Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 468
Filtrar
Más filtros

Banco de datos
País/Región como asunto
Tipo del documento
Intervalo de año de publicación
1.
Nature ; 612(7938): 83-87, 2022 12.
Artículo en Inglés | MEDLINE | ID: mdl-36289345

RESUMEN

Achieving carbon neutrality requires deploying renewable energy at unprecedented speed and scale1,2, yet countries sometimes implement policies that increase costs by restricting the free flow of capital, talent and innovation in favour of localizing benefits such as economic growth, employment and trade surpluses3,4. Here we assess the cost savings from a globalized solar photovoltaic (PV) module supply chain. We develop a two-factor learning model using historical capacity, component and input material price data of solar PV deployment in the United States, Germany and China. We estimate that the globalized PV module market has saved PV installers US$24 (19-31) billion in the United States, US$7 (5-9) billion in Germany and US$36 (26-45) billion in China from 2008 to 2020 compared with a counterfactual scenario in which domestic manufacturers supply an increasing proportion of installed capacities over a ten-year period. Projecting the same scenario forwards from 2020 results in estimated solar module prices that are approximately 20-25 per cent higher in 2030 compared with a future with globalized supply chains. International climate policy benefits from a globalized low-carbon value chain4, and these results point to the need for complementary policies to mitigate welfare distribution effects and potential impacts on technological crowding out.

2.
Plant Cell ; 35(1): 369-389, 2023 01 02.
Artículo en Inglés | MEDLINE | ID: mdl-36173348

RESUMEN

Maize (Zea mays) originated in southern Mexico and has spread over a wide latitudinal range. Maize expansion from tropical to temperate regions has necessitated a reduction of its photoperiod sensitivity. In this study, we cloned a quantitative trait locus (QTL) regulating flowering time in maize and show that the maize ortholog of Arabidopsis thaliana EARLY FLOWERING3, ZmELF3.1, is the causal locus. We demonstrate that ZmELF3.1 and ZmELF3.2 proteins can physically interact with ZmELF4.1/4.2 and ZmLUX1/2, to form evening complex(es; ECs) in the maize circadian clock. Loss-of-function mutants for ZmELF3.1/3.2 and ZmLUX1/2 exhibited delayed flowering under long-day and short-day conditions. We show that EC directly represses the expression of several flowering suppressor genes, such as the CONSTANS, CONSTANS-LIKE, TOC1 (CCT) genes ZmCCT9 and ZmCCT10, ZmCONSTANS-LIKE 3, and the PSEUDORESPONSE REGULATOR (PRR) genes ZmPRR37a and ZmPRR73, thus alleviating their inhibition, allowing florigen gene expression and promoting flowering. Further, we identify two closely linked retrotransposons located in the ZmELF3.1 promoter that regulate the expression levels of ZmELF3.1 and may have been positively selected during postdomestication spread of maize from tropical to temperate regions during the pre-Columbian era. These findings provide insights into circadian clock-mediated regulation of photoperiodic flowering in maize and new targets of genetic improvement for breeding.


Asunto(s)
Arabidopsis , Zea mays , Zea mays/metabolismo , Flores/metabolismo , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Adaptación Fisiológica/genética , Aclimatación/genética , Fotoperiodo , Arabidopsis/metabolismo , Regulación de la Expresión Génica de las Plantas/genética
3.
J Cell Mol Med ; 28(7): e18212, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38516826

RESUMEN

SBFI26, an inhibitor of FABP5, has been shown to suppress the proliferation and metastasis of tumour cells. However, the underlying mechanism by which SBFI26 induces ferroptosis in breast cancer cells remains largely unknown. Three breast cancer cell lines were treated with SBFI26 and CCK-8 assessed cytotoxicity. Transcriptome was performed on the Illumina platform and verified by qPCR. Western blot evaluated protein levels. Malondialdehyde (MDA), total superoxide dismutase (T-SOD), Fe, glutathione (GSH) and oxidized glutathione (GSSG) were measured. SBFI26 induced cell death time- and dose-dependent, with a more significant inhibitory effect on MDA-MB-231 cells. Fer-1, GSH and Vitamin C attenuated the effects but not erastin. RNA-Seq analysis revealed that SBFI26 treatment significantly enriched differentially expressed genes related to ferroptosis. Furthermore, SBFI26 increased intracellular MDA, iron ion, and GSSG levels while decreasing T-SOD, total glutathione (T-GSH), and GSH levels.SBFI26 dose-dependently up-regulates the expression of HMOX1 and ALOX12 at both gene and protein levels, promoting ferroptosis. Similarly, it significantly increases the expression of SAT1, ALOX5, ALOX15, ALOXE3 and CHAC1 that, promoting ferroptosis while downregulating the NFE2L2 gene and protein that inhibit ferroptosis. SBFI26 leads to cellular accumulation of fatty acids, which triggers excess ferrous ions and subsequent lipid peroxidation for inducing ferroptosis.


Asunto(s)
Ferroptosis , Neoplasias de la Mama Triple Negativas , Humanos , Neoplasias de la Mama Triple Negativas/tratamiento farmacológico , Neoplasias de la Mama Triple Negativas/genética , Disulfuro de Glutatión , Ferroptosis/genética , Peroxidación de Lípido , Glutatión , Hierro , Superóxido Dismutasa/genética , Especies Reactivas de Oxígeno , Proteínas de Unión a Ácidos Grasos
4.
J Am Chem Soc ; 146(9): 5952-5963, 2024 Mar 06.
Artículo en Inglés | MEDLINE | ID: mdl-38408428

RESUMEN

The ability of alkylamines to spontaneously liberate hydride ions is typically restrained, except under specific intramolecular reaction settings. Herein, we demonstrate that this reactivity can be unlocked through simple treatment with formaldehyde in hexafluoroisopropanol (HFIP) solvent, thereby enabling various intermolecular hydride transfer reactions of alkylamines under mild conditions. Besides transformations of small molecules, these reactions enable unique late-stage modification of complex peptides. Mechanistic investigations uncover that the key to these intermolecular hydride transfer processes lies in the accommodating conformation of solvent-mediated macrocyclic transition states, where the aggregates of HFIP molecules act as dexterous proton shuttles. Importantly, negative hyperconjugation between the lone electron pair of nitrogen and the antibonding orbital of amine's α C-H bond plays a critical role in the C-H activation, promoting its hydride liberation.

5.
Glob Chang Biol ; 30(3): e17256, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38532549

RESUMEN

Denitrification, anaerobic ammonium oxidation (anammox), and dissimilatory nitrate reduction to ammonium (DNRA) are three competing processes of microbial nitrate reduction that determine the degree of ecosystem nitrogen (N) loss versus recycling. However, the global patterns and drivers of relative contributions of these N cycling processes to soil or sediment nitrate reduction remain unknown, limiting our understanding of the global N balance and management. Here, we compiled a global dataset of 1570 observations from a wide range of terrestrial and aquatic ecosystems. We found that denitrification contributed up to 66.1% of total nitrate reduction globally, being significantly greater in estuarine and coastal ecosystems. Anammox and DNRA could account for 12.7% and 21.2% of total nitrate reduction, respectively. The contribution of denitrification to nitrate reduction increased with longitude, while the contribution of anammox and DNRA decreased. The local environmental factors controlling the relative contributions of the three N cycling processes to nitrate reduction included the concentrations of soil organic carbon, ammonium, nitrate, and ferrous iron. Our results underline the dominant role of denitrification over anammox and DNRA in ecosystem nitrate transformation, which is crucial to improving the current global soil N cycle model and achieving sustainable N management.


Asunto(s)
Compuestos de Amonio , Nitratos , Nitratos/análisis , Ecosistema , Desnitrificación , Carbono , Suelo , Nitrógeno , Oxidación-Reducción
6.
Biomacromolecules ; 25(4): 2574-2586, 2024 Apr 08.
Artículo en Inglés | MEDLINE | ID: mdl-38525818

RESUMEN

Developing biocompatible injectable hydrogels with high mechanical strength and rapid strong tissue adhesion for hemostatic sealing of uncontrolled bleeding remains a prevailing challenge. Herein, we engineer an injectable and photo-cross-linkable hydrogel based on naturally derived gelatin methacrylate (GelMA) and N-hydroxysuccinimide-modified poly(γ-glutamic acid) (γPGA-NHS). The chemically dual-cross-linked hydrogel rapidly forms after UV light irradiation and covalently bonds to the underlying tissue to provide robust adhesion. We demonstrate a significantly improved hemostatic efficacy of the hydrogel using various injury models in rats compared to the commercially available fibrin glue. Notably, the hydrogel can achieve hemostasis in porcine liver and spleen incision, and femoral artery puncture models. Moreover, the hydrogel is used for sutureless repair of the liver defect in a rat model with a significantly suppressed inflammatory response, enhanced angiogenesis, and superior healing efficacy compared to fibrin glue. Together, this study offers a promising bioadhesive for treating severe bleeding and facilitating wound repair.


Asunto(s)
Hemostáticos , Hidrogeles , Ratas , Animales , Porcinos , Hidrogeles/farmacología , Hidrogeles/química , Adhesivo de Tejido de Fibrina , Adhesivos , Materiales Biocompatibles/farmacología , Materiales Biocompatibles/química , Hemostáticos/farmacología , Hemorragia/tratamiento farmacológico , Cicatrización de Heridas
7.
J Org Chem ; 89(9): 6263-6273, 2024 May 03.
Artículo en Inglés | MEDLINE | ID: mdl-38652889

RESUMEN

Herein, we presented a practical methodology for the intermolecular aziridination of alkenes, using HOSA as the aminating agent, alongside pyridine or piperidine as the base, within HFIP solvent system. Notably, this approach showcases excellent reactivity, especially with nonactivated alkenes, and facilitates the transformation of various alkenes substrates, including mono-, di-, tri, and tetra-substituted alkenes, into aziridines with moderate to excellent yield. This method presents a promising avenue for synthesizing aziridines from a wide range of alkenes, featuring the benefits of straightforward operation, mild reaction conditions, extensive substrate compatibility, and scalability.

8.
Environ Sci Technol ; 58(12): 5187-5195, 2024 Mar 26.
Artículo en Inglés | MEDLINE | ID: mdl-38490225

RESUMEN

Clean hydrogen has the potential to serve as an energy carrier and feedstock in decarbonizing energy systems, especially in "hard-to-abate" sectors. Although many countries have implemented policies to promote electrolytic hydrogen development, the impact of these measures on costs of production and greenhouse gas emissions remains unclear. Our study conducts an integrated analysis of provincial levelized costs and life cycle greenhouse gas emissions for all hydrogen production types in China. We find that subsidies are critical to accelerate low carbon electrolytic hydrogen development. Subsidies on renewable-based hydrogen provide cost-effective carbon dioxide equivalent (CO2e) emission reductions. However, subsidies on grid-based hydrogen increase CO2e emissions even compared with coal-based hydrogen because grid electricity in China still relies heavily on coal power and likely will beyond 2030. In fact, CO2e emissions from grid-based hydrogen may increase further if China continues to approve new coal power plants. The levelized costs of renewable energy-based electrolytic hydrogen vary among provinces. Transporting renewable-based hydrogen through pipelines from low- to high-cost production regions reduces the national average levelized cost of renewables-based hydrogen but may increase the risk of hydrogen leakage and the resulting indirect warming effects. Our findings emphasize that policy and economic support for nonfossil electrolytic hydrogen is critical to avoid an increase in CO2e emissions as hydrogen use rises during a clean energy transition.


Asunto(s)
Gases de Efecto Invernadero , Carbón Mineral , Efecto Invernadero , Hidrógeno , Centrales Eléctricas , Dióxido de Carbono/análisis
10.
Pediatr Crit Care Med ; 25(5): 425-433, 2024 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-38353591

RESUMEN

OBJECTIVES: To describe the epidemiological characteristics of pediatric sepsis in Southwest China PICUs. DESIGN: A prospective, multicenter, and observational study. SETTING: Twelve PICUs in Southwest China. PATIENTS: The patients admitted to the PICU from April 1, 2022, to March 31, 2023. The age ranged from 28 days to 18 years. All patients met the criteria of severe sepsis or septic shock. INTERVENTIONS: None. MEASUREMENTS AND MAIN RESULTS: Of the 31 PICUs invited to participate, 12 PICUs (capacity of 292 beds) enrolled patients in the study. During the study period, 11,238 children were admitted to the participating PICUs, 367 (3.3%) of whom met the diagnosis of severe sepsis or septic shock. The most prevalent sites of infection were the respiratory system (55%) and the digestive system (15%). The primary treatments administered to these patients included antibiotics (100%), albumin (61.3%), invasive mechanical ventilation (58.7%), glucocorticoids (55.6%), blood products (51%), gammaglobulin (51%), and vasoactive medications (46.6%). Sepsis-related mortality in the PICU was 11.2% (41/367). Nearly half of the sepsis deaths occurred within the first 3 days of PICU admission (22/41, 53.7%). The mortality rate of septic shock (32/167, 19.2%) was significantly higher than that of severe sepsis (9/200, 4.5%; p < 0.001). The outcomes of a multivariate logistic regression analysis suggested that a higher pediatric Sequential Organ Failure Assessment score, and the use of invasive mechanical ventilation and vasoactive medications were independently associated with PICU mortality in children with sepsis. CONCLUSIONS: This report updates the epidemiological data of pediatric sepsis in PICUs in Southwest China. Sepsis is still a life-threatening disease in children.


Asunto(s)
Unidades de Cuidado Intensivo Pediátrico , Sepsis , Humanos , Estudios Prospectivos , Preescolar , China/epidemiología , Niño , Lactante , Masculino , Femenino , Adolescente , Unidades de Cuidado Intensivo Pediátrico/estadística & datos numéricos , Sepsis/epidemiología , Recién Nacido , Mortalidad Hospitalaria , Choque Séptico/epidemiología
11.
Mikrochim Acta ; 191(6): 353, 2024 May 29.
Artículo en Inglés | MEDLINE | ID: mdl-38809482

RESUMEN

Organic pollutant detection has caused widespread concern regarding due to their potential environmental and human health risks. In this work, a nitrogen-doped titanium dioxide/silver oxide (N-TiO2/Ag2O) composite has been designed as a sensitive photoelectrochemical (PEC) monitoring platform of organic dyes. Sensitive determination relies on the outstanding PEC performance of N-TiO2/Ag2O. The improved PEC performance stems from the effective separation of photocarriers and the extended light response range provided by the narrowing bandgap and a p-n junction with N-TiO2/Ag2O. The N-TiO2/Ag2O electrode exhibits a photocurrent density of up to 2.2 mA/cm2, demonstrating three times increase compared with the photocurrent density observed with the pure TiO2 film. The linear detection range for rhodamine B (RhB), methylene blue (MB), and methyl orange (MO) is 0.2 ng/mL to 10 µg/mL with an ultrasensitive detection limit of 0.2 ng/mL without bias voltage. Due to the outstanding photocurrent density and sensitive response to organic pollutants, the N-TiO2/Ag2O PEC sensor provided a promising analytical method to detect environmental organic dyes.

12.
Sensors (Basel) ; 24(1)2024 Jan 04.
Artículo en Inglés | MEDLINE | ID: mdl-38203161

RESUMEN

Recently, advancements in image sensor technology have paved the way for the proliferation of high-dynamic-range television (HDRTV). Consequently, there has been a surge in demand for the conversion of standard-dynamic-range television (SDRTV) to HDRTV, especially due to the dearth of native HDRTV content. However, since SDRTV often comes with video encoding artifacts, SDRTV to HDRTV conversion often amplifies these encoding artifacts, thereby reducing the visual quality of the output video. To solve this problem, this paper proposes a multi-frame content-aware mapping network (MCMN), aiming to improve the performance of conversion from low-quality SDRTV to high-quality HDRTV. Specifically, we utilize the temporal spatial characteristics of videos to design a content-aware temporal spatial alignment module for the initial alignment of video features. In the feature prior extraction stage, we innovatively propose a hybrid prior extraction module, including cross-temporal priors, local spatial priors, and global spatial prior extraction. Finally, we design a temporal spatial transformation module to generate an improved tone mapping result. From time to space, from local to global, our method makes full use of multi-frame information to perform inverse tone mapping of single-frame images, while it is also able to better repair coding artifacts.

13.
Sensors (Basel) ; 24(5)2024 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-38475167

RESUMEN

The fast development of the sensors in the wireless sensor networks (WSN) brings a big challenge of low energy consumption requirements, and Peer-to-peer (P2P) communication becomes the important way to break this bottleneck. However, the interference caused by different sensors sharing the spectrum and the power limitations seriously constrains the improvement of WSN. Therefore, in this paper, we proposed a deep reinforcement learning-based energy consumption optimization for P2P communication in WSN. Specifically, P2P sensors (PUs) are considered agents to share the spectrum of authorized sensors (AUs). An authorized sensor has permission to access specific data or systems, while a P2P sensor directly communicates with other sensors without needing a central server. One involves permission, the other is direct communication between sensors. Each agent can control the power and select the resources to avoid interference. Moreover, we use a double deep Q network (DDQN) algorithm to help the agent learn more detailed features of the interference. Simulation results show that the proposed algorithm can obtain a higher performance than the deep Q network scheme and the traditional algorithm, which can effectively lower the energy consumption for P2P communication in WSN.

14.
Angew Chem Int Ed Engl ; 63(2): e202312465, 2024 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-37997539

RESUMEN

Herein, we report that bulky alkylphosphines such as PtBu3 can switch the roles from actor to spectator ligands to promote the FeCl2 -catalyzed N-amidation reaction of arylamines with dioxazolones, giving hydrazides in high efficiency and chemoselectivity. Mechanistic studies indicated that the phosphine ligands could facilitate the decarboxylation of dioxazolones on the Fe center, and the hydrogen bonding interactions between the arylamines and the ligands on Fe nitrenoid intermediates might play a role in modulating the delicate interplay between the phosphine ligand, arylamine, and acyl nitrene N, favoring N-N coupling over N-P coupling. The new ligand-promoted N-amidation protocols offer a convenient way to access various challenging triazane compounds via double or sequential N-amidation of primary arylamines.

15.
Angew Chem Int Ed Engl ; 63(6): e202314454, 2024 Feb 05.
Artículo en Inglés | MEDLINE | ID: mdl-38009676

RESUMEN

Quasiperiodic patterns and crystals-having long range order without translational symmetry-have fascinated researchers since their discovery. In this study, we report on new p-terphenyl-based T-shaped facial polyphiles with two alkyl end chains and a glycerol-based hydrogen-bonded side group that self-assemble into an aperiodic columnar liquid quasicrystal with 12-fold symmetry and its periodic liquid-crystalline approximants with complex superstructures. All represent honeycombs formed by the self-assembly of the p-terphenyls, dividing space into prismatic cells with polygonal cross-sections. In the perspective of tiling patterns, the presence of unique trapezoidal tiles, consisting of three rigid sides formed by the p-terphenyls and one shorter, incommensurate, and adjustable side by the alkyl end chains, plays a crucial role for these phases. A delicate temperature-dependent balance between conformational, entropic and space-filling effects determines the role of the alkyl chains, either as network nodes or trapezoid walls, thus resulting in the order-disorder transitions associated with emergence of quasiperiodicity. In-depth analysis suggests a change from a quasiperiodic tiling involving trapezoids to a modified one with a contribution of trapezoid pair fusion. This work paves the way for understanding quasiperiodicity emergence and develops fundamental concepts for its generation by chemical design of non-spherical molecules, aggregates, and frameworks based on dynamic reticular chemistry.

16.
Angew Chem Int Ed Engl ; 63(25): e202405427, 2024 Jun 17.
Artículo en Inglés | MEDLINE | ID: mdl-38603586

RESUMEN

Neutral aqueous organic redox flow batteries (AORFBs) hold the potential to facilitate the transition of renewable energy sources from auxiliary to primary energy, the commercial production of anolyte materials still suffers from insufficient performance of high-concentration and the high cost of the preparation problem. To overcome these challenges, this study provides a hydrothermal synthesis methodology and introduces the charged functional groups into hydrophobic naphthalene diimide cores, and prepares a series of high-performance naphthalene diimide anolytes. Under the synergistic effect of π-π stacking and H-bonding networks, the naphthalene diimide exhibits excellent structural stability and the highest water solubility (1.85 M for dex-NDI) reported to date. By employing the hydrothermal method, low-cost naphthalene diimides are successfully synthesized on a hundred-gram scale of $0.16 g-1 ($2.43 Ah-1), which is also the lowest price reported to date. The constructed full battery achieves a high electron concentration of 2.4 M, a high capacity of 54.4 Ah L-1, and a power density of 318 mW cm-2 with no significant capacity decay observed during long-duration cycling. These findings provide crucial support for the commercialization of AORFBs and pave the way for revolutionary developments in neutral AORFBs.

17.
Angew Chem Int Ed Engl ; : e202407923, 2024 May 13.
Artículo en Inglés | MEDLINE | ID: mdl-38738617

RESUMEN

Although catenated cages have been widely constructed due to their unique and elegant topological structures, cyclic catenanes formed by the connection of multiple catenane units have been rarely reported. Herein, based on the orthogonal metal-coordination-driven self-assembly, we prepare a series of heterometallic [2]catenanes and cyclic bis[2]catenanes, whose structures are clearly evidenced by single-crystal X-ray analysis. Owing to the multiple positively charged nature, as well as the potential synergistic effect of the Cu(I) and Pt(II) metal ions, the cyclic bis[2]catenanes display broad-spectrum antibacterial activity. This work not only provides an efficient strategy for the construction of heterometallic [2]catenanes and cyclic bis[2]catenanes but also explores their applications as superior antibacterial agents, which will promote the construction of advanced supramolecular structures for biomedical applications.

18.
Angew Chem Int Ed Engl ; 63(16): e202318893, 2024 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-38376389

RESUMEN

α-Ketoaldehydes play versatile roles in the ubiquitous natural processes of protein glycation. However, leveraging the reactivity of α-ketoaldehydes for biomedical applications has been challenging. Previously, the reactivity of α-ketoaldehydes with guanidine has been harnessed to design probes for labeling Arg residues on proteins in an aqueous medium. Herein, a highly effective, broadly applicable, and operationally simple protocol for stapling native peptides by crosslinking two amino groups through diverse imidazolium linkers with various α-ketoaldehyde reagents is described. The use of hexafluoroisopropanol as a solvent facilitates rapid and clean reactions under mild conditions and enables unique selectivity for Lys over Arg. The naturally occurring GOLD/MOLD linkers have been expanded to encompass a wide range of modified glyoxal-lysine dimer (OLD) linkers. In a proof-of-concept trial, these modular stapling reactions enabled a convenient two-round strategy to streamline the structure-activity relationship (SAR) study of the wasp venom peptide anoplin, leading to enhanced biological activities.


Asunto(s)
Glioxal , Lisina , Glioxal/química , Lisina/química , Aminas , Aldehídos , Péptidos , Reactivos de Enlaces Cruzados/química
19.
J Am Chem Soc ; 145(16): 9118-9128, 2023 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-37015020

RESUMEN

The novel selenoviologen-based tetracationic cyclophanes (green boxes 3 and 5) with rigid electron-deficient cavities are synthesized via SN2 reactions in two steps. The green boxes exhibit good redox properties, narrow energy gaps, and strong absorption in the visible range (370-470 nm), especially for the green box 5 containing two selenoviologen (SeV2+) units. Meanwhile, the femtosecond transient absorption (fs-TA) reveals that the green boxes have a stabilized dicationic biradical, high efficiency of intramolecular charge transfer (ICT), and long-lived charge separation state due to the formation of cyclophane structure. Based on the excellent photophysical and redox properties, the green boxes are applied to electrochromic devices (ECDs) and visible-light-driven hydrogen production with a high H2 generation rate (34 µmol/h), turnover number (203), and apparent quantum yield (5.33 × 10-2). In addition, the host-guest recognitions are demonstrated between the green boxes and electron-rich guests (e.g., G1:1-naphthol and G2:platinum(II)-tethered naphthalene) in MeCN through C-H···π and π···π interactions. As a one-component system, the host-guest complexes of green box⊃G2 are successfully applied to visible-light photocatalytic hydrogen production due to the intramolecular electron transfer (IET) between platinum(II) of G2 and SeV2+ of the green box, which provides a simplified system for solar energy conversion.

20.
J Am Chem Soc ; 145(25): 13968-13978, 2023 06 28.
Artículo en Inglés | MEDLINE | ID: mdl-37326500

RESUMEN

The three-dimensional structure of medium-sized cyclic peptides accounts for their biological activity and other important physiochemical properties. Despite significant advances in the past few decades, chemists' ability to fine-tune the structure, in particular, the backbone conformation, of short peptides made of canonical amino acids is still quite limited. Nature has shown that cross-linking the aromatic side chains of linear peptide precursors via enzyme catalysis can generate cyclophane-braced products with unusual structures and diverse activities. However, the biosynthetic path to these natural products is challenging to replicate in the synthetic laboratory using practical chemical modifications of peptides. Herein, we report a broadly applicable strategy to remodel the structure of homodetic peptides by cross-linking the aromatic side chains of Trp, His, and Tyr residues with various aryl linkers. The aryl linkers can be easily installed via copper-catalyzed double heteroatom-arylation reactions of peptides with aryl diiodides. These aromatic side chains and aryl linkers can be combined to form a large variety of assemblies of heteroatom-linked multi-aryl units. The assemblies can serve as tension-bearable multijoint braces to modulate the backbone conformation of peptides as an entry to previously inaccessible conformational space.


Asunto(s)
Tirantes , Péptidos , Péptidos/química , Péptidos Cíclicos/química , Conformación Molecular , Aminoácidos/química
SELECCIÓN DE REFERENCIAS
DETALLE DE LA BÚSQUEDA