Photoactive conjugated microporous polymers (CMPs) are emerging as porous materials capable of mediating the photocatalytic evolution of H
2
from water. In this study, we synthesized three ...pyrene-based CMPs (Py-F-CMP, Py-TPA-CMP, Py-TPE-CMP) through Sonogashira-Hagihara cross-couplings of 1,3,6,8-tetraethynylpyrene (Py-T, as a common monomer building block) with 2,7-dibromo-9
H
-fluorene (F-Br
2
), tris(4-bromophenyl)amine (TPA-Br
3
), and 1,1,2,2-tetrakis(4-bromophenyl)ethene (TPE-Br
4
), respectively, in the presence of Pd(PPh
3
)
4
in DMF/Et
3
N. We then characterized the chemical structures, crystallinities, thermal stabilities, surface morphologies, and porosities of these three new CMPs. Brunauer-Emmett-Teller (BET) analyses and tests of photocatalytic H
2
production revealed that Py-TPA-CMP displayed the highest BET surface area (454 m
2
g
−1
), highest total pore volume (0.28 cm
3
g
−1
), highest H
2
evolution rate (19 200 μmol h
−1
g
−1
), and highest apparent quantum yield (15.3%) when compared with those of Py-F-CMP, Py-TPE-CMP, and other organic porous materials.
Pyrene based conjugated microporous polymers (CMPs) as photocatalysts with promising H
2
production efficiencies and very high stability.
Hexagonally ordered covalent organic frameworks (COFs) are interesting new crystalline porous materials that have massive potential for application in gas storage. Herein, we report the synthesis of ...two series of two-dimensional hexagonally ordered COFs—TPA-COFs and TPT-COFs—through one-pot polycondensations of tris(4-aminophenyl)amine (TPA-3NH2) and 2,4,6-tris(4-aminophenyl)triazine (TPT-3NH2), respectively, with triarylaldehydes featuring different degrees of planarity, symmetry, and nitrogen content. All the synthesized COFs exhibited high crystallinity, large BET surface areas (up to 1747 m2 g−1), excellent thermal stability, and pore size distributions from 1.80 to 2.55 nm. The symmetry and planarity of the monomers strongly affected the degrees of crystallinity and the BET surface areas of the resultant COFs. In addition, these COFs displayed excellent CO2 uptake efficiencies of up to 65.65 and 92.38 mg g−1 at 298 and 273 K, respectively. The incorporation of the more planar and higher-nitrogen-content triaryltriazine unit into the backbones of the TPA-COFs and TPT-COFs enhanced the interactions with CO2, leading to higher CO2 uptakes. Moreover, the synthesized COFs exhibited electrochemical properties because of their conjugated structures containing redox-active triphenylamine groups. This study exposes the importance of considering the symmetry and planarity of the monomers when designing highly crystalline COFs; indeed, the structures of COFs can be tailored to vary their functionalities for specific applications.
Certain human traits such as neurodevelopmental disorders (NDs) and congenital anomalies (CAs) are believed to be primarily genetic in origin. However, even after whole-genome sequencing (WGS), a ...substantial fraction of such disorders remain unexplained. We hypothesize that some cases of ND-CA are caused by aberrant DNA methylation leading to dysregulated genome function. Comparing DNA methylation profiles from 489 individuals with ND-CAs against 1534 controls, we identify epivariations as a frequent occurrence in the human genome. De novo epivariations are significantly enriched in cases, while RNAseq analysis shows that epivariations often have an impact on gene expression comparable to loss-of-function mutations. Additionally, we detect and replicate an enrichment of rare sequence mutations overlapping CTCF binding sites close to epivariations, providing a rationale for interpreting non-coding variation. We propose that epivariations contribute to the pathogenesis of some patients with unexplained ND-CAs, and as such likely have diagnostic relevance.
•Heat resistance of S. diastaticus is readily lost in the absence of selection.•S. diastaticus can rapidly acquire heat resistance by exposure to heat.•Increased heat resistance of S. diastaticus is ...likely caused by genomic changes.
The main fungal cause of spoilage of carbonated fermented beverages in the brewing industry is the amylolytic budding yeast Saccharomyces cerevisiae subsp. diastaticus (Saccharomyces diastaticus). Heat treatment is used to avoid microbial spoilage of the fermented beverages. Therefore, the spoilage capacity of S. diastaticus may be linked to its relative high heat resistance. Here, we assessed whether S. diastaticus can acquire heat resistance when exposed to heat stress. To this end, ascospores of S. diastaticus strain MB523 were treated at 60°C for 10 min followed by growing the surviving spores on a glucose-containing medium. The resulting vegetative cells were then allowed to sporulate again in sporulation medium. This cycle of heat treatment, vegetative growth, and sporulation was performed eight times in three independent lineages. After these eight cycles, the sporulation rate was similar to the start (∼75%) but the resulting ascospores were more heat resistant. The time needed to kill 90% of the population at 60°C (i.e. the D60-value) increased from 6.5 to 9.0 min (p = 0.005). The vegetative cells also showed a trend to increased heat resistance with an increase in the D52-value from 9.2 to 16.2 min (p = 0.1). In contrast, heat resistance of the vegetative cells that had not been exposed to heat during the eight cycles had been reduced with a D52-value of 4.2 min (p = 0.003). Together, these data show that S. diastaticus MB523 can easily acquire heat resistance by inbreeding while subjected to heat stress. Conversely, heat resistance can be easily lost in the absence of this stress condition, indicative of a trade-off for heat resistance.
Loss-of-function variants in ANKRD11 were identified as the cause of KBG syndrome, an autosomal dominant syndrome with specific dental, neurobehavioural, craniofacial and skeletal anomalies. We ...present the largest cohort of KBG syndrome cases confirmed by ANKRD11 variants reported so far, consisting of 20 patients from 13 families. Sixteen patients were molecularly diagnosed by Sanger sequencing of ANKRD11, one familial case and three sporadic patients were diagnosed through whole-exome sequencing and one patient was identified through genomewide array analysis. All patients were evaluated by a clinical geneticist. Detailed orofacial phenotyping, including orthodontic evaluation, intra-oral photographs and orthopantomograms, was performed in 10 patients and revealed besides the hallmark feature of macrodontia of central upper incisors, several additional dental anomalies as oligodontia, talon cusps and macrodontia of other teeth. Three-dimensional (3D) stereophotogrammetry was performed in 14 patients and 3D analysis of patients compared with controls showed consistent facial dysmorphisms comprising a bulbous nasal tip, upturned nose with a broad base and a round or triangular face. Many patients exhibited neurobehavioural problems, such as autism spectrum disorder or hyperactivity. One-third of patients presented with (conductive) hearing loss. Congenital heart defects, velopharyngeal insufficiency and hip anomalies were less frequent. On the basis of our observations, we recommend cardiac assessment in children and regular hearing tests in all individuals with a molecular diagnosis of KBG syndrome. As ANKRD11 is a relatively common gene in which sequence variants have been identified in individuals with neurodevelopmental disorders, it seems an important contributor to the aetiology of both sporadic and familial cases.
Abstract
Nickel-based complex oxides have served as a playground for decades in the quest for a copper-oxide analog of the high-temperature superconductivity. They may provide clues towards ...understanding the mechanism and an alternative route for high-temperature superconductors. The recent discovery of superconductivity in the infinite-layer nickelate thin films has fulfilled this pursuit. However, material synthesis remains challenging, direct demonstration of perfect diamagnetism is still missing, and understanding of the role of the interface and bulk to the superconducting properties is still lacking. Here, we show high-quality Nd
0.8
Sr
0.2
NiO
2
thin films with different thicknesses and demonstrate the interface and strain effects on the electrical, magnetic and optical properties. Perfect diamagnetism is achieved, confirming the occurrence of superconductivity in the films. Unlike the thick films in which the normal-state Hall-coefficient changes signs as the temperature decreases, the Hall-coefficient of films thinner than 5.5 nm remains negative, suggesting a thickness-driven band structure modification. Moreover, X-ray absorption spectroscopy reveals the Ni-O hybridization nature in doped infinite-layer nickelates, and the hybridization is enhanced as the thickness decreases. Consistent with band structure calculations on the nickelate/SrTiO
3
heterostructure, the interface and strain effect induce a dominating electron-like band in the ultrathin film, thus causing the sign-change of the Hall-coefficient.
To identify the risk factors associated with failure of tube shunt surgery.
Pooled analysis of 3 prospective multicenter, randomized clinical trials.
A total of 621 patients with medically ...uncontrolled glaucoma were enrolled, including 276 from the Ahmed Baerveldt Comparison Study, 238 from the Ahmed Versus Baerveldt Study, and 107 from the tube group of the Tube Versus Trabeculectomy Study. Patients were randomized to treatment with an Ahmed glaucoma valve (model FP7) or Baerveldt glaucoma implant (model 101-350). The associations between baseline risk factors and tube shunt failure were assessed using a Cox proportional hazards regression model. The primary outcome measure was the rate of surgical failure defined as intraocular pressure (IOP) > 21 mmHg or reduced < 20% from baseline, IOP ≤ 5 mmHg, loss of light perception vision, reoperation for glaucoma, or removal of implant.
The cumulative probability of failure after tube shunt surgery was 38.3% after 5 years. In multivariable analyses, baseline factors that predicted tube shunt failure included preoperative IOP (≤ 21 mmHg compared to IOP > 21 and ≤ 25 mmHg; HR, 2.34; 95% CI, 1.52-3.61; P < .001), neovascular glaucoma (HR, 1.79; 95% CI, 1.28-2.52; P = .001), randomized treatment (for Ahmed glaucoma valve; HR, 1.36; 95% CI, 1.04-1.78; P = .025), and age (for 10 year decrease in age; HR, 1.19; 95% CI, 1.09–1.31; P < .001).
Lower preoperative IOP, neovascular glaucoma, Ahmed implantation, and younger age were predictors of tube shunt failure. This Study provides the largest prospectively collected dataset on tube shunt surgery.
In this study, exome sequencing yielded a genetic diagnosis in 16% of patients who had previously been evaluated to rule out known causes of intellectual disability.
Severe intellectual disability, ...which is also referred to as cognitive impairment or mental retardation, affects approximately 0.5% of the population in Western countries
1
,
2
and represents an important health burden. A clinical diagnosis of severe intellectual disability is generally based on an IQ of less than 50 and substantial limitations in activities of daily living. In early childhood, the diagnosis is based on substantial developmental delays, including motor, cognitive, and speech delays. Children with different nonsyndromic forms of intellectual disability are clinically indistinguishable.
Intellectual disability can be caused by nongenetic factors, such as infections and perinatal asphyxia. In developed countries, . . .
Covalent organic frameworks (COFs) are promising photocatalysts for treating organic pollutants and solar-to-hydrogen conversion; however, their suboptimal energy band structure and rapid charge ...recombination limit their photocatalytic performance. Herein, we synthesized two donor-acceptor hetero6radialene-based TFP 3D COFs, TFP-Py and TFP-BF, with a unique 3,4-linked ffc topological structure for the adsorptive and photocatalytic degradation of the rhodamine B (RhB) dye and photocatalytic hydrogen production from water. The acceptor is hetero6radialene and the donors are planar pyrene (Py) and twisted bifluorenylidene (BF). TFP 3D COFs surpass previously reported COFs in removing RhB from water in 10 min with a maximum adsorption capacity (
Q
m
) of 840 mg g
−1
. Interestingly, the incorporation of the twisted BF structure into the hetero6radialene-based 3D COF backbone improved the band gap structure, charge transport, and photoinduced electron and hole isolation. The TFP-BF 3D COF degrades organic dye (RhB) with 1.4-fold greater catalytic activity (1.5 × 10
−2
min
−1
) than the planar pyrene donor-derived TFP-Py 3D COF (1.1 × 10
−2
min
−1
). It demonstrates a hydrogen evolution (HER) rate of 21.04 mmol g
−1
h
−1
, obviating the need for a Pt cocatalyst, the highest COF-specific capacity ever recorded. This study illuminates how electron donor topology and hetero6radialene 3D structure affect photocatalysis.
By investigating the effects of electron donor topology and the hetero6radialene structure on the 3D COF photocatalytic activity, a twisted BF structure was found to improve organic pollutant degradation and water hydrogen production.
Magnesium-lithium base alloy is one of the lightest metallic engineering materials with a density of 1·35-1·65 g cm
−3
, which is referred to as superlight materials. It has become an attractive ...material in the fields of aerospace, automobiles, portable electronics, etc. In this paper, the developing history and recent progress of superlight magnesium-lithium base alloys are reviewed. The progress on molten electrolysis preparation, processing technologies and surface processing technologies are introduced, and future research directions are suggested based on the current research progress.
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