ABSTRACT
A supramolecular naphthalenediimide radical anion was developed through host-guest interactions between NDI and cucurbit[7]uril (CB[7]), which can be greatly promoted in the presence of chloride ions to obtain ClË and NDI-2CB[7]Ë-. Under the synergistic action of ClË as a hydrogen atom transfer (HAT) agent and NDI-2CB[7]Ë- transferring electrons to O2 to produce O2Ë-, the photocatalytic oxidation reactions of alkylarenes to carbonyls can be realized with universal applicability.
ABSTRACT
Supramolecular polymers, with their specific functional units and structures, can effectively enhance the absorption and utilization of light energy, thereby facilitating more efficient photocatalytic organic reactions. In the present work, we constructed a supramolecular polymer consisting of benzothiazole derivatives (BTBP) and cucurbit[8]uril (CB[8]). The BTBP monomer, known for its unique chemical structure and properties, has been found to exhibit a remarkable capability in generating singlet oxygen (1O2). As a result of the constraining impact of the macrocyclic molecule, the inclusion of CB[8] resulted in an effective enhancement in the ability to generate 1O2 while forming supramolecular polymer BTBP-CB[8]. When evaluating the quantum yield of 1O2 using Rose Bengal (RB) as a reference photosensitizer (75% in water), BTBP-CB[8] demonstrated an enhanced 1O2 quantum yield compared to BTBP, with an impressive yield of 152.4%, demonstrating that the formation of supramolecular polymer contributes to its ability to generate 1O2. Subsequently, BTBP-CB[8], a highly efficient 1O2 generator, was employed for the photocatalytic Minisci alkylation reaction, resulting in an impressive reaction yield of up to 89%. The supramolecular polymer strategies employed in the construction of photocatalytic systems have exhibited remarkable efficacy in the production of 1O2, underscoring their immense prospects in photocatalysis.
ABSTRACT
Employing hydrogen-bonded organic frameworks (HOFs) as mild photocatalysts for organic conversions is still considerably challenging. In this work, we synthesized a hydrogen-bonded organic framework (HOF-16) and achieved the photocatalytic oxidation of silanes to generate silanols. Considering the constraints imposed by the framework structure, a significant improvement in the efficacy of singlet oxygen (1O2) generation is observed. HOF-16 exhibits remarkable photocatalytic performance when it comes to silane hydroxylation, displaying high efficiency, low catalyst loading, and good recyclability. This research highlights the immense potential of HOFs in the realm of organic photocatalysis.
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Making full use of the captured energy by phosphorescence light-harvesting systems (PLHSs) and the tunable photoluminescence in energy transfer process to realize the multiple applications is still the challenge of PLHSs research. In this study, we have successfully constructed a highly effective PLHS with tunable multicolor luminescence and efficient conversion of photosensitizer types, which can further be used in photocatalytic organic conversion, information anti-counterfeiting and storage. The supramolecular polymer of BDBP-CB[8], which is generated by cucurbit[8]uril (CB[8]) and 4-(4-bromophenyl)-pyridine derivative (BDBP), realizes a phosphorescence emission and a change in luminescence color. Notably, white light emission was achieved and the logic gate systems were constructed utilizing the application of adjustable luminescence color. More interestingly, PLHS can be constructed by employing BDBP-CB[8] as energy donors, Sulforhodamine 101 (SR101) and Cyanine5 (Cy5) as energy acceptors, which results in a remarkably tunable multicolor photoluminescence to achieve the information storage. Furthermore, we have also found that BDBP-CB[8] can serve as type II photosensitizer for the effective production of singlet oxygen (1O2) during the photooxidation process of styrene in aqueous environments, attaining a remarkable output rate reaching as high as 89 %. Particularly, compared with 1O2 produced by type II photosensitizer BDBP-CB[8], the construction of PLHS can effectively convert type II photosensitizer to type I photosensitizer and efficiently generate superoxide anion radical (O2â¢-), which can be used for photocatalytic cross-dehydrogenative coupling (CDC) reaction in the aqueous solution with a yield of 90 %. Thus, we have created a PLHS that not only achieves tunable multicolor emission for information anti-counterfeiting and storage, but also realizes the conversion of reactive oxygen species (ROS) for different types photocatalytic oxidation reactions.
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Hydrogel-based wearable sensors eventually experience dehydration, which negatively impacts their function, leading to decreased sensitivity. Monitoring the real-time water retention rate and sensing performance of wearable flexible sensors without dismantling them remains a significant difficulty. In this study, a molecule having aggregation-induced emission (AIE) properties in an aqueous environment has been developed and produced, which can combine with anionic guar gum and acrylic acid to create an AIE hydrogel. Wearable sensing electronic devices have the capability to track motion signals at various joints of the human body. Additionally, they can effectively and visually monitor dehydration status during extended periods of operation. The fluorescence intensity of the hydrogel is primarily influenced by the level of aggregation of luminous monomers inside the network. This level of aggregation is predominantly governed by the hydrogel's water retention rate. Hence, the extended duration of hydrogel dehydration can be manifested through alterations in their fluorescence characteristics, which are employed for strain sensing. This approach enables users to assess the water retention of hydrogels with greater efficiency, eliminating the requirement for disassembling them from the completed electrical gadget. In summary, the use of AIE-based fluorescent hydrogels will advance the progress of intelligent wearable electronics.
ABSTRACT
The limited elasticity and inadequate bonding of hydrogels made from guar gum (GG) significantly hinder their widespread implementation in personalized wearable flexible electronics. In this study, we devise GG-based self-adhesive hydrogels by creating an interpenetrating network of GG cross-linked with acrylic, 4-vinylphenylboronic acid, and Ca2+. With the leverage of the dynamic interactions (hydrogen bonds, borate ester bonds, and coordination bonds) between -OH in GG and monomers, the hydrogel exhibits a high stretchability of 700%, superior mechanical stress of 110 kPa, and robust adherence to several substrates. The adhesion strength of 54 kPa on porcine skin is obtained. Furthermore, the self-adhesive hydrogel possesses stable conductivity, an elevated gauge factor (GF), and commendable durability. It can be affixed to the human body as a strain sensor to obtain precise monitoring of human movement behavior. Our research offers possibilities for the development of GG-based hydrogels and applications in wearable electronics and medical monitoring.
Subject(s)
Electric Conductivity , Galactans , Hydrogels , Mannans , Plant Gums , Hydrogels/chemistry , Mannans/chemistry , Plant Gums/chemistry , Galactans/chemistry , Animals , Wearable Electronic Devices , Humans , Swine , Adhesives/chemistryABSTRACT
Recently, there has been a great interest in the study of photocatalysts (PCs) and photosensitizers (PSs) in the field of organic photocatalysis. In the present study, a pure organic thermally activated delayed fluorescence (TADF) molecule 4,4'-(12-(pyridin-4-yl)dibenzo[f,h]pyrido[2,3-b]quinoxaline-3,6-diyl)bis(N,N-diphenylaniline) (DPQ-TPA) was designed and synthesized, which not only have excellent TADF property and small energy splitting (ΔEST), but also can self-assembly in water to form cross-linked nanoparticles with exceptional aggregation-induced emission (AIE) characteristics. DPQ-TPA exhibits excellent remarkable selectivity and notably enhances the production capacity of reactive oxygen species (ROS), particularly 1O2, which was employed as a highly effective photocatalyst in the photooxidation reaction of phosphine and hydroazobenzenes under blue light irradiation with high yields up to 94% and 91%, respectively. This work expands the potential application of (donor-acceptor) D-A type AIE-TADF molecules in photocatalytic organic transformations through supramolecular self-assembly.
ABSTRACT
Benzaldehydes are indispensable building blocks in chemistry. However, the selective oxidation of toluene to benzaldehyde remains an ongoing challenge due to the low oxidation potential of benzaldehyde compared to toluene. We report herein a mild protocol that combines hydrogen atom transfer (HAT) with encapsulated air conditions and suitable catalyst loading for selective oxidation of toluene with high selectivity as well as good functional-group tolerance and a broad substrate scope for the synthesis of various high-value aromatic aldehydes. Moreover, the compatibility of this reaction with toluene derivatives of bioactive molecules further demonstrated the practicality of this approach. Mechanism studies have demonstrated that the collaboration between the oxygen quantity and the HAT catalytic system has a major impact on the high selectivity of the reaction. This study not only showcases the effectiveness of HAT strategies toward selective oxidation of toluene to benzaldehyde, but also provides an approach to controlling the selectivity of HAT reactions.
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Due to the high C-H bond dissociation energy of alkanes, the utilization of alkanes as alkyl radical precursors for C-H functionalization of heteroarenes is synthetically captivating but practically challenging, especially under metal- and photocatalyst-free conditions. We report herein a mild and practical visible-light-mediated method for C-H alkylation of quinoxalin-2(1H)-ones using trifluoroacetic acid as a hydrogen atom transfer reagent and air as an oxidant. This mild protocol was performed under metal- and photocatalyst-free circumstances and presented good functional-group tolerance as well as a broad substrate scope.
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The competitive nature of type II photosensitizers in the transfer of excitation energy for the generation of singlet oxygen (1O2) presents significant challenges in the design of type I photosensitizers to produce the superoxide anion radical (O2Ë-). In this study, we present an efficient method for the direct transformation of type II photosensitizers into type I photosensitizers through the implementation of an artificial light-harvesting system (ALHSs) involving a two-step sequential energy transfer process. The designed supramolecular complex (DNPY-SBE-ß-CD) not only has the ability to generate 1O2 as type II photosensitizers, but also demonstrates remarkable fluorescence properties in aqueous solution, which renders it an efficient energy donor for the development of type I photosensitizers ALHSs, thereby enabling the efficient generation of O2Ë-. Meanwhile, to ascertain the capability and practicality of this method, two organic reactions were conducted, namely the photooxidation reaction of thioanisole and oxidative hydroxylation of arylboronic acids, both of which display a high level of efficiency and exhibit significant catalytic performance. This work provides an efficient method for turning type II photosensitizers into type I photosensitizers by a two-step sequential energy transfer procedure.
ABSTRACT
Supramolecular organic frameworks (SOFs) mostly require high-energy purple or blue light for photocatalytic reactions, while highly abundant and low-energy light systems have rarely been explored. Therefore, it is necessary to construct 2D SOFs for low-energy light-induced photocatalysis. This study describes the design and synthesis of a water-soluble two-dimensional (2D) supramolecular organic framework (TP-SOF) using the host-guest interaction between a triphenylamine derivative (TP-3Py) and cucurbit[8]uril (CB[8]). The formation of the 2D SOF can be attributed to the synergistic impact resulting from the orientated head-to-tail superposition mode between the vinylpyridine arms of TP-3Py and CB[8], which results in a significant redshift in the UV-vis absorption spectrum, especially displaying a strong absorption band in the green light region. The monomeric TP-3Py can effectively produce singlet oxygen (1O2) and realize the photocatalytic oxidation of thioanisole in the aqueous solution. In comparison to monomeric TP-3Py, the confinement effect of CB[8] results in a notable enhancement in the production efficiency of superoxide anion radicals (O2â¢-), exhibiting promising prospects in the field of photocatalytic oxidation reaction, which facilitates the application of TP-SOF as a very efficient photosensitizer for the promotion of the oxidative hydroxylation of arylboronic acids under green light in the aqueous solution, giving a high yield of 91%. The present study not only presents a compelling illustration of photocatalysis utilizing a 2D SOF derived from triphenylamine, but also unveils promising avenues for the photocatalytic oxidation of SOF employing low-energy light systems.
ABSTRACT
Carbon dots (CDs) are a type of carbon-based luminescent material with a zero-dimensional structure and a size of less than 10â nm, which are composed of sp2/sp3 hybrid carbon nuclei and surface functional groups. Because CDs has strong photoluminescence and good light absorption in the ultraviolet and near visible regions, it is an excellent candidate for photocatalytic applications. However, the use of nonmetallic doped CDs as photosensitizers for direct photocatalytic organic reactions has been limited to several scattered reports. Herein, we present nitrogen-doped carbon dots (N-CDs) that has a capability for not only produce reactive oxygen species (ROS), including superoxide anion radical (O2â -) and singlet oxygen (1O2), but also provide an unprecedented high activity of dehalogenative oxyalkylation of styrene with a yield of 93 %. This work develops a novel opportunity to utilize cost-effective and easily accessible CDs for the advancement of photocatalysis.
ABSTRACT
In recent years, there has been a notable surge of interest in the fields of organic and pharmaceutical research about photocatalysts (PCs) and photosensitizers (PSs). In this study, a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) molecule adorned with quaternary ammonium (TMB) functionality was meticulously designed and synthesized. This compound has remarkable characteristics such as exceptional water solubility, great optical qualities, and commendable photostability. It can form a 1:1 complex (TMB-CB[7]) with cucurbit[7]uril (CB[7]) through host-guest interactions in the aqueous solution and shows obvious fluorescence enhancement. The reactive oxygen species (ROS) including superoxide anion radical (O2·-) and singlet oxygen (1O2) generation ability of TMB-CB[7] were promoted compared with that of TMB in the aqueous solution. More interestingly, the ROS generated from TMB-CB[7] can be used as PCs for aerobic cross dehydrogenation coupling reactions and photooxidation reactions in water with high yields of 89 and 95%, respectively. Therefore, the utilization of a host-guest PS presents a novel and environmentally friendly approach for conducting photocatalyzed organic processes under ambient conditions using visible light.
ABSTRACT
An artificial light-harvesting system (ALHS) was developed in aqueous solution by employing the electrostatic co-assembly of a tetraphenylethylene derivative modified with two sulfonate groups (TPE-BSBO) and hyperbranched polyethyleneimine (PEI) as the energy donors, and 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (DBT) as the energy acceptors. The ALHS exhibits not only high efficiency in energy transfer and conversion but also a significant enhancement in the generation of reactive oxygen species (ROS), especially superoxide anion radicals (O2Ë-), facilitating its utilization in photocatalytic oxidation reactions.
ABSTRACT
The development of stimuli-responsive functional fluorescent hydrogels is of great significance for the realization of artificial intelligence. In the present work, we design and synthesize a stimulus-responsive hydrogel embedded with an aggregation-induced emission (AIE) monomer, in which the fluorescence brightness and intensity can be tuned. The hydrogel embedded with tetraphenylethene-grafted-poly[3-sulfopropyl methacrylate potassium salt] (TPE-PSPMA) as the functional element is prepared by the radical polymerization method. Among them, the TPE core exhibits adaptive fluorescence ability through the AIE effect, while the PSPMA chain provides tunable hydrophilic properties under an external stimulus. The effect of different cationic surfactants with different lengths of hydrophobic tails on the fluorescence properties of TPE-PSPMA in solution is systematically investigated. With cationic surfactants, such as cetyltrimethylammonium bromide (CTAB), the fluorescence intensity is gradually tuned from 1059 to 4623. And the fluorescence intensities increase with the growth of hydrophobic tails of surfactants, which results from hydrophobicity-induced electrostatic interactions among surfactants and polymer chains. Furthermore, an obvious tunable fluorescence feature of hydrogel copolymerized TPE-PSPMA is realized, resulting from the change of brightness and the dynamic increase of fluorescence intensity (from 1031 to 3138) for the hydrogel immersed in CTAB solution with different soaking times. Such a typical fluorescence-regulated behavior can be attributed to the AIE of the TPE-PSPMA chain and the electrostatic interaction between the surfactant and the anionic polymer chain. The designed TPE-PSPMA-based hydrogel is responsive to stimuli, inspiring the development of intelligent systems such as soft robots and smart wearables.
ABSTRACT
In the present work, we have designed and synthesized a triphenylamine modified cyanophenylenevinylene derivative (TPCI), which can self-assembly with cucurbit[6]uril (CB[6]) and cucurbit[8]uril (CB[8]) through host-guest interactions to form supramolecular complexes (TPCI-CB[6]) and supramolecular polymers (TPCI-CB[8]) in the aqueous solution. The supramolecular assemblies of TPCI-CB[6] and TPCI-CB[8] not only exhibited high singlet oxygen (1O2) production efficiency as photosensitizers, but also realized the application in the construction of artificial light-harvesting systems due to the excellent fluorescence properties in the aqueous solution. The production efficiency of 1O2 has been effectively improved after the addition of CB[6] and CB[8] for TPCI, which were applied as efficient photosensitizers in the photooxidation reactions of thioanisole and its derivatives with the highest yield of 98% in the aqueous solution. The excellent fluorescence properties of TPCI-CB[6] and TPCI-CB[8] can be used as energy donors in artificial light-harvesting systems with energy acceptors sulforhodamine 101 (SR101) and cyanine dye 5 (Cy5), in which one-step energy transfer processes of TPCI-CB[6]+SR101 and TPCI-CB[8]+Cy5, and a two-step sequential energy transfer process of TPCI-CB[6]+SR101+Cy5 were constructed to simulate the natural photosynthesis system.
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The diagnosis and classification of soft tissue sarcomas (STS) remain challenging because of the rarity and overlapping morphologic manifestations of diverse STS subtypes. Characteristic gene fusions are commonly detected in STS and represent useful diagnostic markers. This study established and validated a custom-designed RNA sequencing panel that identified 64 gene fusions in STS. The analytical performance validation yielded excellent accuracy, with 100% (95% CI, 94.40%-100%) sensitivity and 93.33% (95% CI, 68.05%-99.83%) specificity. Clinical performances were further confirmed with 145 clinical formalin-fixed and paraffin-embedded (FFPE) samples from STS patients. Fusions were detected in 40% of samples (58/145). The common fusions SS18-SSX family, EWSR1-related fusions, COL1A1-PDGFB, FOXO1-associated fusions, and FUS-associated fusions were identified in corresponding STS subtypes. The RNA panel detected specific fusions in several cases where no conclusive diagnosis can be made based on the morphology and immunohistochemistry results. Data collected in this study demonstrate that the RNA fusions panel can better classify STS subtypes and serve as a good supplement for histopathology, exhibiting a great potential for the STS precise diagnosis.
Subject(s)
Oncogene Fusion , Sarcoma , Sequence Analysis, RNA , Soft Tissue Neoplasms , Humans , Gene Fusion , RNA/genetics , RNA/metabolism , Sarcoma/diagnosis , Sarcoma/genetics , Sarcoma/pathology , Soft Tissue Neoplasms/diagnosis , Soft Tissue Neoplasms/genetics , Soft Tissue Neoplasms/pathology , Sequence Analysis, RNA/methodsABSTRACT
In the present work, we designed and synthesized a cationic cyano-substituted p-phenylenevinylene derivative (PPTA), which can form supramolecular assemblies through electrostatic interaction with a type of polyelectrolyte material anionic guar gum (GP5A). A polyelectrolyte-based artificial light-harvesting system (LHS) was constructed by selecting a fluorescent dye sulforhodamine 101 (SR101) that matched its energy level as an energy acceptor. The energy harvested by the acceptors was used in the aqueous phase cross dehydrogenation coupling (CDC) reaction with a yield of up to 87%. In addition, the general applicability of polyelectrolyte materials to build artificial LHS was demonstrated by three other polyelectrolyte materials sodium polyphenylene sulfonate (RSS), sodium carboxymethyl cellulose (CMC), and sodium polyacrylate (PAAS), in which the CDC reaction was also carried out by these three LHSs and obtained high yields. This work not only provides a new method to construct LHSs by using polyelectrolyte materials, but also provides a beneficial exploration for further applying the energy harvested in LHSs to the field of photocatalysis in an aqueous solution.
Subject(s)
Sodium , PolyelectrolytesABSTRACT
OBJECTIVE@#To investigate the association of isolated thyroid peroxidase antibody (TPOAb) positive in the first trimester with fetal growth.@*METHODS@#A total of 16 446 pregnant women were included in the birth cohort study, whose last menstrual period was between May 2016 and April 2019 and with singleton pregnancy. Maternal serum samples were collected when they firstly came for prenatal care in the first trimester. The pregnant women were consecutively seen and followed in the hospital and the information of pregnant women was extracted from the electronic medical information system. The pregnant women were divided into isolated TPOAb positive group (n=1 654) and euthyroid group (n=14 792). Three fetal ultrasound examinations were scheduled during the routine prenatal visits at the hospital and were performed by trained sonographers. All fetal growth indicators were quantified as gestational age- and gender- adjusted standard deviation score (Z-score) using the generalized additive models for location, scale and shape (GAMLSS). Fetal growth indicators included estimated fetal weight (EFW), abdominal circumference (AC), biparietal diameter (BPD), femur length (FL) and head circumference (HC). Fetal growth restriction (FGR) was defined as AC or EFW Z-score<3rd centile based on clinical consensus. Generalized estimating equation (GEE) analysis was applied to assess the association of maternal isolated TPOAb positive with fetal growth. The generalized linear model was further used to analyze the association between isolated TPOAb positive and fetal growth indicator at different gestational ages when the fetal growth indicator was significantly associated with isolated TPOAb positive in the GEE mo-del.@*RESULTS@#The median gestational age at three ultrasound measurements was 23.6 (23.3, 24.1), 30.3 (29.7, 30.9), 37.3 (37.0, 37.7) weeks, respectively. The BPD Z-score was higher in isolated TPOAb positive women, compared with the euthyroid pregnant women after adjustment (β=0.057, 95%CI: 0.014-0.100, P=0.009). The generalized linear model showed the BPD Z-score was higher in the isolated TPOAb positive women at the end of 21-25 weeks (β=0.052, 95%CI: 0.001-0.103, P=0.044), 29-32 weeks (β=0.055, 95%CI: 0.004-0.107, P=0.035) and 36-40 weeks (β=0.068, 95%CI: 0.011-0.125, P=0.020), compared with the euthyroid pregnant women. There was no difference in other fetal growth indicators (EFW, AC, FL and HC) and FGR between the isolated TPOAb positive and euthyroid pregnant women.@*CONCLUSION@#The BPD Z-score was slightly increased in the isolated TPOAb positive pregnant women in the first trimester, while other fetal growth indicators were not changed. The reproducibility and practical significance of this result need to be confirmed.
Subject(s)
Pregnancy , Female , Humans , Pregnancy Trimester, First , Iodide Peroxidase , Cohort Studies , Reproducibility of Results , Fetal Development , Fetal Weight , Fetal Growth Retardation , Ultrasonography, PrenatalABSTRACT
Objective: To investigate the clinicopathological characteristics, pathological diagnosis of Ewing's sarcoma of the central nervous system. Methods: Six cases of Ewing's sarcoma of the central nervous system diagnosed at the First Affiliated Hospital of Nanjing Medical University, Nanjing, China from 2015 to 2022 were collected. The clinical manifestations, histological morphology, immunophenotype and molecular genetics of these cases were analyzed. The related literature was reviewed. Results: There were four males and two females, with a male to female ratio of 2∶1. The onset age was 17-40 years, with a median age of 23 years. All 6 tumors were located in the spinal cord (2 cases of cervical vertebra, 1 case of thoracic vertebra, 2 cases of lumbar vertebra, and 1 case of sacral vertebra). The patients' clinical manifestations were mostly lumbago, weakness and numbness of lower limbs/limbs. In 1 case, the tumor recurred and metastasized to the suprasellar region and the third ventricle. Microscopically, the tumor showed diffuse infiltrative growth. In some cases, the tumor was closely related to the spinal meninges. The tumor cells were arranged in sheet, lobular, thin-rope, and nest-like patterns. Homer-Wright rosette was visible. The tumor cells were small to medium in size, and most of them had scant cytoplasm. A few cells had clear cytoplasm. Some areas were rhabdoid. The tumor cell nuclei showed focal mild pleomorphism. The chromatin was uniform and delicate while the nucleoli were not obvious. Mitosis was commonly seen. The tumor was separated by fibrous connective tissue and may be accompanied by mucinous degeneration. Immunohistochemistry showed that all tumors were positive for CD99, NKX2.2, Fli1, ERG. ATRX, H3K27me3, INI1 and BRG1 were all retained. Immunohistochemical stains for EMA, GFAP and Olig2 were negative. The Ki-67 proliferation index was 30%-70%. EWSR1 break-apart FISH test was positive. Conclusions: Ewing's sarcoma is rare in the central nervous system and needs to be distinguished from a variety of neoplasms with primitive undifferentiated small cell morphology. Immunohistochemistry and molecular genetics may be required for a proper diagnosis.