Ligand-Directed Shape Reconfiguration in Inorganic Materials.

Polymer elastomers with reversible shape-changing capability have led to significant development of artificial muscles, functional devices, and soft robots. By contrast, reversible shape transformation of inorganic nanoparticles is notoriously challenging due to their relatively rigid lattice structure. Here, the authors demonstrate the synthesis of shape-changing nanoparticles via an asymmetrical surface functionalization process. Various ligands are investigated, revealing the essential role of steric hindrance from the functional groups. By controlling the unbalanced structural hindrance on the surface, the as-prepared clay nanoparticles can transform their shape in a fast, facile, and reversible manner. In addition, such flexible morphology-controlled mechanism provides a platform for developing self-propelled shape-shifting nanocollectors. Owing to the ion-exchanging capability of clay, these self-propelled nanoswimmers (NS) are able to autonomously adsorb rare earth elements with ultralow concentration, indicating the feasibility of using naturally occurring materials for self-powered nanomachine.

Recurrent Cushing Syndrome From Metastatic Adrenocortical Carcinoma With Fumarate Hydratase Allelic Variant.

Background: Adrenal Cushing syndrome (CS) is usually benign in etiology; however, although rarely, it can be due to adrenocortical carcinoma (ACC); in which case, diagnosis and management are quite complicated. Case Report: A 34-year-old woman presented with worsening confusion, weight gain, new-onset diabetes, and hypertension. Her history was significant for a 7.4-cm left adrenal mass and CS, which were treated with left adrenalectomy 2 years ago. She received hydrocortisone replacement therapy after the surgery, which was discontinued on admission when evaluation showed hypokalemia, hypercortisolemia, and undetectable adrenocorticotropic hormone. Subsequent testing included 1-mg and 8-mg dexamethasone suppression tests, which did not suppress cortisol; late-night salivary cortisol measurement, which yielded a very high salivary cortisol level; and 24-hour urinary cortisol measurement. The level of 11-deoxycortisol was elevated. A computed tomography scan revealed multiple hepatic lesions, which were fluorodeoxyglucose avid, and a biopsy confirmed metastatic ACC. She received treatment with mitotane, metyrapone (later changed to mifepristone), doxorubicin, cisplatin, and etoposide. Over 8 weeks, mitotane levels became therapeutic at 20 mcg/mL, the hepatic masses decreased in size, and she transitioned to adrenal insufficiency and improved glycemic control. Next-generation sequencing of liver biopsy and germline testing revealed a frameshift loss-of-function allelic variant in the FH gene that encodes the protein fumarate hydratase. Discussion: We report a case of recurrent CS due to metastatic ACC in a patient with a previously resected adrenal adenoma and FH allelic variant. Conclusion: Metastatic ACC presenting with severe CS presents a diagnostic and management challenge where combination therapy guided by a multidisciplinary team is essential. FH allelic variant may contribute to ACC progression.

Corrigendum: Analysis of clinical related factors of neonatal hand-foot-mouth disease complicated with encephalitis.

[This corrects the article DOI: 10.3389/fneur.2020.543013.].

Zwitterionic Graphene Quantum Dots to Stabilize Pickering Emulsions for Controlled-Release Applications.

Graphene quantum dots (GQDs) are a subset of the nanocarbon material family, which promise a wide spectrum of applications. Herein, we describe amphiphilic graphene quantum dots with zwitterionic features (ZGQDs), which are able to stabilize the oil/water interface. ZGQDs were fabricated by modifying GQDs with tertiary amine groups and alkyl groups. Moreover, the blocking and unblocking behavior of ZGQDs at the oil/water interface could be tuned by adjusting pH values in the aqueous phase. It would provide a flexible and adjustable method to manipulate interfacial properties of ZGQDs, which enabled a switchable molecular diffusion through a fluid-fluid interface. ZGQDs have shown well-controlled interfacial behavior under different pH conditions, indicating great potential for applications in controlled molecular diffusion based on nanoparticles demonstrated in this work.

Engineered two-dimensional nanomaterials: an emerging paradigm for water purification and monitoring.

Water scarcity has become an increasingly complex challenge with the growth of the global population, economic expansion, and climate change, highlighting the demand for advanced water treatment technologies that can provide clean water in a scalable, reliable, affordable, and sustainable manner. Recent advancements on 2D nanomaterials (2DM) open a new pathway for addressing the grand challenge of water treatment owing to their unique structures and superior properties. Emerging 2D nanostructures such as graphene, MoS2, MXene, h-BN, g-C3N4, and black phosphorus have demonstrated an unprecedented surface-to-volume ratio, which promises ultralow material use, ultrafast processing time, and ultrahigh treatment efficiency for water cleaning/monitoring. In this review, we provide a state-of-the-art account on engineered 2D nanomaterials and their applications in emerging water technologies, involving separation, adsorption, photocatalysis, and pollutant detection. The fundamental design strategies of 2DM are discussed with emphasis on their physicochemical properties, underlying mechanism and targeted applications in different scenarios. This review concludes with a perspective on the pressing challenges and emerging opportunities in 2DM-enabled wastewater treatment and water-quality monitoring. This review can help to elaborate the structure-processing-property relationship of 2DM, and aims to guide the design of next-generation 2DM systems for the development of selective, multifunctional, programmable, and even intelligent water technologies. The global significance of clean water for future generations sheds new light and much inspiration in this rising field to enhance the efficiency and affordability of water treatment and secure a global water supply in a growing portion of the world.

Amphiphilicity-adaptable graphene quantum dots to stabilize pH-responsive pickering emulsions at a very low concentration.

HYPOTHESIS: Stimuli-responsive Pickering emulsions have attracted considerable interest due to their widespread potential applications. Especially pH-responsive behavior could be easily implemented. In this work, we reported a pH-responsive Pickering emulsion based on amphiphilic graphene quantum dots at a low concentration which shows a great potential from the environmental and economic perspective. The stimuli responsive properties would make the smart Pickering emulsifiers recyclable and reusable. EXPERIMENTS: The amphiphilic-adaptable graphene quantum dots functionalized by alkyl groups (C-GQDs) were synthesized by a facile one-step pyrolysis method. The pH-responsive emulsion performances were investigated, and the mechanism of pH-responsive of C-GQDs was studied by dynamic light scattering. FINDINGS: The amphiphilicity of C-GQDs could be acquired controllably and effectively by this facile one-step pyrolysis method, which are able to stabilize Pickering emulsion at a very low concentration (0.001%). The amphiphilicity of C-GQDs are capable of changing in response to environmental stimuli. When the pH value of aqueous solution adjusts to 2, these C-GQDs aggregate in contrast to their stability in neutral condition due to the alternation of surface charges. The pH-responsive aggregation/ dispersion behavior of C-GQDs allows us to tune the interactions between oil-in-water emulsion droplets without introduction of destabilization agents. This will provide huge economic benefits in industrial applications in the future.

Analysis of Clinical Related Factors of Neonatal Hand-Foot-Mouth Disease Complicated With Encephalitis.

Objective: To explore the clinical related factors of neonatal hand-foot-mouth disease (HFMD) complicated with encephalitis. Method: The neonatal HFMD complicated with encephalitis treated in our hospital from July 2015 to July 2020 was taken as the object of study. According to the NBNA score at discharge, the patients were divided into normal group and abnormal group. The clinical symptoms, auxiliary examination and prognosis of the two groups were compared. Result: (1) General condition: there was no significant difference in sex, age, duration of fever, treatment time and etiological test between the two groups (P > 0.05). (2) Clinical symptoms and signs: there was significant difference in abnormal consciousness between the two groups (P < 0.05). However, there was no significant difference in skin rash, respiratory system symptoms, digestive system symptoms, signs of high intracranial pressure, increased muscle tone and weakening of primitive reflex (P > 0.05). (3) Auxiliary examination: the number of white blood cells and the level of cytokines (CK-BB, UCH-L1) in cerebrospinal fluid (CSF) in the group with abnormal NBNA score were significantly higher than those in the group with normal NBNA score (P < 0.05). The serum IgM level in the abnormal NBNA score group was higher than that in the normal NBNA score group, and the serum IgG level in the abnormal NBNA score group was lower than that in the normal NBNA score group, and the difference was statistically significant (P < 0.05). The abnormal rate of Craniocerebral MRI in abnormal NBNA score group was higher than that in normal NBNA score group, and there was significant difference between the two groups (P < 0.05). There was no significant difference in the levels of protein, sugar, chloride, lactate dehydrogenase, and MMP-9 in CSF and the abnormal rate of amplitude integrated EEG (aEEG) between the two groups (P > 0.05). (4) The prognoses of patients with normal and abnormal NBNA score are good, and there are not significantly differences in the prognosis between the two groups (P > 0.05). Conclusion: (1) Neonatal HFMD complicated with encephalitis occurs more than 10 days after birth, there is no obvious abnormality in male and female, the vast majority of newborns have febrile symptoms, rash is not its specific manifestation, and most of them are atypical. (2) The positive rate of HFMD-related virus detected in CSF of neonatal HFMD is high. For newborns with abnormal consciousness, CSF examination should be accomplished in time, which has certain clinical significance for early diagnosis and treatment of severe newborns. (3) The increase of white blood cell count and cytokines (CK-BB, UCH-L1) in CSF of neonatal HFMD complicated with encephalitis has a certain clinical reference value for early diagnosis and identification of severe newborns. (4) There is a certain humoral immune disorder in newborns with HFMD complicated with encephalitis, but the overall prognosis is better due to the protective effect of maternal IgG.

Colloidal Nanosurfactants for 3D Conformal Printing of 2D van der Waals Materials.

Printing techniques using nanomaterials have emerged as a versatile tool for fast prototyping and potentially large-scale manufacturing of functional devices. Surfactants play a significant role in many printing processes due to their ability to reduce interfacial tension between ink solvents and nanoparticles and thus improve ink colloidal stability. Here, a colloidal graphene quantum dot (GQD)-based nanosurfactant is reported to stabilize various types of 2D materials in aqueous inks. In particular, a graphene ink with superior colloidal stability is demonstrated by GQD nanosurfactants via the π-π stacking interaction, leading to the printing of multiple high-resolution patterns on various substrates using a single printing pass. It is found that nanosurfactants can significantly improve the mechanical stability of the printed graphene films compared with those of conventional molecular surfactant, as evidenced by 100 taping, 100 scratching, and 1000 bending cycles. Additionally, the printed composite film exhibits improved photoconductance using UV light with 400 nm wavelength, arising from excitation across the nanosurfactant bandgap. Taking advantage of the 3D conformal aerosol jet printing technique, a series of UV sensors of heterogeneous structures are directly printed on 2D flat and 3D spherical substrates, demonstrating the potential of manufacturing geometrically versatile devices based on nanosurfactant inks.

Accelerated Design of Catalytic Water-Cleaning Nanomotors via Machine Learning.

The ability of self-propelled nanoparticles to convert environmental energy into locomotion has led to several nanomotor prototypes that are promising in numerous real-world applications. However, the vast variety of nanoparticle designs prevents rapid identification of the optimal composition for a given application. In this study, we applied machine learning methods to predict the self-propulsion speed and water-cleaning efficiency of micro/nanomotors (MNMs), where the quality of machine learning predictions was evaluated based on the statistical values. The average absolute error of predicted velocity and predicted efficiency are determined to be as low as 0.10 and 0.12, respectively. In addition, by comparing the prediction results based on 13 features using four different machine learning algorithms, we are able to identify several key features that are important to effectively environmental decontamination, such as particle size, catalyst type, and aspect ratio. Following the guidelines deduced from these models, a high-efficiency Pt-coated nanomotor was designed and synthesized, of which the experimental results were compared with the machine learning predictions, showing an accurate prediction with a less than 15% of prediction error. In the range of our theoretical/experimental conditions, we showed that a gradient boosting algorithm is the most promising method for predicting the environmental decontamination behavior of MNMs, a machine-learning algorithm rarely used in the nanomaterial field in current practice.

Growth of Colloidal Nanoplate Liquid Crystals Using Temperature Gradients.

Controlling colloidal self-assemblies using external forces is essential to develop modern electro-optical and biomedical devices. Importantly, shape anisotropic colloids can provide optical properties such as birefringence. Here we demonstrate that external temperature gradients can be effective in controlling nematic liquid crystalline (LC) order in suspensions of plate-like colloids also known as nanoplates. Nanoplates, in an isotropic suspension, wherein their orientations are random, could be effectively moved using a temperature gradient environment causing a phase transition to LC nematic phase. Such controllably formed nematic phase featured large nematic monodomains and enabled topologically more stable structures that were evident from the absence of hedgehog-type defects which are typically found in nematics formed spontaneously via nucleation and growth mechanism in a sufficiently high concentration suspension of nanoplates. Due to their high surface area-to-volume ratio and excellent thermophoretic properties, nanoplates can prove to be ideal candidates for transport of biomolecules through temperature varying environments.

Iridescence in nematics: Photonic liquid crystals of nanoplates in absence of long-range periodicity.

Photonic materials with positionally ordered structure can interact strongly with light to produce brilliant structural colors. Here, we found that the nonperiodic nematic liquid crystals of nanoplates can also display structural color with only significant orientational order. Owing to the loose stacking of the nematic nanodiscs, such colloidal dispersion is able to reflect a broad-spectrum wavelength, of which the reflection color can be further enhanced by adding carbon nanoparticles to reduce background scattering. Upon the addition of electrolytes, such vivid colors of nematic dispersion can be fine-tuned via electrostatic forces. Furthermore, we took advantage of the fluidity of the nematic structure to create a variety of colorful arts. It was expected that the concept of implanting nematic features in photonic structure of lyotropic nanoparticles may open opportunities for developing advanced photonic materials for display, sensing, and art applications.

Facile one-step microwave-assisted modification of kaolinite and performance evaluation of pickering emulsion stabilization for oil recovery application.

A facile one-step microwave-assisted method was proposed for kaolinite intercalation and grafting. The structure, morphology, composition, and size distribution of kaolinite sheets were investigated using various methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric (TG) analysis. The potential application of the modified kaolinite as an oil/water emulsion stabilizer was studied. The results verified that intact kaolinite sheets were obtained. The dodecane/water emulsion stabilized by the modified kaolinite remained stable for more than 60 days. The effective performance suggests that the effectiveness of the proposed kaolinite modification method may be useful for Pickering emulsion stabilization in oil recovery applications.

Natural Halloysites-Based Janus Platelet Surfactants for the Formation of Pickering Emulsion and Enhanced Oil Recovery.

Janus colloidal surfactants with opposing wettabilities are receiving attention for their practical application in industry. Combining the advantages of molecular surfactants and particle-stabilized Pickering emulsions, Janus colloidal surfactants generate remarkably stable emulsions. Here we report a straightforward and cost-efficient strategy to develop Janus nanoplate surfactants (JNPS) from an aluminosilicate nanoclay, halloysite, by stepwise surface modification, including an innovative selective surface modification step. Such colloidal surfactants are found to be able to stabilize Pickering emulsions of different oil/water systems. The microstructural characterization of solidified polystyrene emulsions indicates that the emulsion interface is evenly covered by JNPS. The phase behaviors of water/oil emulsion generated by these novel platelet surfactants were also investigated. Furthermore, we demonstrate the application of JNPS for enhanced oil recovery with a microfluidic flooding test, showing a dramatic increase of oil recovery ratio. This research provides important insights for the design and synthesis of two-dimensional Janus colloidal surfactants, which could be utilized in biomedical, food and mining industries, especially for circumstances where high salinity and high temperature are involved.

Electrostatic-Driven Dynamic Jamming of 2D Nanoparticles at Interfaces for Controlled Molecular Diffusion.

Dynamically engineering the interfacial interaction of nanoparticles has emerged as a new approach for bottom-up fabrication of smart systems to tailor molecular diffusion and controlled release. Janus zwitterionic nanoplates are reported that can be switched between a locked and unlocked state at interfaces upon changing surface charge, allowing manipulation of interfacial properties in a fast, flexible, and switchable manner. Combining experimental and modeling studies, an unambiguous correlation is established among the electrostatic energy, the interface geometry, and the interfacial jamming states. As a proof-of-concept, the well-controlled interfacial jamming of nanoplates enabled the switchable molecular diffusion through liquid-liquid interfaces, confirming the feasibility of using nanoparticle-based surfactants for advanced controlled release.

Hierarchical, Self-Healing and Superhydrophobic Zirconium Phosphate Hybrid Membrane Based on the Interfacial Crystal Growth of Lyotropic Two-Dimensional Nanoplatelets.

We demonstrate a facile route to in situ growth of lyotropic zirconium phosphate (ZrP) nanoplates on textiles via an interfacial crystal growing process. The as-prepared hybrid membrane shows a hierarchical architecture of textile fibers (porous platform for fluid transport), ZrP nanoplatelets (layered scaffolds for chemical barriers), and octadecylamine (organic species for superhydrophobic functionalization). Interestingly, such a hybrid membrane is able to separate the oily wastewater with a high separation efficiency of 99.9%, even at in harsh environments. After being chemically etched, the hybrid membrane is able to restore its hydrophobicity autonomously and repeatedly, owing to the hierarchical structure that enables facile loading of healing agent. We anticipate that the concept of implanting superhydrophobic self-healing features in anisotropic structure of lyotropic nanoparticles will open up new opportunities for developing advanced multifunctional materials for wastewater treatment, fuel purification, and oil spill mitigation.

Occurrence and distribution of antibiotics in mariculture farms, estuaries and the coast of the Beibu Gulf, China: Bioconcentration and diet safety of seafood.

The occurrence, distribution, bioconcentration and diet safety via seafood consumption of 19 antibiotics were investigated in eight closed mariculture ponds, four estuaries, two nearshore areas and one offshore area from the Beibu Gulf. Seventeen, 16, 15 and 7 antibiotics were detected at total concentrations of 43.2 - 885 ng L-1, 22.4 - 118 ng L-1, 22.7 - 24.5 ng L-1, and 1.81-3.23 ng L-1 in the water of the above different areas, respectively. This indicates that the mariculture ponds are important sources of antibiotic pollution on the coast of the Beibu Gulf. Ten antibiotics were detected in feed samples with concentrations ranging from 0.03 to 95.4 ng g-1, demonstrating the presence of antibiotics in the feed and/or residual antibiotics in the raw material of the feed. The field bioconcentration factors (BCFs) of the antibiotics calculated in different culture organisms ranged from 0.55 to 10,774 L kg-1. The estimated daily intakes (EDIs) of sulphonamides, fluoroquinolones, macrolides and chloramphenicols via aquatic products were 19.8-105, 33.7-178, 34.9-186 and 6.9-37.1 ng d-1, respectively. According to the acceptable daily intakes (ADIs) and maximum residue limits (MRLs) proposed by different organisations, these aquatic products (shrimp, crab and oyster) reached the standard of safe consumption and could not pose a health risk to humans. However, a potential elevated risk to humans may remain because of the occurrence of multiple antibiotics in the cultured organisms, particularly for sensitive populations, such as pregnant women, the elderly and children.

Biomimetic colloidal photonic crystals by coassembly of polystyrene nanoparticles and graphene quantum dots.

Biomimetic nanostructured materials with iridescent structural colors have attracted great attention due to their potential in photonic devices, materials science, and biomedical engineering. The technological applications of artificial photonic crystals (PCs), however, are often hindered by their low color visibility. Herein, we report colloidal PCs with enhanced color visibility through the coassembly of thioglycerol-modified graphene quantum dots (GQDs) into the close-packed array of polystyrene (PS) nanospheres. The enhanced polystyrene PCs were fabricated by both centrifugal sedimentation and drop-casting methods. The color visibility of the resulting PCs was found to be strongly dependent on the hydrothermal time (i.e., carbonization) and the doping concentrations of GQDs. The PCs with brilliant reflection colors with red, green and blue (RGB) regions have been achieved by controlling the size of the constituent PS nanoparticles. As a proof of concept for photonic ink applications, we demonstrated a number of photonic images with RGB colors on multiple substrates including paper, silicon wafer and glass. This work is expected to provide new insight into the development of emerging advanced photonic crystals with high color visibility for applications such as colloidal paints, textile fabrics, and wearable displays.

Aqueous Exfoliation of Graphite into Graphene Assisted by Sulfonyl Graphene Quantum Dots for Photonic Crystal Applications.

We investigate the π-π stacking of polyaromatic hydrocarbons (PAHs) with graphene surfaces, showing that such interactions are general across a wide range of PAH sizes and species, including graphene quantum dots. We synthesized a series of graphene quantum dots with sulfonyl, amino, and carboxylic functional groups and employed them to exfoliate and disperse pristine graphene in water. We observed that sulfonyl-functionalized graphene quantum dots were able to stabilize the highest concentration of graphene in comparison to other functional groups; this is consistent with prior findings by pyrene. The graphene nanosheets prepared showed excellent colloidal stability, indicating great potential for applications in electronics, solar cells, and photonic displays which was demonstrated in this work.

Tumoral TP53 and/or CDKN2A alterations are not reliable prognostic biomarkers in patients with localized Ewing sarcoma: a report from the Children's Oncology Group.

BACKGROUND: A growing collection of retrospective studies have suggested that TP53 mutations and/or CDKN2A deletions have prognostic significance in Ewing sarcoma. We sought to evaluate these variables in patients with localized disease treated prospectively on a single Children's Oncology Group protocol. PROCEDURE: Of the 568 patients enrolled on Children's Oncology Group protocol AEWS0031 (NCT00006734), 112 had tumor specimens of sufficient quality and quantity to allow for analysis of TP53 mutations status by DNA sequencing, and CDKN2A deletion by dual color fluorescent in situ hybridization. RESULTS: Eight of 93 cases (8.6%) were found to have TP53 point mutations and 12 of 107 cases (11.2%) demonstrated homozygous CDKN2A deletion. Two cases were found to have an alteration in both genes. There was no significant difference in event-free survival of patients with TP53 mutations and/or CDKN2A deletions compared to patients with normal TP53/CDKN2A gene status, as demonstrated by log rank test (p = 0.58). CONCLUSIONS: Although previous retrospective studies suggest their significance, TP53 mutation and/or CDKN2A deletion are not reliable prognostic biomarkers in localized Ewing sarcoma.