Recent Advances in Visible-Light-Mediated Amide Synthesis

Visible-light photoredox catalysis has attracted tremendous interest within the synthetic community. As such, the activation mode potentially provides a more sustainable and efficient platform for the activation of organic molecules, enabling the invention of many controlled radical-involved reactions under mild conditions. In this context, amide synthesis via the strategy of photoredox catalysis has received growing interest due to the ubiquitous presence of this structural motif in numerous natural products, pharmaceuticals and functionalized materials. Employing this strategy, a wide variety of amides can be prepared effectively from halides, arenes and even alkanes under irradiation of visible light. These methods provide a robust alternative to well-established strategies for amide synthesis that involve condensation between a carboxylic acid and amine mediated by a stoichiometric activating agent. In this review, the representative progresses made on the synthesis of amides through visible light-mediated radical reactions are summarized.

Thiol-Functionalization Carbonaceous Adsorbents for the Removal of Methyl-Mercury from Water in the ppb Levels

Mercury is a highly toxic pollutant of major public health concern, and human exposure is mainly related to the aqueous phase, where its dominant form is methyl-mercury (MeHg). In the current work, two carbon-based adsorbents, i.e., a commercial activated carbon and a sunflower seeds’ biochar, were modified by the introduction of thiol-active groups onto their surfaces for the MeHg removal from natural-like water in ppb concentration levels. The examined thiol-functionalization was a two-step process, since the raw materials were initially treated with nitric acid (6 N), which is a reagent that favors the formation of surface carboxyl groups, and subsequently by the thiol surface bonding groups through an esterification reaction in methanol matrix. The adsorbents’ capacity was evaluated toward the Hgtotal legislative regulation limit (1 μg/L) in drinking water (denoted as Q1). The respective isothermal adsorption results revealed an increased affinity between MeHg and thiol-functionalized materials, where the commercial carbon showed slightly higher capacity (0.116 μg Hg/mg) compared with the biochar (0.108 μg Hg/mg). This variation can be attributed to the respective higher surface area, resulting, also, to higher thiol groups loading. Regarding the proposed mechanism, it was proved that the S-Hg bond was formed, based on the characterization of the best performed saturated adsorbent.

Electrospun Ultrafine Cationic Cellulose Fibers Produced from Sugarcane Bagasse for Potential Textile Applications

Sugarcane bagasse (SCB) is an abundant by-product of sugar refining that can be utilized as a raw material for cellulose isolation for several industrial applications. Electrospinning has garnered attention in recent years because it allows the preparation of cellulosic materials with unique properties. In this study, cellulose was isolated from sugarcane bagasse and acetylated to fabricate fine acetate cellulose fibers through electrospinning. Subsequently, the electrospun fibers were deacetylated and cationized in order to produce functionalized materials with potential textile applications. The functional fibers were colored with an anionic dye (vinyl sulfone) with and without the presence of salt and were evaluated according to dye fixation, color attributes, morphological characteristics, and thermal stability. Cationic cellulose fibers that were dyed without added salt were found to be brighter and demonstrated better color fixation than those with added salt. In addition, morphological analysis performed using scanning electron microscopy demonstrated that cationized fibers dyed without added salt were better preserved at this stage. The cationic fiber also evidenced a high-temperature resistance, exhibiting a degradation temperature above 236 °C. The results suggest that cellulose fibers dyed in this manner can potentially be considered for use in textile applications due to their suitable dye fixation and tunable porosity (i.e., breathability).

The Electrospray (ESI) and Flowing Atmosphere-Pressure Afterglow (FAPA) Mass Spectrometry Studies of Nitrophenols (Plant Growth Stimulants) Removed Using Strong Base-Functionalized Materials

The functional silica-based materials functionalized with a strong nitrogen base TBD (SiO2-TBD) deposited via a linker or with a basic poly(amidoamine) dendrimer containing multiple terminal amine groups -NH2 (SiO2-EDA) and functional polymers containing a strong phosphazene base (Polymer-Phosphazene) or another basic poly(amidoamine) dendrimer (PMVEAMA-PAMAM) were tested as sorbents dedicated to a mixture of nitrophenols (p-nitrophenol and 2-methoxy-5-nitrophenol), which are analogs of nitrophenols used in plant growth biostimulants. The adsorptive potential of the studied materials reached 0.102, 0.089, 0.140, and 0.074 g of the nitrophenols g−1, for SiO2-TBD, SiO2-EDA, polymer-phosphazene, and PMVEAMA-PAMAM, respectively. The sorptive efficiency of the analytes, i.e., their adsorption on the functional materials, the desorption from the obtained [(sorbent)H+ − nitrophenolates–] complexes, and interactions with the used soil, were monitored using mass spectrometry (MS) technique with electrospray (ESI) and flowing atmosphere-pressure afterglow (FAPA) ionizations, for the analysis of the aqueous solutions and the solids, respectively. The results showed that the adsorption/desorption progress is determined by the structures of the terminal basic domains anchored to the materials, which are connected with the strength of the proton exchange between the sorbents and nitrophenols. Moreover, the conducted comprehensive MS analyses, performed for both solid and aqueous samples, gave a broad insight into the interactions of the biostimulants and the presented functional materials.

Development of Amino Acids Functionalized SBA-15 for the Improvement of Protein Adsorption

Ordered mesoporous materials and their modification with multiple functional groups are of wide scientific interest for many applications involving interaction with biological systems and biomolecules (e.g., catalysis, separation, sensor design, nano-science or drug delivery). In particular, the immobilization of enzymes onto solid supports is highly attractive for industry and synthetic chemistry, as it allows the development of stable and cheap biocatalysts. In this context, we developed novel silylated amino acid derivatives (Si-AA-NH2) that have been immobilized onto SBA-15 materials in biocompatible conditions avoiding the use of toxic catalyst, solvents or reagents. The resulting amino acid-functionalized materials (SBA-15@AA) were characterized by XRD, TGA, EA, Zeta potential, nitrogen sorption and FT-IR. Differences of the physical properties (e.g., charges) were observed while the structural ones remained unchanged. The adsorption of the enzyme lysozyme (Lyz) onto the resulting functionalized SBA-15@AA materials was evaluated at different pHs. The presence of different functional groups compared with bare SBA-15 showed better adsorption results, for example, 79.6 nmol of Lyz adsorbed per m2 of SBA-15@Tyr compared with the 44.9 nmol/m2 of the bare SBA-15.

Silane Modification of Mesoporous Materials for the Optimization of Antiviral Drug Adsorption and Release Capabilities in Vaginal Media

Three different functionalities have been incorporated into mesoporous materials by means of a coupling reaction with the siloxanes 3-glycidoxypropyl-trimethoxysilane (GLYMO), 3-methacryloxypropyl-trimethoxysilane (MEMO), and 3-mercaptopropyl-trimethoxysilane (MPTMS). The disposition of the different functional groups, as well as the interaction mechanism, with the mesoporous substrate has been identified. The amount of the antiviral drug acyclovir (ACV) adsorbed depends not only on the available surface area but also on the chemical or physicochemical interactions between functionalities. The drug adsorption isotherm of the materials functionalized with GLYMO and MPTMS follow mechanisms dependent on the different surface coverage and the possibilities to establish physicochemical interactions between the drug molecule and the functionalities. On the contrary, when functionalizing with MEMO, the dominant adsorption mechanism is characteristic of chemically bonded adsorbates. The ACV release kinetics is best fitted to the Weibull model in all the functionalized materials. When the MTPMS is used as a functionalizing agent, the drug diffusion occurs at low kinetics and homogeneously along the mesoporous channels.

Reductive Amination Reaction for the Functionalization of Cellulose Nanocrystals

Cellulose nanocrystals (CNCs) represent intriguing biopolymeric nanocrystalline materials, that are biocompatible, sustainable and renewable, can be chemically functionalized and are endowed with exceptional mechanical properties. Recently, studies have been performed to prepare CNCs with extraordinary photophysical properties, also by means of their functionalization with organic light-emitting fluorophores. In this paper, we used the reductive amination reaction to chemically bind 4-(1-pyrenyl)butanamine selectively to the reducing termini of sulfated or neutral CNCs (S_CNC and N_CNC) obtained from sulfuric acid or hydrochloric acid hydrolysis. The functionalization reaction is simple and straightforward, and it induces the appearance of the typical pyrene emission profile in the functionalized materials. After a characterization of the new materials performed by ATR-FTIR and fluorescence spectroscopies, we demonstrate luminescence quenching of the decorated N_CNC by copper (II) sulfate, hypothesizing for these new functionalized materials an application in water purification technologies.