Harnessing instability for work hardening in multi-principal element alloys.

The strength-ductility trade-off has long been a Gordian knot in conventional metallic structural materials and it is no exception in multi-principal element alloys. In particular, at ultrahigh yield strengths, plastic instability, that is, necking, happens prematurely, because of which ductility almost entirely disappears. This is due to the growing difficulty in the production and accumulation of dislocations from the very beginning of tensile deformation that renders the conventional dislocation hardening insufficient. Here we propose that premature necking can be harnessed for work hardening in a VCoNi multi-principal element alloy. Lüders banding as an initial tensile response induces the ongoing localized necking at the band front to produce both triaxial stress and strain gradient, which enables the rapid multiplication of dislocations. This leads to forest dislocation hardening, plus extra work hardening due to the interaction of dislocations with the local-chemical-order regions. The dual work hardening combines to restrain and stabilize the premature necking in reverse as well as to facilitate uniform deformation. Consequently, a superior strength-and-ductility synergy is achieved with a ductility of ~20% and yield strength of 2 GPa during room-temperature and cryogenic deformation. These findings offer an instability-control paradigm for synergistic work hardening to conquer the strength-ductility paradox at ultrahigh yield strengths.

Visual Sensor with Host-Guest Specific Recognition and Light-Electrical Co-Controlled Switch.

Perception of UV radiation has important applications in medical health, industrial production, electronic communication, etc. In numerous application scenarios, there is an increasing demand for the intuitive and low-cost detection of UV radiation through colorimetric visual behavior, as well as the efficient and multi-functional utilization of UV radiation. However, photodetectors based on photoconductive modes or photosensitive colorimetric materials are not conducive to portable or multi-scene applications owing to their complex and expensive photosensitive components, potential photobleaching, and single-stimulus response behavior. Here, a multifunctional visual sensor based on the "host-guest photo-controlled permutation" strategy and the "lock and key" model is developed. The host-guest specific molecular recognition and electrochromic sensing platform is integrated at the micro-molecular scale, enabling multi-functional and multi-scene applications in the convenient and fast perception of UV radiation, military camouflage, and information erasure at the macro level of human-computer interaction through light-electrical co-controlled visual switching characteristics. This light-electrical co-controlled visual sensor based on an optoelectronic multi-mode sensing system is expected to provide new ideas and paradigms for healthcare, microelectronics manufacturing, and wearable electronic devices owing to its advantages of signal visualization, low energy consumption, low cost, and versatility.

A comprehensive metabolic map reveals major quality regulations in red-flesh kiwifruit (Actinidia chinensis).

Kiwifruit (Actinidia chinensis) is one of the popular fruits world-wide, and its quality is mainly determined by key metabolites (sugars, flavonoids, and vitamins). Previous works on kiwifruit are mostly done via a single omics approach or involve only limited metabolites. Consequently, the dynamic metabolomes during kiwifruit development and ripening and the underlying regulatory mechanisms are poorly understood. In this study, using high-resolution metabolomic and transcriptomic analyses, we investigated kiwifruit metabolic landscapes at 11 different developmental and ripening stages and revealed a parallel classification of 515 metabolites and their co-expressed genes into 10 distinct metabolic vs gene modules (MM vs GM). Through integrative bioinformatics coupled with functional genomic assays, we constructed a global map and uncovered essential transcriptomic and transcriptional regulatory networks for all major metabolic changes that occurred throughout the kiwifruit growth cycle. Apart from known MM vs GM for metabolites such as soluble sugars, we identified novel transcription factors that regulate the accumulation of procyanidins, vitamin C, and other important metabolites. Our findings thus shed light on the kiwifruit metabolic regulatory network and provide a valuable resource for the designed improvement of kiwifruit quality.

Integrative Analysis of Metabolome and Transcriptome Reveals the Mechanism of Color Formation in Yellow-Fleshed Kiwifruit.

During the development of yellow-fleshed kiwifruit (Actinidia chinensis), the flesh appeared light pink at the initial stage, the pink faded at the fastest growth stage, and gradually changed into green. At the maturity stage, it showed bright yellow. In order to analyze the mechanism of flesh color change at the metabolic and gene transcription level, the relationship between color and changes of metabolites and key enzyme genes was studied. In this study, five time points (20 d, 58 d, 97 d, 136 d, and 175 d) of yellow-fleshed kiwifruit were used for flavonoid metabolites detection and transcriptome, and four time points (20 d, 97 d, 136 d, and 175 d) were used for targeted detection of carotenoids. Through the analysis of the content changes of flavonoid metabolites, it was found that the accumulation of pelargonidin and cyanidin and their respective anthocyanin derivatives was related to the pink flesh of young fruit, but not to delphinidin and its derivative anthocyanins. A total of 140 flavonoid compounds were detected in the flesh, among which anthocyanin and 76% of the flavonoid compounds had the highest content at 20 d, and began to decrease significantly at 58 d until 175 d, resulting in the pale-pink fading of the flesh. At the mature stage of fruit development (175 d), the degradation of chlorophyll and the increase of carotenoids jointly led to the change of flesh color from green to yellow, in addition to chlorophyll degradation. In kiwifruit flesh, 10 carotenoids were detected, with none of them being linear carotenoids. During the whole development process of kiwifruit, the content of ß-carotene was always higher than that of α-carotene. In addition, ß-cryptoxanthin was the most-accumulated pigment in the kiwifruit at 175 d. Through transcriptome analysis of kiwifruit flesh, seven key transcription factors for flavonoid biosynthesis and ten key transcription factors for carotenoid synthesis were screened. This study was the first to analyze the effect of flavonoid accumulation on the pink color of yellow-fleshed kiwifruit. The high proportion of ß-cryptoxanthin in yellow-fleshed kiwifruit was preliminarily found. This provides information on metabolite accumulation for further revealing the pink color of yellow-fleshed kiwifruit, and also provides a new direction for the study of carotenoid biosynthesis and regulation in yellow-fleshed kiwifruit.

Phase Transition to Heptagonal-Cluster-Packed Structure of Gold Nanoribbons.

Transforming periodic crystals into packing of atomic clusters is attracting enormous interest for both fundamental research and potential application, but it still remains a big challenge for noble metals. Here, we have observed gold nanoribbons packed with heptagonal clusters, where every two or three constituent clusters connect edge-to-edge with their neighbors. This is the first reported metallic structure packed from building blocks with heptagonal symmetry. The cluster-packed nanoribbons transited from two-dimensional hexagonal structure under tensile condition and a reverse transition occurred by compression, resolved by in situ observation. The cluster-packed structure was stabilized by the s-d orbital hybridization. Theoretical calculations demonstrate that the conductance of the ribbons undergoes a quantized change from 6 to 4 G0 (G0 = 2e2/h) during the phase transition and backward for the reverse transition.

Integrative analyses of metabolome and genome-wide transcriptome reveal the regulatory network governing flavor formation in kiwifruit (Actinidia chinensis).

Soluble sugars, organic acids and volatiles are important components that determine unique fruit flavor and consumer preferences. However, the metabolic dynamics and underlying regulatory networks that modulate overall flavor formation during fruit development and ripening remain largely unknown for most fruit species. In this study, by integrating flavor-associated metabolism and transcriptome data from 12 fruit developmental and ripening stages of Actinidia chinensis cv Hongyang, we generated a global map of changes in the flavor-related metabolites throughout development and ripening of kiwifruit. Using this dataset, we constructed complex regulatory networks allowing to identify key structural genes and transcription factors that regulate the metabolism of soluble sugars, organic acids and important volatiles in kiwifruit. Moreover, our study revealed the regulatory mechanism involving key transcription factors regulating flavor metabolism. The modulation of flavor metabolism by the identified key transcription factors was confirmed in different kiwifruit species providing the proof of concept that our dataset provides a suitable tool for clarification of the regulatory factors controlling flavor biosynthetic pathways that have not been previously illuminated. Overall, in addition to providing new insight into the metabolic regulation of flavor during fruit development and ripening, the outcome of our study establishes a foundation for flavor improvement in kiwifruit.

Diastereoselective Access to Triazolo[1,2-a]indolines via a Bio-Inspired Oxidative Cyclization of NH-Indoles.

Establishing three-dimensional chemicals by using the C2-C3 π bond of indoles has always been a research hotspot in organic synthesis; however, employing the oxidative C2-C3 π bond of indoles to generate imine which would lead to the N1-C2 π bond cyclization under metal-free conditions is still rare. Here, we report a bio-inspired synthesis of triazolo[1,2-a]indolines by the oxidative cyclization between NH-indoles and azomethine imines with 3,3-dimethyldioxirane as the sole oxidant under metal-free and mild conditions. This finding represents an elegant instance of tri-functionalization of NH-indoles, which provides rapid access to a broad range of triazolo[1,2-a]indolines with tetrahydroisoquinolines in one single step. Up to 86% yield and above 20:1 dr value are observed. The radical mechanism and proton migration process have been speculated.

Design, synthesis, biological evaluation and molecular modeling of N-isobutyl-N-((2-(p-tolyloxymethyl)thiazol-4yl)methyl)benzo[d][1,3] dioxole-5-carboxamides as selective butyrylcholinesterase inhibitors.

Butyrylcholinesterase (BuChE) is recently regarded as a biomarker in progressed Alzheimer's disease (AD). Development of selective BuChE inhibitors has attracted a great deal of interest and may be a viable therapeutic strategy for AD. Recently, we reported the N-isobutyl-N-((2-(p-tolyloxymethyl)thiazol-4-yl)methyl)benzo[d][1,3]dioxole-5-carboxamide (1) as a selective BuChE inhibitor. Subsequently, 33 analogs were synthesized and assessed by AChE/BuChE activities, indicating an optimal compound 23. Further kinetic tests suggested a competitive manner. Molecular docking and Molecular dynamics (MD) simulation showed that it interacted with several residues in active site gorge of BuChE, possibly contributing to its selectivity and competitive pattern. Moreover, it showed low cytotoxicity and high blood brain barrier (BBB) permeability. Taken together, 23 was a promising BuChE inhibitor for the treatment of AD.

Recent Advances in Two-Photon AIEgens and Their Application in Biological Systems.

Two-photon fluorescence imaging technology has the advantages of high light stability, little light damage, and high spatiotemporal resolution, which make it a powerful biological analysis method. However, due to the high concentration or aggregation state of traditional organic light-emitting molecules, the fluorescence intensity is easily reduced or disappears completely, and is not conducive to optimal application. The concept of aggregation-induced emission (AIE) provides a solution to the problem of aggregation-induced luminescence quenching (ACQ), and realizes the high fluorescence quantum yield of luminescent molecules in the aggregation state. In addition, two-photon absorption properties can readily be improved just by increasing the loading content of AIE fluorogen (AIEgen). Therefore, the design and preparation of two-photon fluorescence probes based on AIEgen to achieve high-efficiency fluorescence imaging in vitro/in vivo has become a major research hotspot. This review aims to summarize representative two-photon AIEgens based on triphenylamine, tetraphenylethene, quinoline, naphthalene and other new structures from the past five years, and discuss their great potential in bioimaging applications.

Utility of Ultra-Wide-Field Imaging for Screening of AIDS-Related Cytomegalovirus Retinitis.

PURPOSE: To explore the potential use of ultra-wide-field (UWF) imaging for screening of cytomegalovirus retinitis (CMVR) in AIDS patients. METHODS: Ninety-four patients whose CD4 count was below 200 cells/µL were enrolled in a prospective study. Each patient underwent UWF imaging and indirect ophthalmoscopy. The main outcome measures were the concordance and detection rates of these 2 approaches and the sensitivity and specificity of UWF imaging. RESULTS: Twenty-seven eyes in 18 patients were diagnosed with CMVR by the indirect ophthalmoscopy. UWF imaging missed the diagnosis in 1 eye because of a zone 3 CMVR lesion. The UWF image showed several CMVR patterns and locations: hemorrhagic necrotizing lesion, granular lesion, frosted branch angiitis, and optic neuropathy lesion. The concordance of the 2 approaches was excellent for the diagnosis of CMVR, classification of CMVR pattern, and location of CMVR. The detection rates of UWF imaging and indirect ophthalmoscopy were 14.0% (26/186; 95% CI 0.089-0.190) and 14.5% (27/186; 95% CI 0.094-0.196), respectively (p = 1.000). The sensitivity and specificity of UWF imaging were 96.3 and 100%, respectively. CONCLUSIONS: UWF imaging is capable of documentation of different CMVR lesions and AIDS-related CMVR screening when examination by an ophthalmologist is not available.

Free-standing Monatomic Thick Two-dimensional Gold.

Monolayer metal membranes have attracted research attention owing to their fascinating physical properties. Unlike layered materials with weak interlayer van der Waals bonding, metallic monolayer membranes are difficult to exfoliate due to strong metallic bonding between layers. Here, we fabricate free-standing monatomic-thick Au membranes and nanoribbons framed in bulk crystals using in situ dealloying inside transmission electron microscope. The Au membranes are robust under high energy electron beam. Monatomic-thick nanoribbons with a minimal width of 0.6 nm are observed. First-principles calculations reveal that zigzag-edged nanoribbons are ferromagnetic with magnetic moments ranging 0.38-0.51 µB per unit-cell for a width less than 0.9 nm. In addition, a linear relationship between the bond length and the coordination number of atoms is directly investigated using atomic resolution images of monolayer and bilayer Au membranes. This work provides a pathway for direct fabrication of metal membranes and nanoribbons and to achieve novel physical properties.

Nutritional component analyses of kiwifruit in different development stages by metabolomic and transcriptomic approaches.

BACKGROUND: Metabolites in kiwifruit greatly influence nutritional values; however, the dynamic changes in nutrient composition and the gene expression level of yellow kiwifruit have not been studied so far. To investigate the types and accumulation patterns of metabolites, a metabolomics approach utilizing liquid chromatography-electrospray ionization mass spectrometry and transcriptomics were used to analyze the yellow flesh of kiwifruit cultivar 'jinshi 1' collected at different stages of days after full bloom. RESULTS: In total, 285 metabolites were identified over the kiwifruit developmental stages. The composition of the metabolites of kiwifruit at different stages of development was different. The organic acids contents and their derivatives were higher at the initial stage of development and then gradually decreased. The lipids and amino acids contents fluctuated at different stages of development but did not change significantly. Transcript profiles throughout yellow kiwifruit development were constructed and analyzed, with a focus on the biosynthesis and metabolism of compounds such as sugars, organic acids and ascorbic acid, which are indispensable for the development and formation of quality fruit. The transcript levels of genes involved in sucrose and starch metabolism were consistent with the change in soluble sugar and starch content throughout kiwifruit development. The metabolism of ascorbic acid was primarily through the l-galactose pathway. CONCLUSION: Our metabolome and transcriptome approach identified dynamic changes in five types of nutrient metabolite levels, and correlations among such levels, in developing fruit. The results provide information that can be used by metabolic engineers and molecular breeders to improve kiwifruit quality. © 2020 Society of Chemical Industry.

Adsorption and mechanistic study of the invasive plant-derived biochar functionalized with CaAl-LDH for Eu(III) in water.

Herein, we developed the invasive plant-derived biochar (IPB) functionalized with CaAl-LDH at five mass ratios using a physical mixture method, assessed their adsorption perform for Eu(III), and explored the relative mechanisms. Results show that the IPB successfully loaded CaAl-LDH in five composites and their Eu(III) sorption affinities were strongly affected by solution pH, contact time, temperature, and the mass ratio of LDH and IPB. All the sorpiton process for Eu(III) occurred on the heterogeneous surface of five composites and the boundary layer diffusion limited the chemical sorption rate. Interestingly, the CaAl-LDH/IPB composite with high ratio of IPB had higher sorption capacity than the one with high ratio of LDH due to larger porosity of the former. Three mechanisms containing ion exchange between Al and Eu ions, surface complexation with carboxyl- and oxygen-containing functional groups, and precipitation were involved in the Eu(III) sorption, but the dominant sorption mechanism for each CaAl-LDH/IPB composite differed with different mass ratio of CaAl-LDH and IPB. In composite with more IPB (e.g., CaAl-LDH/IPB-13), both ion exchange and surface complexes dominated the sorption process and the intensity of Eu3+ was identified with the one of Eu2O3. Whereas in composites with high LDH, ion exchange dominated the sorption and the intensity of Eu3+ was obviously higher than the one of Eu2O3. This research will provide a new perspective for the application of the LDH/biochar materials.

Design and synthesis of a new fluorescent probe for cascade detection of Zn2+ and H2 PO4 - in water and targeted imaging of living cells.

Design and synthesis of new fluorescence probes with good water-solubility is of great importance to better understanding the significant role of ions which are related to biology and the environment. As important ions, zinc ion (Zn2+ ) and dihydrogen phosphate ion (H2 PO4 - ) display essential roles in living systems, and quantitative detection of these ions in water is still a challenge. In order to consider the significant role of the galactose moiety in the design of a water-soluble fluorescence sensor, herein, we have developed a novel probe, Gal-AQTF, for the cascade detection of Zn2+ and H2 PO4 - with excellent selectivity in water. Through the introduction of the galactose moiety onto the sensor AQTF, which has been reported earlier by us, the water-solubility, cell compatibility and targeting ability were enhanced. Gal-AQTF has been successfully applied in the imaging of the living cells of HepG2 and A549, and illustrated good selectivity for the HepG2 cells which overly express the asialoglycoprotein (ASGP) receptor.

Size-Dependent Grain-Boundary Structure with Improved Conductive and Mechanical Stabilities in Sub-10-nm Gold Crystals.

Low-angle grain boundaries generally exist in the form of dislocation arrays, while high-angle grain boundaries (misorientation angle >15°) exist in the form of structural units in bulk metals. Here, through in situ atomic resolution aberration corrected electron microscopy observations, we report size-dependent grain-boundary structures improving both stabilities of electrical conductivity and mechanical properties in sub-10-nm-sized gold crystals. With the diameter of a nanocrystal decreasing below 10 nm, the high-angle grain boundary in the crystal exists as an array of dislocations. This size effect may be of importance to a new generation of interconnects applications.

Synthesis and anti-tumor activity of glycosyl oxadiazoles derivatives.

A new series of glycosyl oxadiazoles compounds were synthesized and characterized through (1)H NMR, (13)C NMR, IR and HRMS. The anti-tumor activities for MDA-MB-231 of all these new compounds were screened in vitro by MTT assay. Due to the modification of gastrodin analogues, the anti-tumor activities of these 1,3,4-oxadiazoles derivatives were greatly improved. Six compounds (6 c, 6 d, 6 i, 6 j, 6 k and 6 l) displayed relatively higher MDA-MB-231 potency with IC50 values (0.89, 0.26, 1.35, 3.60, 0.95 and 1.08 µM) compared with the reference medicine Rosiglitazone (5.23 µM).

Subfoveal choroidal thickness: the Beijing Eye Study.

PURPOSE: To study subfoveal choroidal thickness (SFCT) in adult Chinese subjects and its correlation with ocular biometric parameters, refractive error, and age. DESIGN: Population-based longitudinal study. PARTICIPANTS: The population-based Beijing Eye Study 2011 included 3468 individuals with a mean age of 64.6±9.8 years (range, 50-93 years). METHODS: A detailed ophthalmic examination was performed, including spectral-domain optical coherence tomography (SD-OCT) with enhanced depth imaging for measurement of SFCT. MAIN OUTCOME MEASURES: Subfoveal choroidal thickness. RESULTS: The SFCT measurements were available for 3233 subjects (93.2%). Mean SFCT was 253.8±107.4 µm (range, 8-854 µm). In multivariate analysis, SFCT increased with younger age (P<0.001; correlation coefficient r=4.12; beta coefficient=0.37), shorter axial length (P<0.001; r=44.7; beta coefficient=0.46), male gender (P<0.001; r=28.5; beta coefficient=-0.13), deeper anterior chamber depth (P<0.001; r=39.3; beta coefficient=0.13), thicker lens (P<0.001; r=26.8; beta coefficient=0.08), flatter cornea (P<0.001; r=46.0; beta coefficient=0.11), and better best-corrected visual acuity (BCVA) (logarithm of minimal angle of resolution; P=0.001; r=48.4; beta coefficient=0.06). In multivariate analysis, SFCT was not significantly associated with blood pressure, ocular perfusion pressure, intraocular pressure, cigarette smoking, alcohol consumption, serum concentrations of lipids and glucose, diabetes mellitus, and arterial hypertension. In the myopic refractive error range of more than -1 diopter (D), SFCT decreased by 15 µm (95% confidence interval [CI], 11.9-18.5) for every increase in myopic refractive error of 1 D, or by 32 µm (95% CI, 37.1-26.0) for every increase in axial length of 1 mm. For each year increase in age, the SFCT decreased by 4.1 µm (95% CI, 4.6-3.7) (multivariate analysis). CONCLUSIONS: Subfoveal choroidal thickness with a mean of 254±107 µm in elderly subjects with a mean age of 65 years decreased with age (4 µm per year of age) and myopia (15 µm per diopter [D] of myopia). It was also associated with male gender and the ocular biometric parameters of a deeper anterior chamber and thicker lens. The association between SFCT and BCVA indicates a functional aspect of SFCT. FINANCIAL DISCLOSURE(S): The author(s) have no proprietary or commercial interest in any materials discussed in this article.

Subfoveal choroidal thickness in diabetes and diabetic retinopathy.

PURPOSE: To examine subfoveal choroidal thickness (SFCT) in patients with diabetes mellitus and patients with diabetic retinopathy. DESIGN: Population-based, cross-sectional study. PARTICIPANTS: The population-based Beijing Eye Study 2011 included 3468 individuals with a mean age of 64.6 ± 9.8 years (range, 50-93 years). METHODS: A detailed ophthalmic examination was performed including spectral-domain optical coherence tomography (OCT) with enhanced depth imaging for measurement of SFCT and fundus photography for the assessment of diabetic retinopathy. MAIN OUTCOME MEASURES: Subfoveal choroidal thickness. RESULTS: Fasting blood samples, fundus photographs, and choroidal OCT images were available for 2041 subjects (58.8%), with 246 subjects (12.1 ± 0.7%) fulfilling the diagnosis of diabetes mellitus and 23 subjects having diabetic retinopathy. Mean SFCT did not differ significantly between patients with diabetes mellitus and nondiabetic subjects (266 ± 108 vs. 261 ± 103 µm; P=0.43) nor between patients with diabetic retinopathy and subjects without retinopathy (249 ± 86 vs. 262 ± 104 µm; P = 0.56). After adjustment for age, sex, axial length, lens thickness, anterior chamber depth, corneal curvature radius, and best-corrected visual acuity, SFCT was associated with a higher glycosylated hemoglobin (HbA1c) value (P<0.001; regression coefficient B, 8.18; 95% confidence interval [CI], 4.02-12.3); standardized coefficient ß, 0.08) or with the presence of diabetes mellitus (P = 0.001; B, 21.3; 95% CI, 9.12-33.5) but not with presence of diabetic retinopathy (P = 0.61) or stage of diabetic retinopathy (P = 0.14). As a corollary, after adjusting for age, region of habitation, body mass index, systolic and diastolic blood pressure, and level of education, diabetes mellitus was associated with a thicker SFCT (P<0.001). In contrast, neither presence of diabetic retinopathy (P = 0.61) nor stage of diabetic retinopathy (P = 0.09) were associated significantly with SFCT after adjusting for body mass index, diastolic and systolic blood pressure, and level of education and after adjusting for blood glucose concentrations, HbA1c value, diagnosis of diabetes mellitus, and systolic and diastolic blood pressure, respectively. CONCLUSIONS: Patients with diabetes mellitus had a slightly, but statistically significantly, thicker subfoveal choroid, whereas presence and stage of diabetic retinopathy were not associated additionally with an abnormal SFCT. Whereas diabetes mellitus as a systemic disease leads to a slight thickening of the choroid, diabetic retinopathy as an ocular disorder was not associated with choroidal thickness abnormalities after adjusting for the presence of diabetes mellitus. FINANCIAL DISCLOSURE(S): The author(s) have no proprietary or commercial interest in any materials discussed in this article.

A novel enzyme-catalyzed synthesis of N-substituted pyrrole derivatives.

A novel method for the synthesis of substituted pyrroles catalyzed by α-amylase from hog pancreas via Paal-Knorr reaction was developed. A series of pyrrole derivatives were synthesized under mild conditions and the products were obtained with good to excellent yields (60-99 %). The impact of factors, such as solvents, enzyme amount, and temperature, on the reaction were investigated. This study reports an efficient route for the synthesis of N-substituted pyrrole derivatives.