High Degree Of Functionalization Research Articles

Efficient Cross-Linking through C-H Bond Insertion of Unfunctionalized Commodity Materials Using Diazirine-Containing Polymers.

The synthesis and application of multifunctional diazirine-containing polymers for on-demand cross-linking of unfunctionalized commodity polymers through C-H bond insertion is demonstrated. While small-molecule diazirine cross-linkers have seen important applications such as plastic compatibilization and photopatterning, the high degree of functionalization of polymer-based diazirine cross-linkers offers promise for enhanced compatibility based on polymer blending and increased efficiency due to controllable multivalency. As a demonstrative example, unfunctionalized linear poly(n-butyl acrylate) (PnBA) can be cross-linked using various polymeric cross-linkers with diazirine contents as low as 0.8 wt % in 1 min under photochemical conditions. With gel fractions up to 95%, tunable rheological behavior is observed with increasing cross-linker loadings, consistent with a transition from entangled branched polymers to a cross-linked network. Moreover, the synthetic stability of the diazirine units can be exploited to prepare diazirine-containing polymers based on a variety of different backbones, from vinyl copolymers to poly(dimethylsiloxane) (PDMS), which allows successful photopatterning using a commercial 3D printer.

Repurposing ABS to Produce Polyamide 6 (PA6)-Based Blends: Reactive Compatibilization with SAN-g-MA of a High Degree of Functionalization

In this study, recycled acrylonitrile-butadiene-styrene terpolymer (ABSr) was reused to produce polyamide 6 (PA6)-based blends. This was achieved through reactive compatibilization using styrene-acrylonitrile-maleic anhydride (SAN-g-MA) copolymer with a high degree of functionalization (6–10% MA). The PA6/ABSr and PA6/ABSr/SAN-g-MA blends were prepared through melt processing and injection molding and then analyzed for their rheological, mechanical, thermomechanical, thermal, and structural properties, as well as morphology. The torque rheometry revealed a maximum reactivity of the PA6/ABSr (70/30 wt%) blend with low SAN-g-MA (5 phr—parts per hundred resin) content, while above this threshold, torque began to decline, indicating compatibilizer saturation in the interface. These findings were further substantiated by the increase in complex viscosity and the lower melt flow index (MFI) of the PA6/ABSr/SAN-g-MA (5 phr) blend. The 5 phr SAN-g-MA reactive compatibilization of the PA6/ABSr blends significantly enhanced its impact strength, elongation at break, tensile strength, and heat deflection temperature (HDT) by 217%, 631%, 12.6%, and 9.5%, respectively, compared to PA6/ABSr. These findings are promising for the plastic recycling field, paving the way for the production of new tailor-made materials at a reduced price.

Modular Synthesis of Heterobenzylic Amines via Carbonyl Azinylative Amination.

Transformations enabling the synthesis of α-alkyl, α'-2-azinyl amines by addition of 2-heteroaryl-based nucleophiles to in situ-generated and non-activated alkyl-substituted iminium ions are extremely rare. Approaches involving classical 2-azinyl organometallics, such as the corresponding Grignard reagents, often fail to produce the desired products. Here, we report an operationally straightforward solution to this problem through the development of a multicomponent coupling process wherein a soft 2-azinyl indium nucleophile, generated in situ from the corresponding 2-iodo heteroarene and indium powder, adds to an iminium ion that is also formed directly in the reaction. This modular carbonyl azinylative amination (CAzA) displays a broad scope and only a metal reductant is needed to generate a reactive 2-azinyl nucleophile. Beyond the addition to iminium ions, the 2-azinyl addition to polyfluoromethyl ketones forms the corresponding tertiary alcohols. Together, the products of these reactions possess a high degree of functionality, are typically challenging to synthesize by other methods, and contain motifs recognized as privileged in the context of pharmaceuticals and agrochemicals.

Characterization of pentenoate-functionalized hyaluronic acid and pentenoate-functionalized gelatin hydrogels for printing and future surgical placement in regenerative medicine applications

Injectable hydrogels with in situ crosslinking may be more suitable than pre-fabricated scaffolds for surgical delivery to clinical injuries. However, low viscosity hydrogel precursors may be challenging to surgically place into an injury if the precursor leaks or is washed out. The biomaterials field for extrusion bioprinting is a fertile ground for discovering biomaterials with injectable and paste-like precursor rheology with in situ gelation capabilities, which may promote better material retention in clinical injuries. We previously developed and evaluated one formulation of a pentenoate-functionalized hyaluronic acid (PHA) / pentenoate-functionalized gelatin (PGel) hydrogel with a paste-like, printable precursor and rapid photocrosslinking in a spinal cord injury application. Further characterization of the material and cell response to PHA/PGel hydrogel formulations is needed to expand the bioprinting and other regenerative medicine opportunities for PHA/PGel hydrogels. In the current study, we utilized 2D NMR methods (i.e., 1H–1H TOCSY) to confirm and quantify a high degree of pentenoate functionalization of PGel and PHA. We characterized the stiffness, swelling, and cell viability using varying formulations of PGel or PHA/PGel hydrogels. For compression testing, a straightforward application of the Ogden model enabled evaluation of the full stress-strain range for improved moduli comparisons. We identified two formulations that best supported cell viability (i.e., 3%/10% and 4%/5% PHA/PGel). Furthermore, one of the identified formulations (4%/5% PHA/PGel) had superior printability compared to the other. With better printability and potentially better clinical surgical placement, the new PHA/PGel hydrogel formulations may be more widely applied in the bioprinting and regenerative medicine fields.

Modular Synthesis of Heterobenzylic Amines via Carbonyl Azinylative Amination

AbstractTransformations enabling the synthesis of α‐alkyl, α′‐2‐azinyl amines by addition of 2‐heteroaryl‐based nucleophiles to in situ‐generated and non‐activated alkyl‐substituted iminium ions are extremely rare. Approaches involving classical 2‐azinyl organometallics, such as the corresponding Grignard reagents, often fail to produce the desired products. Here, we report an operationally straightforward solution to this problem through the development of a multicomponent coupling process wherein a soft 2‐azinyl indium nucleophile, generated in situ from the corresponding 2‐iodo heteroarene and indium powder, adds to an iminium ion that is also formed directly in the reaction. This modular carbonyl azinylative amination (CAzA) displays a broad scope and only a metal reductant is needed to generate a reactive 2‐azinyl nucleophile. Beyond the addition to iminium ions, the 2‐azinyl addition to polyfluoromethyl ketones forms the corresponding tertiary alcohols. Together, the products of these reactions possess a high degree of functionality, are typically challenging to synthesize by other methods, and contain motifs recognized as privileged in the context of pharmaceuticals and agrochemicals.

Continuous Flow Synthesis of Functional Isocyanate-Free Poly(oxazolidone)s by Step-Growth Polymerization.

Flow chemistry presents many advantages over batch processes for the fast and continuous production of polymers under more robust, safer, and easily scalable conditions. Although largely exploited for chain-growth polymerizations, it has rarely been applied to step-growth polymerizations (SGP) due to their inherent limitations. Here, we report the facile and fast preparation of an emerging class of nonisocyanate polyurethanes, i.e., CO2-based poly(oxazolidone)s, by SGP in continuous flow reactors. Importantly, we also demonstrate that functional poly(oxazolidone)s are easily prepared by telescoping a flow module where SGP occurs with reagents able to simultaneously promote two polymer derivatizations in a second module, i.e., dehydration followed by cationic thiol-ene to yield poly(N,S-acetal oxazolidone)s. The functional polymer is produced at a high rate and functionalization degree, without requiring the isolation of any intermediates. This work demonstrates the enormous potential of flow technology for the facile and fast continuous production of functional polymers by SGP.

Effect of Amine, Carboxyl, or Thiol Functionalization of Mesoporous Silica Particles on Their Efficiency as a Quercetin Delivery System in Simulated Gastrointestinal Conditions.

Quercetin (Q) dietary supplements exhibit poor oral bioavailability because of degradation throughout gastrointestinal digestion (GD), which may be overcome using mesoporous silica particles (MSPs) as an oral delivery system (ODS). This study aimed to elucidate the effect of the functionalization of MSPs with amine-(A-MSP), carboxyl-(C-MSP), or thiol-(T-MSP) groups on their efficiency as a quercetin ODS (QODS). The type and degree of functionalization (DF) were used as factors in an experimental design. The Q-loaded F-MSP (F-MSP/Q) was characterized by gas physisorption analysis, loading capacity (LC), and dynamic light scattering and kinetics of Q release at gastric and intestinal pHs. Antioxidant capacity and Q concentration of media containing F-MSP/Q were evaluated after simulated GD. A-MSP showed the highest LC (19.79 ± 2.42%). C-MSP showed the lowest particle size at pH 1.5 or 7.4 (≈200 nm). T-MSP exhibited the maximum Q release at pH 7.4 (11.43%). High DF of A-MSP increased Q retention, regardless of pH. A-MSP preserved antioxidant capacity of Q-released gastric media (58.95 ± 3.34%). Nonetheless, MSP and F-MSP did not protect antioxidant properties of Q released in intestinal conditions. C-MSP and T-MSP showed essential features for cellular uptake and Q release within cells that need to be assessed.

Ultrafast exciton trapping dynamics in oxygen-functionalized single-walled carbon nanotubes

Artificial zero-dimensional quantum defects within single-walled carbon nanotubes hold immense promise for diverse optoelectronic applications such as bioimaging, near-infrared light emission, nanolasing, and single-photon generation. This study delves into the temporal behavior of excitons within oxygen-functionalized single-walled carbon nanotubes, employing ultrafast transient absorption spectroscopy. Our investigation unveils the emergence of functionalization-induced excitonic states, distinguished by a long-lasting induced transmittance signal. Remarkably, even at low degree of functionalization, we observe a reduction in the lifetime of band-edge excitons. In contrast, the population dynamics of deep-band excitons exhibit resilience against low and moderate functionalization degrees, with a pronounced reduction manifesting only at high degrees of functionalization. Our findings align closely with a kinetic model that accounts for an additional relaxation channel prompted by functionalization. This empirical evidence provides a significant breakthrough, establishing that the formation of functionalization-induced excitonic states within oxygen-functionalized single-walled carbon nanotubes is a consequence of the diffusive trapping of free band edge excitons, while interaction of deep band excitons with oxygen defect sites rather yields in exciton recombination. These insights shed light on the intricate dynamics of excitons within single-walled carbon nanotube with artificially embedded quantum defects, advancing our understanding and potential applications in the realm of optoelectronics.

Mechanochemical and aging-based reductive amination with chitosan and aldehydes affords high degree of substitution functional biopolymers

A solid-phase method favors the formation of Shiff-bases from chitosan and aldehydes and subsequent reduction. This provides access to alkylated chitosans with high degrees of functionalization with low process mass intensity.

Advances in multifunctional metal-organic framework (MOF)-based nanoplatforms for cancer starvation therapy.

Cancer remains a significant threat to human health today. Even though starvation therapy and other treatment methods have recently advanced to a new level of rapid development in tumour treatment, their limited therapeutic effectiveness and unexpected side effects prevent them from becoming the first option in clinical treatment. With rapid advancement in nanotechnology, the utilization of nanomaterials in therapeutics offers the potential to address the shortcomings in cancer treatment. Notably, multifunctional metal-organic framework (MOF) has been widely employed in cancer therapy due to their customizable shape, adjustable diameter, high porosity, diverse compositions, large specific surface area, high degree of functionalization and strong biocompatibility. This paper reviews the current progress and success of MOF-based multifunctional nanoplatforms for cancer starvation therapy, as well as the prospects and potential barriers for the application of MOF nanoplatforms in cancer starvation therapy.

Enantioselective organocatalytic strategies to access noncanonical α-amino acids.

Organocatalytic asymmetric synthesis has evolved over the years and continues to attract the interest of many researchers worldwide. Enantiopure noncanonical amino acids (ncAAs) are valuable building blocks in organic synthesis, medicinal chemistry, and chemical biology. They are employed in the elaboration of peptides and proteins with enhanced activities and/or improved properties compared to their natural counterparts, as chiral catalysts, in chiral ligand design, and as chiral building blocks for asymmetric syntheses of complex molecules, including natural products. The linkage of ncAA synthesis and enantioselective organocatalysis, the subject of this perspective, tries to imitate the natural biosynthetic process. Herein, we present contemporary and earlier developments in the field of organocatalytic activation of simple feedstock materials, providing potential ncAAs with diverse side chains, unique three-dimensional structures, and a high degree of functionality. These asymmetric organocatalytic strategies, useful for forging a wide range of C-C, C-H, and C-N bonds and/or combinations thereof, vary from classical name reactions, such as Ugi, Strecker, and Mannich reactions, to the most advanced concepts such as deracemisation, transamination, and carbene N-H insertion. Concurrently, we present some interesting mechanistic studies/models, providing information on the chirality transfer process. Finally, this perspective highlights, through the diversity of the amino acids (AAs) not selected by nature for protein incorporation, the most generic modes of activation, induction, and reactivity commonly used, such as chiral enamine, hydrogen bonding, Brønsted acids/bases, and phase-transfer organocatalysis, reflecting their increasingly important role in organic and applied chemistry.

Chaotic behavior and construction of a variety of wave structures related to a new form of generalized q-Deformed sinh-Gordon model using couple of integration norms

<abstract><p>The generalized q-deformed sinh Gordon equation (GDSGE) serves as a significant nonlinear partial differential equation with profound applications in physics. This study investigates the GDSGE's mathematical and physical properties, examining its solutions and clarifying the essence of the q-deformation parameter. The Sardar sub-equation method (SSEM) and sine-Gordon expansion method (SGEM) are employed to solve this GDSGE. The synergistic application of these techniques improves our knowledge of the GDSGE and provides a thorough foundation for investigating different evolution models arising in various branches of mathematics and physics. A positive aspect of the proposed methods is that they offer a wide variety of solitons, including bright, singular, dark, combination dark-singular, combined dark-bright, and periodic singular solitons. Obtained solutions demonstrate the method's high degree of reliability, simplicity, and functionalization for various nonlinear equations. To better describe the physical characterization of solutions, a few 2D and 3D visualizations are generated by taking precise values for parameters using mathematical software, Mathematica.</p></abstract>

High degree of silanization of olive wood shell stone and its use in polyester biocomposites

A full optimization of the reaction conditions for the high degree of functionalization of olive wood shell stone (OS) with silanes of different nature has been conducted.

Dual-vat photopolymerization 3D printing of vitrimers

Herein, the processing of multi-material vitrimers with heterogenous properties along their x-,y- and z-axis is demonstrated using dual-vat digital light processing (DLP) 3D printing. The printer is based on a conventional vat exchange set-up containing two vats and a cleaning station, which are positioned on a linearly moving platform, and are exchanged automatically during the layer-by-layer build-up of the object. Two thiol-acrylate resins are selected bearing ample -OH and ester moieties, which undergo thermo-activated transesterification in the presence of an organic phosphate as catalyst. Based on the functionality of the acrylate monomers, printing of multi-material structures with flexible (σ = 1.1 MPa, ε = 14.0%) and rigid (σ = 33.3 MPa, ε = 4.4%) domains is feasible. A good interlayer adhesion between the soft and hard domains is evidenced by uniaxial tensile tests, whilst optical microscopy is used to study the interface. Dynamic mechanical analysis further shows that the stiffness of the photopolymers varies over several orders of magnitude (E’23 °C = 209 kPa - 507 MPa). Jacobs working curves of the two different resins reveal comparable printing parameters at higher exposure doses, which do not only facilitate the printing of multiple materials between individual layers (z-heterogeneity) but also within the same layer (x,y-heterogeneity). This is confirmed by the printing of a multi-material gripper as “proof of concept” demonstrator, which contains soft inner teeth and a stiff outer core. Gripping and releasing of objects is shown by exploiting the glass transition-based shape memory properties of the stiff domains. Moreover, due to the dynamic nature of the covalent bonds, damages inserted into the gripper are intrinsically repairable due to a thermo-activated macroscopic reflow. Shape memory experiments further confirmed that the multi-material gripper fully regains its function after the thermal mending process. Thus, the results clearly show that objects with a high degree of functionality can be realized by combining multi-material 3D printing with the chemistry of vitrimers. This is of particular interest for future soft robotic applications and for mimicking biological composite structures.

Recent progress on non-noble metal catalysts for the deoxydehydration of biomass-derived oxygenates

Abstract The utilization of renewable energy represents an effective way to address current issues associated with fossil fuels. Biomass is considered one type of renewable energy resources with abundant reserves on earth. However, the high oxygen contents and high degree of functionalization of biomass have hindered the direct exploitation of biomass for the production of fuels and chemicals. Considerable efforts have been devoted to developing effective deoxygenation methods capable of reducing the oxygen contents of biomass and its derivatives. The deoxydehydration (DODH) of biomass derivatives to generate olefins over oxophilic metal catalysts is considered a very useful approach in eliminating vicinal OH groups. In recent years, catalysts based on non-noble metals such as Mo, W, and V featuring good catalytic performance have emerged as promising alternatives to classical noble Re-based catalysts for DODH. This review aims to summarize the progress on the DODH of biomass-derived vicinal diols catalyzed by non-noble metals such as Mo, W, and V, with an emphasis on the preparation of catalysts, optimization of experimental conditions, and mechanistic studies. By surveying the performance of non-noble metal catalysts, key factors that determine the DODH activity were proposed, including the choice of reductant, the electronic and steric effects of ligand, and the interaction between solid support and metal center. The latter two could adjust the redox properties of metal centers by directly bonding with ligand or solid support.

Synthesis and Characterization of Highly Thiolated Silk Fibroin

AbstractCovalent attachment of thiols to the tyrosine residues of silk fibroin is accomplished with a high degree of functionalization through the reaction of a pyridyldithiol‐containing N‐hydroxysuccinimidal‐ester and an amino‐tyrosine silk intermediate. The extent of thiol modification is characterized by 1H NMR and UV–vis spectroscopy. Further modification of the thiol groups is probed by reacting with an iodoacetamide‐containing small molecule resulting in a novel fluorescent silk derivative. Last, the ability of the thiolated silk to form hydrogels in situ is investigated.

Differential functional reorganization of ventral and dorsal visual pathways following childhood hemispherectomy

Hemispherectomy is a surgical procedure in which an entire hemisphere of a patient’s brain is resected or functionally disconnected to manage seizures in individuals with drug-resistant epilepsy. Despite the extensive loss of both ventral and dorsal visual pathways in one hemisphere, pediatric patients who have undergone hemispherectomy show a remarkably high degree of perceptual function across many domains. In the current study, we sought to understand the extent to which functions of the ventral and dorsal visual pathways reorganize to the contralateral hemisphere following childhood hemispherectomy. To this end, we collected fMRI data from an equal number of left and right hemispherectomy patients who completed tasks that typically elicit lateralized responses from the ventral or the dorsal pathway, namely, word (left ventral), face (right ventral), tool (left dorsal), and global form (right dorsal) perception. Overall, there was greater evidence of functional reorganization in the ventral pathway than in the dorsal pathway. Importantly, because ventral and dorsal reorganization was tested within the very same patients, these results cannot be explained by idiosyncratic factors such as disease etiology, age at the time of surgery, or age at testing. These findings suggest that because the dorsal pathway may mature earlier, it may have a shorter developmental window of plasticity than the ventral pathway and, hence, be less malleable after perturbation.

Synthesis and characterization of novel chitosan derivatives (containing dipyridinium quaternary salts) with antimicrobial potential

Chitosan derivatives are versatile materials, biocompatible and biodegradable, that can be tailor-made to suit specific biomedical applications. In this study, two N-heterocyclic salts (N,N′-diphenacyl-[4,4′-dipyridinium] dibromide (DP) and N,N′-diphenacyl-1,2-bis-(4-pyridinium)ethane dibromide (DPE)) were used for chitosan functionalization to enhance its antimicrobial potential. Physico-chemical characterization of the newly synthesized derivatives (Ch-DP and Ch-DPE) was performed by elemental analysis, spectrometry (UV–Vis, FTIR), electrochemistry (OCP, CV), and electron microscopy (SEM) proving that the highest degree of functionalization was obtained for Ch-DP. The antimicrobial effect of chitosan functionalization was further tested in terms of its interaction with Listeria monocytogenes Scott A, and Staphylococcus aureus ATCC 25923, as Gram-positive bacteria and Escherichia coli ATCC 25922, as Gram-negative bacterium, respectively, showing that the Ch-DP had a good inhibitory activity compared with Ch-DPE.

Purification of functional mouse skeletal muscle mitochondria using percoll density gradient centrifugation

ObjectiveOur goal was to isolate purified mitochondria from mouse skeletal muscle using a Percoll density gradient and to assess bioenergetic function and purity via Seahorse Extracellular Flux (XF) Analyses and mass spectrometry.ResultsMitochondria isolated from murine quadriceps femoris skeletal muscle using a Percoll density gradient method allowed for minimally contaminated preparations with time from tissue harvest to mitochondrial isolation and quantification in about 3–4 h. Percoll purification from 100 to 200 mg fresh tissue yielded ~ 200–400 ug protein. Mitochondrial bioenergetics evaluated using the Seahorse XFe96 analyzer, a high-throughput respirometry platform, showed optimum mitochondrial input at 500 ng with respiratory control ratio ranging from 3.9 to 7.1 using various substrates demonstrating a high degree of functionality. Furthermore, proteomic analysis of Percoll-enriched mitochondria isolated from skeletal muscle using this method showed significant enrichment of mitochondrial proteins indicating high sample purity. This study established a methodology that ensures sufficient high quality mitochondria for downstream analyses such as mitochondrial bioenergetics and proteomics.

Highly Functionalized SWCNTs with a Dopamine Derivative as a Support for Pd Nanoparticles: A Recyclable Catalyst for the Reduction of Nitro Compounds and the Heck Reaction.

Single-walled carbon nanotubes (SWCNTs) were functionalized with a dopamine derivative in which the amine group was converted to azide (dopamine azide). The direct reaction of SWCNTs and dopamine azide in o-dichlorobenzene at high temperature (160 °C) led to very highly functionalized CNTs (≈60 wt%). Surprisingly, despite this high degree of functionalization, Raman spectroscopy detected a low disruption of the π-network of the carbonaceous support. This finding was justified by the rehybridization from sp3 to sp2 of the sidewall carbon atoms of CNTs involved in the functionalization process. Further characterization by means of different techniques such as X-ray photoelectron spectroscopy (XPS) analysis and transmission electron microscopy (TEM) allowed to shed some light on the chemical composition and morphology of the obtained material. Moreover, the estimation of the total content of phenolic units and their reducing potential after CNTs functionalization was also assessed using Folin and Ciocalteu and 2,2-diphenyl-1-picryl hydrazide (DPPH) assays. The functionalization of CNTs was exploited to immobilize palladium(II) species that were subsequently reduced with NaBH4 leading to the formation of Pd nanoparticles (NPs). The so obtained hybrid material was used as a recyclable heterogeneous catalyst for the reduction of nitro compounds and the Heck reaction.