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The photolyase family consists of flavoproteins with enzyme activity able to repair ultraviolet light radiation damage by photoreactivation. DNA damage by the formation of a cyclobutane pyrimidine dimer (CPD) and a pyrimidine-pyrimidone (6-4) photoproduct can lead to multiple affections such as cellular apoptosis and mutagenesis that can evolve into skin cancer. The development of integrated applications to prevent the negative effects of prolonged sunlight exposure, usually during outdoor activities, is imperative. This study presents the functions, characteristics, and types of photolyases, their therapeutic and cosmetic applications, and additionally explores some photolyase-producing microorganisms and drug delivery systems.
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Desoxirribodipirimidina Fotoliase , Reparo do DNA , Desoxirribodipirimidina Fotoliase/genética , Desoxirribodipirimidina Fotoliase/metabolismo , Flavoproteínas , Dímeros de Pirimidina , Pirimidinas , Pirimidinonas , Raios Ultravioleta/efeitos adversosRESUMO
Pork production has expanded in the world in recent years. This growth has caused a significant increase in waste from this industry, especially of wastewater. Although there has been an increase in wastewater treatment, there is a lack of useful technologies for the treatment of wastewater from the pork industry. Swine farms generate high amounts of organic pollution, with large amounts of nitrogen and phosphorus with final destination into water bodies. Sadly, little attention has been devoted to animal wastes, which are currently treated in simple systems, such as stabilization ponds or just discharged to the environment without previous treatment. This uncontrolled release of swine wastewater is a major cause of eutrophication processes. Among the possible treatments, phyco-remediation seems to be a sustainable and environmentally friendly option of removing compounds from wastewater such as nitrogen, phosphorus, and some metal ions. Several studies have demonstrated the feasibility of treating swine wastewater using different microalgae species. Nevertheless, the practicability of applying this procedure at pilot-scale has not been explored before as an integrated process. This work presents an overview of the technological applications of microalgae for the treatment of wastewater from swine farms and the by-products (pigments, polysaccharides, lipids, proteins) and services of commercial interest (biodiesel, biohydrogen, bioelectricity, biogas) generated during this process. Furthermore, the environmental benefits while applying microalgae technologies are discussed.
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Microalgas , Águas Residuárias , Animais , Biocombustíveis , Biomassa , Nitrogênio , Fósforo , SuínosRESUMO
A vast growing problem in orthopaedic medicine is the increase of clinical cases with antibiotic resistant pathogenic microbes, which is predicted to cause higher mortality than all cancers combined by 2050. Bone infectious diseases limit the healing ability of tissues and increase the risk of future injuries due to pathologic tissue remodelling. The traditional treatment for bone infections has several drawbacks and limitations, such as lengthy antibiotic treatment, extensive surgical interventions, and removal of orthopaedic implants and/or prosthesis, all of these resulting in long-term rehabilitation. This is a huge burden to the public health system resulting in increased healthcare costs. Current technologies e.g. co-delivery systems, where antibacterial and osteoinductive agents are delivered encounter challenges such as site-specific delivery, sustained and prolonged release, and biocompatibility. In this review, these aspects are highlighted to promote the invention of the next generation biomaterials to prevent and/or treat bone infections and promote tissue regeneration.
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Antibacterianos/química , Materiais Biocompatíveis/química , Ortopedia/métodos , Antibacterianos/uso terapêutico , Anti-Infecciosos/química , Anti-Infecciosos/uso terapêutico , Regeneração Óssea/efeitos dos fármacos , Humanos , Osteogênese/efeitos dos fármacosRESUMO
The cooperation and interplay between organic and metal catalyst systems is of utmost importance in nature and chemical synthesis. Here innovative and selective cooperative catalyst systems can be designed by combining two catalysts that complement rather than inhibit one another. This refined strategy can permit chemical transformations unmanageable by either of the catalysts alone. This review summarizes innovations and developments in selective organic synthesis that have used cooperative dual catalysis by combining simple aminocatalysts with metal catalysts. Considerable efforts have been devoted to this fruitful field. This emerging area employs the different activation modes of amine and metal catalysts as a platform to address challenging reactions. Here, aminocatalysis (e.g., enamine activation catalysis, iminium activation catalysis, single occupied molecular orbital (SOMO) activation catalysis, and photoredox activation catalysis) is employed to activate unreactive carbonyl substrates. The transition metal catalyst complements by activating a variety of substrates through a range of interactions (e.g., electrophilic π-allyl complex formation, Lewis acid activation, allenylidene complex formation, photoredox activation, C-H activation, etc.), and thereby novel concepts within catalysis are created. The inclusion of heterogeneous catalysis strategies allows for "green" chemistry development, catalyst recyclability, and the more eco-friendly synthesis of valuable compounds.
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Aminas/química , Técnicas de Química Sintética/métodos , Metais Pesados/química , Alquilação , Catálise , Reação de Cicloadição , OxirreduçãoRESUMO
Herein is described a versatile and broad synergistic strategy for expansion of chemical space and the synthesis of valuable molecules (e.g. carbocycles and heterocycles), with up to three quaternary stereocenters, in a highly enantioselective fashion from simple alcohols (31 examples, 95:5 to >99.5:0.5 e.r.) using integrated heterogeneous metal/chiral amine multiple relay catalysis and air/O2 as the terminal oxidant. A novel highly 1,4-selective heterogeneous metal/amine co-catalyzed hydrogenation of enals was also added to the relay catalysis sequences.
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A sustainable and efficient multicatalytic chemical transformation approach is devised for the development of all-biobased environmentally adaptable polymers and gels with multifunctional properties. The catalytic system, utilizing Lignin aluminum nanoparticles (AlNPs)-aluminum ions (Al3+ ), synergistically combines multiple catalytic cycles to create robust, mechanically stable, and versatile organohydrogels. Single catalytic cycles alone fail to achieve desired results, highlighting the importance of cooperatively combining different cycles for successful outcomes. The transformation involves free radical crosslinking, reversible quinone-catechol reactions, and an autocatalytic mechanism, resulting in a dual crosslinking strategy that incorporates both covalent and ionic crosslinking. This approach creates a dynamic gel system with combined energy dissipation and storage mechanisms. The engineered organohydrogels demonstrate vital multifunctionalities such as good thermal stability, self-healing, and adhesive properties, flame-retardancy, mechanical resilience and durability, conductivity, viscoelastic properties, environmental adaptability, and resistance to extreme conditions such as freezing and drying. The developed catalytic technology and resulting gels hold significant potential for applications in flexible electronics, energy storage, actuators, and sensors.
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Capsaicin (CAP) has been implicated as a gastroprotective agent in the treatment of peptic ulcers. However, its oral administration is hampered by its poor aqueous solubility and caustic effect at high administered doses. To address these limitations, we describe the development of gastric floating, sustained release electrospun films loaded with CAP. The nanofiber films were formulated using the polymers Eudragit RL/RS and sodium bicarbonate (SB) as the effervescent agent. The films were tested for their physicochemical properties, and film buoyancy and in vitro release of CAP were assessed in simulated gastric fluid. The cytocompatibility and anti-inflammatory properties of the films were evaluated in lipopolysaccharide (LPS)-stimulated Caco-2 cells. The amorphous films showed improved wettability, a short floating lag time (<1 s) and a total floating time of over 24 h accompanied by sustained CAP release for up to 24 h. CAP-loaded films demonstrated biocompatibility with Caco-2 cells and potential cytoprotective effects by attenuating inflammatory cytokine and reactive oxygen species (ROS) production in LPS-stimulated Caco-2 cells. The gastric floating electrospun films could serve as a platform for sustained and stomach-specific drug delivery applications.
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Capsaicina , Lipopolissacarídeos , Humanos , Preparações de Ação Retardada/química , Células CACO-2 , Sistemas de Liberação de Medicamentos , Solubilidade , ComprimidosRESUMO
Polysubstituted 5- and 6-membered carbocycles were synthesized by the title reaction. The one-pot dynamic relay process generates four new stereocenters, including a quaternary carbon center, in a highly enantioselective fashion (99.5:0.5â99:0.5 e.r.) by using a simple combination of palladium and chiral amine co-catalysts.
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Aminas/química , Hidrocarbonetos Cíclicos/síntese química , Paládio/química , Aldeídos , Catálise , Ciclização , Hidrocarbonetos Cíclicos/química , Estrutura Molecular , Estrutura Quaternária de Proteína , EstereoisomerismoRESUMO
The production and engineering of sustainable materials through green chemistry will have a major role in our mission of transitioning to a more sustainable society. Here, combined catalysis, which is the integration of two or more catalytic cycles or activation modes, provides innovative chemical reactions and material properties efficiently, whereas the single catalytic cycle or activation mode alone fails in promoting a successful reaction. Polyphenolic lignin with its distinctive structural functions acts as an important template to create materials with versatile properties, such as being tough, antimicrobial, self-healing, adhesive, and environmentally adaptable. Sustainable lignin-based materials are generated by merging the catalytic cycle of the quinone-catechol redox reaction with free radical polymerization or oxidative decarboxylation reaction, which explores a wide range of metallic nanoparticles and metal ions as the catalysts. In this review, we present the recent work on engineering lignin-based multifunctional materials devised through combined catalysis. Despite the fruitful employment of this concept to material design and the fact that engineering has provided multifaceted materials able to solve a broad spectrum of challenges, we envision further exploration and expansion of this important concept in material science beyond the catalytic processes mentioned above. This could be accomplished by taking inspiration from organic synthesis where this concept has been successfully developed and implemented.
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The sustainable production of polymers and materials derived from renewable feedstocks such as biomass is vital to addressing the current climate and environmental challenges. In particular, finding a replacement for current widely used curable resins containing undesired components with both health and environmental issues, such as bisphenol-A and styrene, is of great interest and vital for a sustainable society. In this work, we disclose the preparation and fabrication of an all-biobased curable resin. The devised resin consists of a polyester component based on fumaric acid, itaconic acid, 2,5-furandicarboxylic acid, 1,4-butanediol, and reactive diluents acting as both solvents and viscosity enhancers. Importantly, the complete process was performed solvent-free, thus promoting its industrial applications. The cured biobased resin demonstrates very good thermal properties (stable up to 415 °C), the ability to resist deformation based on the high Young's modulus of â¼775 MPa, and chemical resistance based on the swelling index and gel content. We envision the disclosed biobased resin having tailorable properties suitable for industrial applications.
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The field of precision medicine allows for tailor-made treatments specific to a patient and thereby improve the efficiency and accuracy of disease prevention, diagnosis, and treatment and at the same time would reduce the cost, redundant treatment, and side effects of current treatments. Here, the combination of organ-on-a-chip and bioprinting into engineering high-content in vitro tissue models is envisioned to address some precision medicine challenges. This strategy could be employed to tackle the current coronavirus disease 2019 (COVID-19), which has made a significant impact and paradigm shift in our society. Nevertheless, despite that vaccines against COVID-19 have been successfully developed and vaccination programs are already being deployed worldwide, it will likely require some time before it is available to everyone. Furthermore, there are still some uncertainties and lack of a full understanding of the virus as demonstrated in the high number new mutations arising worldwide and reinfections of already vaccinated individuals. To this end, efficient diagnostic tools and treatments are still urgently needed. In this context, the convergence of bioprinting and organ-on-a-chip technologies, either used alone or in combination, could possibly function as a prominent tool in addressing the current pandemic. This could enable facile advances of important tools, diagnostics, and better physiologically representative in vitro models specific to individuals allowing for faster and more accurate screening of therapeutics evaluating their efficacy and toxicity. This review will cover such technological advances and highlight what is needed for the field to mature for tackling the various needs for current and future pandemics as well as their relevancy towards precision medicine.
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COVID-19 , Humanos , Vacinas contra COVID-19 , SARS-CoV-2 , Medicina de PrecisãoRESUMO
The first direct intermolecular regiospecific and highly enantioselective α-allylic alkylation of linear aldehydes by a combination of achiral bench-stable Pd(0) complexes and simple chiral amines as co-catalysts is disclosed. The co-catalytic asymmetric chemoselective and regiospecific α-allylic alkylation reaction is linked in tandem with in situ reduction to give the corresponding 2-alkyl alcohols with high enantiomeric ratios (up to 98:2 e.r.; e.r.=enantiomeric ratio). It is also an expeditious entry to valuable 2-alkyl substituted hemiacetals, 2-alkyl-butane-1,4-diols, and amines. The concise co-catalytic asymmetric total syntheses of biologically active natural products (e.g., Arundic acid) are disclosed.
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Overexpression of the platelet-derived growth factor receptor (PDGFR) was already associated with the loss of p53 function as cancer progresses in lung, breast, and cervical cancers. Cancer biomarker detection has faced challenges and barriers due to various limitations, including a high limit of detection, low sensitivity, time-consuming techniques, and expensive equipment. Hence, the present investigation is designed to develop a cost-effective novel biosensor based on a charge-based affinity bait molecule to detect the PDGFR, thus overcoming the limitations and challenges with an immune technique based on antigen-antibody interactions. We employed EDC-NHS coupling between poly (diallyl dimethylammonium chloride) and poly(acrylic acid) to attach the multiwall carbon nanotube surface. As a result, we performed electrochemical PDGFR conversion sensing with a dynamic range of 1-10,000 ng/mL and a detection limit of 1.5 pg/mL, which is comparable to the best current results. The biosensor also displayed good selectivity, 2.51% repeatability (RSD, n = 5), and 30 days of stability. Our study provides a pathway for the design of diagnostic interfaces in biosystems, as well as the emergence of new sensor types based on ligand-receptor interactions.
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Biomarcadores Tumorais , Neoplasias , Técnicas Eletroquímicas/métodos , Eletrodos , Humanos , Limite de Detecção , Neoplasias/diagnóstico , Receptores do Fator de Crescimento Derivado de PlaquetasRESUMO
During the last decades, the use of nanotechnology in medicine has effectively been translated to the design of drug delivery systems, nanostructured tissues, diagnostic platforms, and novel nanomaterials against several human diseases and infectious pathogens. Nanotechnology-enabled vaccines have been positioned as solutions to mitigate the pandemic outbreak caused by the novel pathogen severe acute respiratory syndrome coronavirus 2. To fast-track the development of vaccines, unprecedented industrial and academic collaborations emerged around the world, resulting in the clinical translation of effective vaccines in less than one year. In this article, we provide an overview of the path to translation from the bench to the clinic of nanotechnology-enabled messenger ribonucleic acid vaccines and examine in detail the types of delivery systems used, their mechanisms of action, obtained results during each phase of their clinical development and their regulatory approval process. We also analyze how nanotechnology is impacting global health and economy during the COVID-19 pandemic and beyond.
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The quest for an ideal biomaterial perfectly matching the microenvironment of the surrounding tissues and cells is an endless challenge within biomedical research, in addition to integrating this with a facile and sustainable technology for its preparation. Engineering hydrogels through click chemistry would promote the sustainable invention of tailor-made hydrogels. Herein, we disclose a versatile and facile catalyst-free click chemistry for the generation of an innovative hydrogel by combining chondroitin sulfate (CS) and polyethylene glycol (PEG). Various multi-armed PEG-Norbornene (A-PEG-N) with different molecular sizes were investigated to generate crosslinked copolymers with tunable rheological and mechanical properties. The crosslinked and mechanically stable porous hydrogels could be generated by simply mixing the two clickable Tetrazine-CS (TCS) and A-PEG-N components, generating a self-standing hydrogel within minutes. The leading candidate (TCS-8A-PEG-N (40 kD)), based on the mechanical and biocompatibility results, was further employed as a scaffold to improve wound closure and blood flow in vivo. The hydrogel demonstrated not only enhanced blood perfusion and an increased number of blood vessels, but also desirable fibrous matrix orientation and normal collagen deposition. Taken together, these results demonstrate the potential of the hydrogel to improve wound repair and hold promise for in situ skin tissue engineering applications.
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Branching out! The first co-catalytic enantioselective (up to 98:2 e.r.) ß-alkylation of α,ß-unsaturated aldehydes by combination of simple chiral amine and copper catalysts provides ß-branched aldehydes in a one-pot protocol. The methodology was applied to the short total syntheses of bisabolane sesquiterpenes (S)-(+)-curcumene, (E)-(S)-(+)-3-dehydrocurcumene and (S)-(+)-tumerone.
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Aldeídos/química , Sesquiterpenos/química , Sesquiterpenos/síntese química , Elementos de Transição/química , Alquilação , Catálise , Estrutura Molecular , EstereoisomerismoRESUMO
Currently, oxygen supply for in vitro cell culture is one of the major challenges in tissue engineering, especially in three-dimensional (3D) structures, such as polymeric hydrogels, because oxygen is an essential element for cells survival. In this context, oxygen levels must be maintained in articular cartilage to promote the differentiation, viability, and proliferation of chondrocytes due to the low level of oxygen presence in this region. Although some technologies employ oxygen-generating materials to add sufficient oxygen levels, the limitations and challenges of current technologies include the lack of controlled, sustained, and prolonged release of the oxygen. Moreover, the fabrication methods may leave some impurities or residues resulting in toxicity to the cells. "Click" chemistry is a facile, versatile, and compatible chemical strategy to engineer hydrogels for tissue engineering applications. Herein, we disclose the engineering of oxygen-generating microparticles in chondrocytes-laden hydrogels through a versatile catalyst-free tetrazine and norbornene inverse electron demand DielsâAlder (iEDDA) click reaction. The hydrogels combine chondroitin sulfate (CS) and poly(ethylene glycol) (PEG) crosslinked in situ, displaying tunable rheological and mechanical properties, for sustained and prolonged oxygen-release. Gene expression analysis of the chondrocytes by real-time reverse transcription polymerase chain reaction (RT-PCR) demonstrated promising cell response within the engineered hydrogel.
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Condrócitos , Hidrogéis , Química Click , Oxigênio , Engenharia TecidualRESUMO
The engineering of multifunctional surgical bactericidal nanofibers with inherent suitable mechanical and biological properties, through facile and cheap fabrication technology, is a great challenge. Moreover, hernia, which is when organ is pushed through an opening in the muscle or adjacent tissue due to damage of tissue structure or function, is a dire clinical challenge that currently needs surgery for recovery. Nevertheless, post-surgical hernia complications, like infection, fibrosis, tissue adhesions, scaffold rejection, inflammation, and recurrence still remain important clinical problems. Herein, through an integrated electrospinning, plasma treatment and direct surface modification strategy, multifunctional bactericidal nanofibers were engineered showing optimal properties for hernia repair. The nanofibers displayed good bactericidal activity, low inflammatory response, good biodegradation, as well as optimal collagen-, stress fiber- and blood vessel formation and associated tissue ingrowth in vivo. The disclosed engineering strategy serves as a prominent platform for the design of other multifunctional materials for various biomedical challenges.
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Antibacterianos/farmacologia , Materiais Biocompatíveis , Gelatina/farmacologia , Hérnia Abdominal/cirurgia , Herniorrafia/instrumentação , Metacrilatos/farmacologia , Nanofibras , Poliésteres/farmacologia , Infecção da Ferida Cirúrgica/prevenção & controle , Alicerces Teciduais , Animais , Antibacterianos/química , Modelos Animais de Doenças , Gelatina/química , Hérnia Abdominal/patologia , Metacrilatos/química , Camundongos , Células NIH 3T3 , Nanomedicina , Poliésteres/química , Ratos , Infecção da Ferida Cirúrgica/microbiologia , Cicatrização/efeitos dos fármacosRESUMO
With the increasing volume of cardiovascular surgeries and the rising adoption rate of new methodologies that serve as a bridge to cardiac transplantation and that require multiple surgical interventions, the formation of postoperative intrapericardial adhesions has become a challenging problem that limits future surgical procedures, causes serious complications, and increases medical costs. To prevent this pathology, we developed a nanotechnology-based self-healing drug delivery hydrogel barrier composed of silicate nanodisks and polyethylene glycol with the ability to coat the epicardial surface of the heart without friction and locally deliver dexamethasone, an anti-inflammatory drug. After the fabrication of the hydrogel, mechanical characterization and responses to shear, strain, and recovery were analyzed, confirming its shear-thinning and self-healing properties. This behavior allowed its facile injection (5.75 ± 0.15 to 22.01 ± 0.95 N) and subsequent mechanical recovery. The encapsulation of dexamethasone within the hydrogel system was confirmed by 1H NMR, and controlled release for 5 days was observed. In vitro, limited cellular adhesion to the hydrogel surface was achieved, and its anti-inflammatory properties were confirmed, as downregulation of ICAM-1 and VCAM-1 was observed in TNF-α activated endothelial cells. In vivo, 1 week after administration of the hydrogel to a rabbit model of intrapericardial injury, superior efficacy was observed when compared to a commercial adhesion barrier, as histological and immunohistochemical examination revealed reduced adhesion formation and minimal immune infiltration of CD3+ lymphocytes and CD68+ macrophages, as well as NF-κß downregulation. We presented a novel nanostructured drug delivery hydrogel system with unique mechanical and biological properties that act synergistically to prevent cellular infiltration while providing local immunomodulation to protect the intrapericardial space after a surgical intervention.
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Sistemas de Liberação de Medicamentos/métodos , Nanomedicina/métodos , Nanoestruturas , Pericárdio/cirurgia , Aderências Teciduais/prevenção & controle , Animais , Procedimentos Cirúrgicos Cardíacos/efeitos adversos , Preparações de Ação Retardada/química , Preparações de Ação Retardada/farmacologia , Modelos Animais de Doenças , Hidrogéis/química , Hidrogéis/farmacologia , Masculino , Polietilenoglicóis/química , Polietilenoglicóis/farmacologia , Complicações Pós-Operatórias/prevenção & controle , CoelhosRESUMO
More than 90% of surgical patients develop postoperative adhesions, and the incidence of hospital re-admissions can be as high as 20%. Current adhesion barriers present limited efficacy due to difficulties in application and incompatibility with minimally invasive interventions. To solve this clinical limitation, we developed an injectable and sprayable shear-thinning hydrogel barrier (STHB) composed of silicate nanoplatelets and poly(ethylene oxide). We optimized this technology to recover mechanical integrity after stress, enabling its delivery though injectable and sprayable methods. We also demonstrated limited cell adhesion and cytotoxicity to STHB compositions in vitro. The STHB was then tested in a rodent model of peritoneal injury to determine its efficacy preventing the formation of postoperative adhesions. After two weeks, the peritoneal adhesion index was used as a scoring method to determine the formation of postoperative adhesions, and STHB formulations presented superior efficacy compared to a commercially available adhesion barrier. Histological and immunohistochemical examination showed reduced adhesion formation and minimal immune infiltration in STHB formulations. Our technology demonstrated increased efficacy, ease of use in complex anatomies, and compatibility with different delivery methods, providing a robust universal platform to prevent postoperative adhesions in a wide range of surgical interventions.