Non-local and non-Hermitian acoustic metasurfaces.

Acoustic metasurfaces are at the frontier of acoustic functional material research owing to their advanced capabilities of wave manipulation at an acoustically vanishing size. Despite significant progress in the last decade, conventional acoustic metasurfaces are still fundamentally limited by their underlying physics and design principles. First, conventional metasurfaces assume that unit cells are decoupled and therefore treat them individually during the design process. Owing to diffraction, however, the non-locality of the wave field could strongly affect the efficiency and even alter the behavior of acoustic metasurfaces. Additionally, conventional acoustic metasurfaces operate by modulating the phase and are typically treated as lossless systems. Due to the narrow regions in acoustic metasurfaces' subwavelength unit cells, however, losses are naturally present and could compromise the performance of acoustic metasurfaces. While the conventional wisdom is to minimize these effects, a counter-intuitive way of thinking has emerged, which is to harness the non-locality as well as loss for enhanced acoustic metasurface functionality. This has led to a new generation of acoustic metasurface design paradigm that is empowered by non-locality and non-Hermicity, providing new routes for controlling sound using the acoustic version of 2D materials. This review details the progress of non-local and non-Hermitian acoustic metasurfaces, providing an overview of the recent acoustic metasurface designs and discussing the critical role of non-locality and loss in acoustic metasurfaces. We further outline the synergy between non-locality and non-Hermiticity, and delineate the potential of using non-local and non-Hermitian acoustic metasurfaces as a new platform for investigating exceptional points, the hallmark of non-Hermitian physics. Finally, the current challenges and future outlook for this burgeoning field are discussed.

Bioinspired simultaneous regulation in fluorescence of AIEgen-embedded hydrogels.

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.

The Efficacy of Senna Bowel Preparation for Colonoscopy: A Systematic Review and Meta-analysis.

The quality of bowel preparation is an extremely important determinant of colonoscopy results. However, the efficacy of senna regimens in improving bowel cleanliness is uncertain. We conducted a systematic review and meta-analysis to synthesize data on whether using a senna bowel preparation regimen enhances the bowel cleanliness. We searched Web of Science Core Collection, MEDLINE, PubMed, Embase, Cochrane Library, and Scopus databases (from the inception to August 2021). The primary efficacy outcome was bowel cleanliness. Secondary outcomes included patient compliance, tolerance, and adverse events. Eleven trials fulfilled the inclusion criteria (3,343 patients. Overall, we found no significant differences in bowel cleanliness between the senna regimen and other bowel preparation regimens (odds ratio [95% confidence interval]: 1.02 [0.63, 1.67], p = 0.93). There was significant difference in tolerance (odds ratio [95% confidence interval]: 1.66 [1.08, 2.54], p = .02) and compliance (odds ratio [95% confidence interval]: 3.05 [1.42, 6.55], p = .004). The senna regimen yielded a significantly greater proportion of no nausea (odds ratio [95% confidence interval]: 1.84 [1.45, 2.32]) and vomiting (odds ratio [95% confidence interval]: 1.65 [0.81, 3.35]). Compared with other bowel preparation regimens, the senna regimen may be effective and safe in bowel cleaning before colonoscopy, with superior compliance and tolerance.

A supramolecular photosensitizer based on triphenylamine and pyrazine with aggregation-induced emission properties for high-efficiency photooxidation reactions.

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.

Visible-light-mediated direct C3 alkylation of quinoxalin-2(1H)-ones using alkanes.

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.

Tunable multicolor supramolecular assemblies based on phosphorescence cascade energy transfer for photocatalytic organic conversion and anti-counterfeiting.

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 (O2•-), 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.

Exosomes: Another intercellular lipometabolic communication mediators in digestive system neoplasms?

Neoplasms are one of the most concerned public health problems worldwide. Digestive system neoplasms, with a high morbidity and mortality, is one of the most common malignant tumors in human being. It is found that exosomes act as an intercellular communication media to carry the metabolic and genetic information of parental cells to target cells. Likely, exosomes participate in lipid metabolism and regulates multiple processes in digestive system neoplasms, including the information transmission among cancer cells, the formation of neoplastic microenvironment, and the neoplastic biological behaviors like metastasis, invasion, and the chemotherapy resistance. In this review, we firstly introduce the main mechanisms whereas exosomes act as intercellular lipometabolic communication mediator in digestive system neoplasms. Thereafter we introduce the relationship between exosomes lipid metabolism and various type of digestive system neoplasms, including gastric cancer, hepatocellular carcinoma, pancreatic cancer, and colorectal cancer. Eventually, we summarized and prospected the development and implication of exosomes in digestive system neoplasms. The further research of exosomes as intercellular lipid metabolism mediator will contribute to accurate and efficient diagnosis and treatment of digestive system neoplasms.

Construction of an efficient artificial light-harvesting system based on hyperbranched polyethyleneimine and improvement of photocatalytic performance.

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 (O2˙-), facilitating its utilization in photocatalytic oxidation reactions.

Host-Guest Photosensitizer of a Cationic BODIPY Derivative and Cucurbit[7]uril for High-Efficiency Visible Light-Induced Photooxidation Reactions.

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.

Construction of artificial light-harvesting systems based on a variety of polyelectrolyte materials and application in photocatalysis.

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.

Rational Utilization of Intramolecular Hydrogen Bonds to Achieve Blue TADF with EQEs of Nearly 30% and Single Emissive Layer All-TADF WOLED.

A series of highly efficient blue thermally activated delayed fluorescence (TADF) compounds, SON-Cz, SON-tBuCz, and SON-PhCz, were developed. Pyridinyl was introduced as the bridging unit between carbazole donors and sulfone acceptor. Intramolecular hydrogen bonds between the pyridine N atom and carbazole H atoms were detected in single crystals, which suppressed the twisting of carbazole rings and dramatically increased the molecular rigidity. At the same time, tert-butyl or phenyl were incorporated at the 3,6-sites of carbazole ring to tune electron donating ability or enlarge HOMO delocalization. All these hydrogen bonds featured TADF compounds exhibited much improved photoluminescence quantum yields (PLQYs) and excellent efficiencies in their doped blue organic light-emitting diodes. In particular, SON-tBuCz and SON-PhCz exhibited the maximum external quantum efficiencies (EQEs) of 29.59% and 28.22% with CIE coordinates of (0.17, 0.22) and (0.21, 0.36), respectively. The excellent performance benefits from the carbazole structure modification and the intramolecular hydrogen bonds, which bring more rigid structures and eliminate nonradiative transitions. Furthermore, a single emissive layer all-TADF white OLED was fabricated using SON-tBuCz as the blue emitter and 4CzTPN-Ph as the orange emitter to give an EQE of 23.51% with a high CRI of 71, which is among the top efficiencies ever reported for all-TADF WOLEDs so far.

Nf1 Haploinsufficiency Alters Myeloid Lineage Commitment and Function, Leading to Deranged Skeletal Homeostasis.

Although nullizygous loss of NF1 leads to myeloid malignancies, haploinsufficient loss of NF1 (Nf1) has been shown to contribute to osteopenia and osteoporosis which occurs in approximately 50% of neurofibromatosis type 1 (NF1) patients. Bone marrow mononuclear cells of haploinsufficient NF1 patients and Nf1(+/-) mice exhibit increased osteoclastogenesis and accelerated bone turnover; however, the culprit hematopoietic lineages responsible for perpetuating these osteolytic manifestations have yet to be elucidated. Here we demonstrate that conditional inactivation of a single Nf1 allele within the myeloid progenitor cell population (Nf1-LysM) is necessary and sufficient to promote multiple osteoclast gains-in-function, resulting in enhanced osteoclastogenesis and accelerated osteoclast bone lytic activity in response to proresorptive challenge in vivo. Surprisingly, mice conditionally Nf1 heterozygous in mature, terminally differentiated osteoclasts (Nf1-Ctsk) do not exhibit any of these skeletal phenotypes, indicating a critical requirement for Nf1 haploinsufficiency at a more primitive/progenitor stage of myeloid development in perpetuating osteolytic activity. We further identified p21Ras-dependent hyperphosphorylation of Pu.1 within the nucleus of Nf1 haploinsufficient myelomonocytic osteoclast precursors, providing a novel therapeutic target for the potential treatment of NF1 associated osteolytic manifestations.

Hyperactive transforming growth factor-ß1 signaling potentiates skeletal defects in a neurofibromatosis type 1 mouse model.

Dysregulated transforming growth factor beta (TGF-ß) signaling is associated with a spectrum of osseous defects as seen in Loeys-Dietz syndrome, Marfan syndrome, and Camurati-Engelmann disease. Intriguingly, neurofibromatosis type 1 (NF1) patients exhibit many of these characteristic skeletal features, including kyphoscoliosis, osteoporosis, tibial dysplasia, and pseudarthrosis; however, the molecular mechanisms mediating these phenotypes remain unclear. Here, we provide genetic and pharmacologic evidence that hyperactive TGF-ß1 signaling pivotally underpins osseous defects in Nf1(flox/-) ;Col2.3Cre mice, a model which closely recapitulates the skeletal abnormalities found in the human disease. Compared to controls, we show that serum TGF-ß1 levels are fivefold to sixfold increased both in Nf1(flox/-) ;Col2.3Cre mice and in a cohort of NF1 patients. Nf1-deficient osteoblasts, the principal source of TGF-ß1 in bone, overexpress TGF-ß1 in a gene dosage-dependent fashion. Moreover, Nf1-deficient osteoblasts and osteoclasts are hyperresponsive to TGF-ß1 stimulation, potentiating osteoclast bone resorptive activity while inhibiting osteoblast differentiation. These cellular phenotypes are further accompanied by p21-Ras-dependent hyperactivation of the canonical TGF-ß1-Smad pathway. Reexpression of the human, full-length neurofibromin guanosine triphosphatase (GTPase)-activating protein (GAP)-related domain (NF1 GRD) in primary Nf1-deficient osteoblast progenitors, attenuated TGF-ß1 expression levels and reduced Smad phosphorylation in response to TGF-ß1 stimulation. As an in vivo proof of principle, we demonstrate that administration of the TGF-ß receptor 1 (TßRI) kinase inhibitor, SD-208, can rescue bone mass deficits and prevent tibial fracture nonunion in Nf1(flox/-) ;Col2.3Cre mice. In sum, these data demonstrate a pivotal role for hyperactive TGF-ß1 signaling in the pathogenesis of NF1-associated osteoporosis and pseudarthrosis, thus implicating the TGF-ß signaling pathway as a potential therapeutic target in the treatment of NF1 osseous defects that are refractory to current therapies.