exemplify how green synthesized bimetallic nanoparticles have been used to resolve each target SDG. This review also outlines the current scenario regarding the utilization of metallic nanomaterials in the market, together with the upscaling challenges and the lack of understanding of the long-term effects and hazards to the environment regarding bimetallic nanoparticles.

Effect of Basic Amino Acids on Folic Acid Solubility.

To prevent neural tube defects and other cardiovascular diseases in newborns, folic acid (FA) is recommended in pregnant women. A daily dose of 600 µg FA consumption is widely prescribed for women during pregnancy and 400 µg for women with childbearing potential. FA is a class IV compound according to the Biopharmaceutics Classification System (BCS) due to its low permeability (1.7 × 10-6 cm/s) and low solubility (1.6 mg/L); therefore, it must be administered via a formulation that enhances its solubility. Studies reported in the literature have proved that co-amorphization and salt formation of a poorly soluble drug with amino acids (AA) can significantly increase its solubility. Although arginine has been used with FA as a supplement, there is no information on the effect of basic AA (arginine and lysine) on the physical and chemical properties of FA-AA binary formulations. The present study implemented a conductimetric titration methodology to find the effective molar ratio to maximize FA solubility. The results showed that a 1:2.5 FA:AA molar ratio maximized solubility for arginine and lysine. Binary formulations were prepared using different methods, which led to an amorphous system confirmed by the presence of a glass transition, broad FTIR bands, and the absence of an X-ray diffraction pattern. Results of FA:AA (1:2.5) solubility increased in the range of 5500-6000 times compared with pure FA. In addition to solubility enhancement, the binary systems presented morphological properties that depend on the preparation method and whose consideration could be strategic for scaling purposes.

Galvanostatically Deposited PtNi Thin-Films as Electrocatalysts for the Hydrogen Evolution Reaction.

The synthesis of hybrid platinum materials is fundamental to enable alkaline water electrolysis for cost-effective H2 generation. In this work, we have used a galvanostatic method to co-deposit PtNi films onto polycrystalline gold. The surface concentrations of Ni (ΓNi ) and Pt (ΓPt ) were calculated from electrochemical measurements; the ΓPt /ΓNi ratio and electrocatalytic activity of these materials towards hydrogen evolution reaction (HER) in 1 M KOH show a strong dependence on the current density pulse applied during the electrodeposition. Analysis of the Tafel parameters hints that, on these deposits, HER proceeds through a Volmer-Heyrovsky mechanism. The galvanostatically deposited PtNi layers present a high current output per Pt gram, 3199 A gPt -1 , which is significantly larger compared to other PtNi-based materials obtained by more extended and more complex synthesis methods.

Green synthesis of starch-capped Cu2O nanocubes and their application in the direct electrochemical detection of glucose.

Glucose determination is an essential procedure in different fields, used in clinical analysis for the prevention and monitoring of diabetes. In this work, modified carbon paste electrodes with Cu2O nanocubes (Cu2O NCs) were developed to test electrochemical glucose detection. The synthesis of the Cu2O NCs was achieved by a green method using starch as the capping agent, obtaining cubic-like morphologies and particle sizes from 227 to 123 nm with increasing amounts of the capping agent, as corroborated by electron microscopy analysis. Their crystalline structure and purity were determined by X-ray diffraction. The capability of starch as a capping agent was verified by Fourier-transform infrared spectroscopy, in which the presence of functional groups of this biopolymer in the Cu2O NCs were identified. The electrochemical response to glucose oxidation was determined by cyclic voltammetry, obtaining a linear response of the electrical current as a function of glucose concentration in the range 100-700 µM, with sensitivities from 85.6 to 238.8 µA mM-1 cm-2, depending on the amount of starch used in the synthesis of the Cu2O NCs.

Understanding Disorder in 2D Materials: The Case of Carbon Doping of Silicene.

We investigate the effect of lattice disorder and local correlation effects in finite and periodic silicene structures caused by carbon doping using first-principles calculations. For both finite and periodic silicene structures, the electronic properties of carbon-doped monolayers are dramatically changed by controlling the doping sites in the structures, which is related to the amount of disorder introduced in the lattice and electron-electron correlation effects. By changing the position of the carbon dopants, we found that a Mott-Anderson transition is achieved. Moreover, the band gap is determined by the level of lattice disorder and electronic correlation effects. Finally, these structures are ferromagnetic even under disorder which has potential applications in Si-based nanoelectronics, such as field-effect transistors (FETs).

Bicontinuous microemulsion as confined reaction media for the synthesis of plasmonic silver self-assembled hierarchical superstructures.

Plasmonic superstructures may concentrate hot spots both on the external surface and within the inner gaps of the assembly. However, these materials are usually obtained by two-steps procedures from synthesis of plasmonic nanoparticles to their 3D assembly. The interconnected nano-network of water and oil channels in a bicontinuous microemulsion (BµE) may act as a preorganized reaction system giving reticulated materials. In this work, a silver hierarchical superstructure (HSS-AgCt) was obtained in the water channels of a BµE in a one-pot procedure. The characterization of the morphology and crystalline structure revealed that this superstructure is composed of silver nanoparticles embedded in polymeric silver citrate forming a 3D mesh of interconnected fibers with mean width of 30 nm. The aging of HSS-AgCt in the BµE allowed the degradation of the citrate fibers giving rise to interconnected spherical silver nanoparticles (HSS-Ag) of 8 nm as measured from TEM images. Rhodamine 6-G was detected by SERS up to 10-12 M with an analytical enhancement factor of 109 for both materials using a 633 nm laser operating at 0.85 mW (5% of the nominal power). These results introduce a novel route to obtain highly sensitive SERS substrates in one-pot procedures by using BµE as a nanoreactor and template.

Highly Soluble Glimepiride and Irbesartan Co-amorphous Formulation with Potential Application in Combination Therapy.

One-third of the population of the USA suffers from metabolic syndrome (MetS). Treatment of patients with MetS regularly includes drugs prescribed simultaneously to treat diabetes and cardiovascular diseases. Therefore, the development of novel multidrug formulations is recommended. However, the main problem with these drugs is their low solubility. The use of binary co-amorphous systems emerges as a promising strategy to increase drug solubility. In the present study, irbesartan (IBS) and glimepiride (GMP), class II active pharmaceutical ingredients (API), widely used in the treatment of arterial hypertension and diabetes, were selected to develop a novel binary co-amorphous system with remarkable enhancement in the dissolution of both APIs. The phase diagram of IBS-GMP was constructed and co-amorphous systems were prepared by melt-quench, in a wide range of compositions. Dissolution profile (studied at pH 1.2 and 37°C for mole fractions 0.01, 0.1, and 0.5) demonstrated that the xGMP = 0.01 formulation presents the highest enhancement in its dissolution. GMP went from being practically insoluble to reach 3.9 ± 0.9 µg/mL, and IBS showed a 12-fold increment with respect to the dissolution of its crystalline form. Infrared studies showed that the increase in the dissolution profile is related to the intermolecular interactions (hydrogen bonds), which were dependent of composition. Results of structural and thermal characterization performed by XRD and DSC showed that samples have remained in amorphous state for more than 10 months of storage. This work contributes to the development of a highly soluble co-amorphous drugs with potential used in the treatment of MetS.

Co-Amorphous Simvastatin-Nifedipine with Enhanced Solubility for Possible Use in Combination Therapy of Hypertension and Hypercholesterolemia.

The high index of simultaneous incidence of hypertension and hypercholesterolemia in the population of many countries demands the preparation of more efficient drugs. Therefore, there is a significant area of opportunity to provide as many alternatives as possible to treat these illnesses. Taking advantage of the solubility enhancement that can be achieved when an active pharmaceutical ingredient (API) is obtained and stabilized in its amorphous state, in the present work, new drug-drug co-amorphous formulations (Simvastatin SIM- Nifedipine NIF) with enhanced solubility and stability were prepared and characterized. Results show that the co-amorphous system (molar ratio 1:1) is more soluble than the pure commercial APIs studied separately. Aqueous dissolution profiles showed increments of solubility of 3.7 and 1.7 times for SIM and NIF, correspondingly, in the co-amorphous system. The new co-amorphous formulations, monitored in time, (molar fractions 0.3, 0.5 and 0.7 of SIM) remained stable in the amorphous state for more than one year when stored at room temperature and did not show any signs of crystallization when re-heating. Inspection on the remainder of a sample after six hours of dissolution showed no recrystallization, confirming the stability of co-amorphous system. The enhanced solubility of the co-amorphous formulations makes them promising for simultaneously targeting of hypertension and hypercholesterolemia through combination therapy.

The frequency-dependent AC photoresistance behavior of ZnO thin films grown on different sapphire substrates.

Zinc oxide (ZnO) thin films were grown by pulsed layer deposition under an N2 atmosphere at low pressures on a- and r-plane sapphire substrates. Structural studies using X-ray diffraction confirmed that all films had a wurtzite phase. ZnO thin films on a- and r-plane sapphire have grown with orientations along the [0002] and [112[combining macron]0] directions, respectively. Room temperature photoluminescence measurements indicate that the presence of native point defects (interstitial zinc, oxygen vacancies, oxygen antisites and zinc vacancies) is more preponderant for ZnO thin films grown on the r-plane sapphire substrate than the sample grown on the a-plane sapphire substrate. Room temperature impedance spectroscopy measurements were performed in an alternating current frequency range from 40 to 105 Hz in the dark and under normal light. An unusual positive photoresistance effect is observed at frequencies above 100 kHz, which we suggest to be due to intrinsic defects present in the ZnO thin films. Furthermore, an analysis of the optical time response revealed that the film grown on the r-plane sapphire substrate responds faster (characteristic relaxation times for τ1, τ2 and τ3 of 0.05, 0.26 and 6.00 min, respectively) than the film grown on the a-plane sapphire substrate (characteristic relaxation times for τ1, τ2 and τ3 of 0.10, 0.73 and 4.02 min, respectively).

Two-phase amorphous-amorphous solid drug dispersion with enhanced stability, solubility and bioavailability resulting from ultrasonic dispersion of an immiscible system.

Amorphization of active pharmaceutical ingredients (APIs) and the preparation of solid dispersions are strategies that can be synergized to improve the solubility of oral drugs. Immiscibility between an API and a carrier in the molten state that could be perceived as a problem in the preparation of solid dispersions, may actually introduce an advantage. In the present work, a two-phase amorphous-amorphous solid dispersion (AASD) was prepared by ultrasonicating a molten immiscible mixture of indomethacin (IND) and glucose (GLU) prior quenching. By introducing this novel ultrasound assisted method, the immiscible API particles were uniformly dispersed as microscopic glassy clusters of the drug in the solid amorphous GLU matrix; particle sizes of IND in the AASD range from 600nm to 1.4µm. As a result of the amorphization and particle size reduction of IND, its aqueous solubility increased to reach almost 40ppm (8 times more soluble compared to indomethacin in its crystalline state). In addition, the oral bioavailability and its resistance against crystallization were also enhanced; AASD samples have remained amorphous for more than two years of storage.

Long-Term Stability of New Co-Amorphous Drug Binary Systems: Study of Glass Transitions as a Function of Composition and Shelf Time.

The amorphous state is of particular interest in the pharmaceutical industry due to the higher solubility that amorphous active pharmaceutical ingredients show compared to their respective crystalline forms. Due to their thermodynamic instability, drugs in the amorphous state tend to recrystallize; in order to avoid crystallization, it has been a common strategy to add a second component to hinder the crystalline state and form a thermally stable co-amorphous system, that is to say, an amorphous binary system which retains its amorphous structure. The second component can be a small molecule excipient (such as a sugar or an aminoacid) or a second drug, with the advantage that a second active pharmaceutical ingredient could be used for complementary or combined therapeutic purposes. In most cases, the compositions studied are limited to 1:1, 2:1 and 1:2 molar ratios, leaving a gap of information about phase transitions and stability on the amorphous state in a wider range of compositions. In the present work, a study of novel co-amorphous formulations in which the selection of the active pharmaceutical ingredients was made according to the therapeutic effect is presented. Resistance against crystallization and behavior of glass transition temperature ( T g were studied through calorimetric measurements as a function of composition and shelf time. It was found that binary formulations with T g temperatures higher than those of pure components presented long-term thermal stability. In addition, significant increments of T g values, of as much as 15 ∘ C, were detected as a result of glass relaxation at room temperature during storage time; this behavior of glass transition has not been previously reported for co-amorphous drugs. Based on these results, it can be concluded that monitoring behavior of T g and relaxation processes during the first weeks of storage leads to a more objective evaluation of the thermomechanical stability of an amorphous formulation.

Substituent Inductive Effects on the Electrochemical Oxidation of Flavonoids Studied by Square Wave Voltammetry and Ab Initio Calculations.

Flavonoids are natural products commonly found in the human diet that show antioxidant, anti-inflammatory and anti-hepatotoxic activities. These nutraceutical properties may relate to the electrochemical activity of flavonoids. To increase the understanding of structure-electrochemical activity relations and the inductive effects that OH substituents have on the redox potential of flavonoids, we carried out square-wave voltammetry experiments and ab initio calculations of eight flavonoids selected following a systematic variation in the number of hydroxyl substituents and their location on the flavan backbone: three flavonols, three anthocyanidins, one anthocyanin and the flavonoid backbone flavone. We compared the effect that the number of -OH groups in the ring B of flavan has on the oxidation potential of the flavonoids considered, finding linear correlations for both flavonols and anthocyanidins ( R 2 = 0.98 ). We analyzed the effects that position and number of -OH substituents have on electron density distributions via ab initio quantum chemical calculations. We present direct correlations between structural features and oxidation potentials that provide a deeper insight into the redox chemistry of these molecules.

Application of ATR-FTIR spectroscopy to the study of thermally induced changes in secondary structure of protein molecules in solid state.

FTIR spectroscopy in combination with ATR sampling technique is the most accessible analytical technique to study secondary structure of proteins both in solid and aqueous solution. Although several studies have demonstrated the applications of ATR-FTIR to study conformational changes of solid dried proteins due to dehydration, there are no reports that demonstrate the application of ATR-FTIR in the study of thermally induced changes of secondary structure of biomolecules directly on the solid state. In this study, four biomolecules of pharmaceutical interest, lysozyme, myoglobine, chymotripsin and human growth hormone (hGH), were studied on the solid state before and after different thermal treatments in order to relate changes of secondary structure to partial or total thermal denaturation processes. The results obtained provide experimental evidence that protein thermal denaturation in the solid state can be detected by displacement of carbonyl bands which correspond to conformational transformations between α-helix to ß-sheet or intermolecular ß-sheet; the molecules studied undergo this transformation when exposed to a temperature close to their denaturation temperature which may become irreversible depending on the extent of the heating treatment. These findings demonstrate that ATR-FTIR is an effective and time efficient technique that allows the monitoring of the protein thermal denaturation process of solid samples without further reconstitution or prior sample preparation.

Stabilization of amorphous paracetamol based systems using traditional and novel strategies.

There is a special interest in having pharmaceutical active ingredients in the amorphous state due to their increased solubility and therefore, higher bioavailability. Nevertheless, not all of them present stable amorphous phases. In particular, paracetamol is an active ingredient widely known for its instability when prepared in the amorphous state. In the present work thermally stable amorphous binary paracetamol based systems were obtained showing stability on a wide range of temperatures: below its glass transition temperature (Tg) as amorphous solids in the glassy state and above their glass transition temperature, where these materials exist as stable supercooled liquids. To achieve stabilization of the binary paracetamol based system several strategies were applied and optimized, being the selection of the container material a key and novel approach to control the mechanical stress during cooling, eliminating cracks which act as nucleation centers leading to crystallization.

Origins of the selectivity for borylation of primary over secondary C-H bonds catalyzed by Cp*-rhodium complexes.

Detailed experimental and computational studies of the high selectivity for functionalization of primary over secondary sp(3) C-H bonds in alkanes by borane reagents catalyzed by Cp*Rh complexes are reported. Prior studies have shown that Cp*Rh(X)(Bpin) (X = H or Bpin), generated from Cp*Rh(H)(2)(Bpin)(2) and Cp*Rh(H)(2)(Bpin)(3), are likely intermediates in these catalytic reactions. To allow analysis of the system by H/D exchange, the current studies focused on reactions of Cp*Rh(D)(2)(Bpin)(2) through the 16-electron species Cp*Rh(D)(Bpin). Density functional theory (DFT) calculations of the reaction between Cp*Rh(H)(BO(2)C(2)H(4)) and the primary and secondary C-H bonds of propane indicate that the lowest energy pathway for C-H bond cleavage occurs to form an isomer in which the alkyl and boryl groups are trans to each other, while the lowest energy pathway for functionalization of the primary C-H bond occurs by formation of the isomer in which these two groups are cis to each other. The barrier for formation of the rhodium complex by cleavage of secondary C-H bonds is higher than that by cleavage of primary C-H bond. The alkyl intermediates are formed reversibly, and steric effects cause the barrier for B-C bond formation from the secondary alkyl intermediate to be higher than that from the primary alkyl intermediate. Experimental studies are consistent with this computational analysis. H/D exchange occurs between (Cp*d(15))Rh(D)(2)(Bpin)(2) and n-octane, indicating that C-H bond cleavage occurs reversibly and occurs faster at primary over secondary C-H bonds. The observation of small amounts of H/D exchange into the secondary C-H bonds of linear alkanes and the clear observation of H/D exchange into the secondary positions of cyclic alkanes without formation of products from functionalization are consistent with the high barrier calculated for B-C bond formation from the secondary alkyl intermediate. A series of kinetic experiments are consistent with a mechanism for H/D exchange between (Cp*d(15))Rh(D)(2)(Bpin)(2) and n-octane occurring by dissociation of borane-d(1) to form (Cp*d(15))Rh(D)(Bpin). Thus, the origin of the selectivity for borylation of primary over secondary C-H bonds is due to the cumulative effects of selective C-H bond cleavage and selective C-B bond formation.