Complex Pathways Drive Pluripotent Fmoc-Leucine Self-Assemblies.

Nature uses complex self-assembly pathways to access distinct functional non-equilibrium self-assemblies. This remarkable ability to steer same set of biomolecules into different self-assembly states is done by avoiding thermodynamic pit. In synthetic systems, on demand control over 'Pathway Complexity' to access self-assemblies different from equilibrium structures remains challenging. Here we show versatile non-equilibrium assemblies of the same monomer via alternate assembly pathways. The assemblies nucleate using non-classical or classical nucleation routes into distinct metastable (transient hydrogels), kinetic (stable hydrogels) and thermodynamic structures [(poly)-crystals and 2D sheets]. Initial chemical and thermal inputs force the monomers to follow different assembly pathways and form soft-materials with distinct molecular arrangements than at equilibrium. In many cases, equilibrium structures act as thermodynamic sink which consume monomers from metastable structures giving transiently formed materials. This dynamics can be tuned chemically or thermally to slow down the dissolution of transient hydrogel, or skip the intermediate hydrogel altogether to reach final equilibrium assemblies. If required this metastable state can be kinetically trapped to give strong hydrogel stable over days. This method to control different self-assembly states can find potential use in similar biomimetic systems to access new materials for various applications.

Carbon Dot as Visible-Light Photoredox Catalysts for a Myriad of Organic Transformations.

Metal-free catalysts for various organic transformations are of high demand now. In this study, we present a new carbon dot as an efficient metal-free nanophotocatalyst for carrying out a series of organic bond formation reactions. Using a single photocatalyst carbon dot, Csp2-Csp2, Csp2-B, Csp2-S, Csp2-Se, and C-P bond formation reactions were performed with a high yield of the corresponding products. Moreover, Csp2-H activation of the aromatic ring was achieved by merging the carbon dot photocatalyst with a transition metal. Interestingly, these carbon nanodot-based catalysts show good recyclability a few times without any significant loss of catalytic activity. The development of catalytic systems based on carbon dots has its merits vested in the advantageous properties of this nanomaterial, such as a robust chemical nature and cheap cost of preparation. This report demonstrates that a carbon dot indeed holds the potential to replace expensive metal-based catalysts as well as organic dyes in five different photoredox reactions.

Impact of core-shell perovskite nanocrystals for LED applications: successes, challenges, and prospects.

Perovskite nanocrystals (PeNCs) synthesized by colloidal solution methods are an outstanding case of study due to their remarkable optical features, different from their bulk counterpart, such as a tuneable band gap and narrower photoluminescence emission, altered by the size and shape. However, the stability of these systems needs to be improved to consolidate their application in optoelectronic devices. Improved PeNC quality is associated with a less defective structure, as it affects negatively the photoluminescence quantum yield (PLQY), due to the essential, but at the same time labile interaction between the colloidal capping ligands and the perovskite core. In this sense, it would be extremely effective to obtain an alternative method to stabilize the PeNC phases and passivate the surface, in order to improve both stability and optical properties. This objective can be reached exploiting the structural benefits of the interaction between the perovskite and other organic or inorganic materials with a compatible structure and optical properties and limiting the optical drawbacks. This perspective contemplates different combinations of core/shell PeNCs and the critical steps during the synthesis, including drawbacks and challenges based on their optical properties. Additionally, it provides insights for future light emitting diode (LED) applications and advanced characterization. Finally, the existing challenges and opportunities for core/shell PeNCs are discussed.

Surface modification of carbon dots via peptide covalent conjugation.

Surface modification of carbon dots via covalent conjugation with a dipeptide resulted in a dramatic change in the fluorescence emission from green to red. The hydrophobic peptide units linked to the surface of the modified carbon dots helped them to aggregate by generating a nanodot-fabricated nanofibrous network. This nanofibrous network showed excellent electrical conductivity and photo-switching behavior, better than those of the non-aggregated dots.

Potential Role of High-Dose Steroids in the Treatment of COVID-19-Associated Nephropathy.

With the increasing number of COVID-19-associated nephropathy (COVAN), biopsy-proven cases of collapsing variety of focal segmental glomerulosclerosis (FSGS) are emerging. Though the recommendations on treatment for COVID-19-associated respiratory symptoms are evolving, there is still no definitive treatment for the collapsing FSGS secondary to COVAN. We report a case of a 47-year-old male admitted with acute kidney injury from COVID-19 infection and found to have collapsing FSGS on renal biopsy. Almost all the patients who were found to have similar conditions were treated with a relatively smaller dose of steroids and ultimately required dialysis. Our patient showed improvement with the trial of higher doses of steroids and never required dialysis. Hence, our case report emphasizes the need for a randomized controlled trial (RCT) with regard to the use of high-dose steroids in COVAN.

Real-world assessment: effectiveness and safety of extended-release calcifediol and other vitamin D therapies for secondary hyperparathyroidism in CKD patients.

INTRODUCTION: Extended-release calcifediol (ERC), active vitamin D hormones and analogs (AVD) and nutritional vitamin D (NVD) are commonly used therapies for treating secondary hyperparathyroidism (SHPT) in adults with stage 3-4 chronic kidney disease (CKD) and vitamin D insufficiency (VDI). Their effectiveness for increasing serum total 25-hydroxyvitamin D (25D) and reducing elevated plasma parathyroid hormone (PTH), the latter of which is associated with increased morbidity and mortality, has varied across controlled clinical trials. This study aimed to assess real-world experience of ERC and other vitamin D therapies in reducing PTH and increasing 25D. METHODS: Medical records of 376 adult patients with stage 3-4 CKD and a history of SHPT and VDI from 15 United States (US) nephrology clinics were reviewed for up to 1 year pre- and post-ERC, NVD or AVD initiation. Key study variables included patient demographics, concomitant usage of medications and laboratory data. The mean age of the study population was 69.5 years, with gender and racial distributions representative of the US CKD population. Enrolled patients were grouped by treatment into three cohorts: ERC (n = 174), AVD (n = 55) and NVD (n = 147), and mean baseline levels were similar for serum 25D (18.8-23.5 ng/mL), calcium (Ca: 9.1-9.3 mg/dL), phosphorus (P: 3.7-3.8 mg/dL) and estimated glomerular filtration rate (eGFR: 30.3-35.7 mL/min/1.73m2). Mean baseline PTH was 181.4 pg/mL for the ERC cohort versus 156.9 for the AVD cohort and 134.8 pg/mL (p < 0.001) for the NVD cohort. Mean follow-up during treatment ranged from 20.0 to 28.8 weeks. RESULTS: Serum 25D rose in all cohorts (p < 0.001) during treatment. ERC yielded the highest increase (p < 0.001) of 23.7 ± 1.6 ng/mL versus 9.7 ± 1.5 and 5.5 ± 1.3 ng/mL for NVD and AVD, respectively. PTH declined with ERC treatment by 34.1 ± 6.6 pg/mL (p < 0.001) but remained unchanged in the other two cohorts. Serum Ca increased 0.2 ± 0.1 pg/mL (p < 0.001) with AVD but remained otherwise stable. Serum alkaline phosphatase remained unchanged. CONCLUSIONS: Real-world clinical effectiveness and safety varied across the therapies under investigation, but only ERC effectively raised mean 25D (to well above 30 ng/mL) and reduced mean PTH levels without causing hypercalcemia.

Yellow-Emitting Carbon Dots for Selective Fluorescence Imaging of Lipid Droplets in Living Cells.

This study shows a one-pot preparation of carbon dots by a solvothermal method in ethylene glycol. The carbon dots show yellow-colored fluorescence emission in water. The carbon dots showed distinct preference to be present in the hydrophobic environment which was evident from their efficient transfer from aqueous phase to organic phase. They were also found to locate themselves in the vesicle bilayer and micelle core. This inherent lipophilic character of these carbon dots has been successfully utilized for the selective imaging of lipid droplets inside the living cells. The selective imaging of lipid droplets was confirmed by similar staining patterns with other staining dyes and the starvation study.

A multi-center retrospective cohort study defines the spectrum of kidney pathology in Coronavirus 2019 Disease (COVID-19).

Kidney failure is common in patients with Coronavirus Disease-19 (COVID-19), resulting in increased morbidity and mortality. In an international collaboration, 284 kidney biopsies were evaluated to improve understanding of kidney disease in COVID-19. Diagnoses were compared to five years of 63,575 native biopsies prior to the pandemic and 13,955 allograft biopsies to identify diseases that have increased in patients with COVID-19. Genotyping for APOL1 G1 and G2 alleles was performed in 107 African American and Hispanic patients. Immunohistochemistry for SARS-CoV-2 was utilized to assess direct viral infection in 273 cases along with clinical information at the time of biopsy. The leading indication for native biopsy was acute kidney injury (45.4%), followed by proteinuria with or without concurrent acute kidney injury (42.6%). There were more African American patients (44.6%) than patients of other ethnicities. The most common diagnosis in native biopsies was collapsing glomerulopathy (25.8%), which was associated with high-risk APOL1 genotypes in 91.7% of cases. Compared to the five-year biopsy database, the frequency of myoglobin cast nephropathy and proliferative glomerulonephritis with monoclonal IgG deposits was also increased in patients with COVID-19 (3.3% and 1.7%, respectively), while there was a reduced frequency of chronic conditions (including diabetes mellitus, IgA nephropathy, and arterionephrosclerosis) as the primary diagnosis. In transplants, the leading indication was acute kidney injury (86.4%), for which rejection was the predominant diagnosis (61.4%). Direct SARS-CoV-2 viral infection was not identified. Thus, our multi-center large case series identified kidney diseases that disproportionately affect patients with COVID-19 and demonstrated a high frequency of APOL1 high-risk genotypes within this group, with no evidence of direct viral infection within the kidney.

Tuning of the optoelectronic properties of peptide-appended core-substituted naphthalenediimides: the role of self-assembly of two positional isomers.

This study demonstrates how the self-assembly pattern of two different and isomeric peptide-appended core-substituted naphthalenediimides (NDIs) affects the modulation of their optoelectronic properties. Two isomeric peptide-attached NDIs were synthesized, purified and characterized. Interchanging the position of attachment of the peptide units and the alkyl chains in the NDI has altered the respective self-assembling patterns of these isomeric molecules in the aggregated states. The isomer having a peptide moiety in the core position and the alkyl chain in the imide position (compound N1) forms face to face stacking or 'H' aggregates in aliphatic solvents including n-hexane, and n-decane, whereas compound N2, in which the peptide moiety is at the imide position and the alkyl chain is attached at the core position of NDI exhibits edge to edge stacking or J aggregates under the same conditions as it is evident from their UV-vis studies. The H aggregated species (obtained from N1) show inter-connected nanofibers, whereas the J aggregated species (obtained from N2) exhibit the morphology of helical nanoribbons. FT-IR and X-ray diffraction studies are in favor of the same aggregation behavior. The individual packing patterns of these two peptide-based isomers have a direct impact on their respective electrical conductivity. Interestingly, the H aggregated species shows 100 times greater current conductivity than that of the J aggregate. Moreover, it is only the H aggregated species that exhibits a photocurrent, and no such photocurrent response is observed with the J aggregates. Computational studies also support that different types of aggregation patterns are formed by these two isomeric molecules in the same solvent system. This unique example of tuning of optoelectronic behavior holds future promise for the development of new peptide-conjugated π-functional materials.

Solvent-Directed Transformation of the Self-assembly and Optical Property of a Peptide-Appended Core-Substituted Naphthelenediimide and Selective Detection of Nitrite Ions in an Aqueous Medium.

This study vividly displays the different self-assembling behavior and consequent tuning of the fluorescence property of a peptide-appended core-substituted naphthalenediimide (N1) in the aliphatic hydrocarbon solvents (n-hexane/n-decane/methyl cyclohexane) and in an aqueous medium within micelles. The N1 is highly fluorescent in the monomeric state and self-aggregates in a hydrocarbon solvent, exhibiting "H-type" or "face-to-face" stacking as indicated by a blue shift of absorption maxima in the UV-vis spectrum. In the H-aggregated state, the fluorescence emission of N1 changes to green from the yellow emission obtained in the monomeric state. In the presence of a micelle-forming surfactant, cetyl trimethylammonium bromide (CTAB), the N1 is found to be dispersed in a water medium. Interestingly, upon encapsulation of N1 into the micelle, the molecule alters its self-assembling pattern and optical property compared to its behavior in the hydrocarbon solvent. The N1 exhibits "edge-to-edge" stacking or J aggregates inside the micelle as indicated by the UV-vis spectroscopic study, which shows a red shift of the absorption maxima compared to that in the monomeric state. The fluorescence emission also differs in the water medium with the NDI derivative exhibiting red emission. FT-IR studies reveal that all amide NHs of N1 are hydrogen-bonded within the micelle (in the J-aggregated state), whereas both non-bonding and hydrogen-bonding amide NHs are present in the H-aggregated state. This is a wonderful example of solvent-mediated transformation of the aggregation pattern (from H to J) and solvatochromism of emission over a wide range from green in the H-aggregated state to yellow in the monomeric state and orangish-red in the J-aggregated state. Moreover, the J aggregate has been successfully utilized for selective and sensitive detection of nitrite ions in water even in the presence of other common anions (NO3-, SO42-, HSO4-, CO32-, and Cl-).

Stimuli responsive multicolour fluorescence emission in carbon nanodots and application in metal free hydrogen evolution from water.

The present study convincingly demonstrates visible light induced continuous tuning of the fluorescence of carbon nanodots from yellow to cyan within two hours. These carbon dots are well characterized using field emission gun transmission electron microscopy (FEG-TEM), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FT-IR), fluorescence spectroscopy and UV-visible spectroscopy. Moreover, solid state fluorescence of different wavelengths has also been obtained from these colour tunable carbon dots by circumventing the common problem of aggregation induced quenching of fluorescence in the solid state. These carbon dots have also shown a very low band gap and the yellow emissive C-dots have been successfully utilized as a photocathode in metal free photo-electrochemical hydrogen evolution from water.

Improved Electrochemical and Mechanical Properties of Poly(vinylpyrrolidone)/Nafion® Membrane for Fuel Cell Applications.

A novel blend of membranes made of Nafion® and poly(vinylpyrrolidone) (PVP) was prepared and characterized to investigate its applicability in proton exchange membrane fuel cells (PEMFCs). In addition to being effectively proton conductive, the membranes exhibited better mechanical strength, chemical stability, and adequate water retention ability, as well as ion exchange capacity comparable to that of cast Nafion® membrane. The data obtained from an electrochemical impedance spectroscopy (EIS) fitting of the fuel cells revealed the membrane electrode assemblies (MEAs) made of 0.5 wt.% PVP/Nafion® had lower ohmic and charge transfer resistance compared with that of the Nafion® membrane. The intermolecular interactions and morphology of these membranes were assessed using Fourier-transform infrared spectroscopy and field-emission scanning electron microscopy. The results of the performance curve indicate that the introduction of PVP as a modifier played a vital role in improving membrane performance. Accordingly, this solution-casted polymer electrolyte membrane with suitable PVP content offers a simple way to improve electrochemical, mechanical, and chemical properties, and thereby promises the prospect of use in low-temperature PEMFCs.

Carbon nanodot-induced gelation of a histidine-based amphiphile: application as a fluorescent ink, and modulation of gel stiffness.

This is a unique example of fluorescent carbon dot-induced hydrogelation of an amino acid-based amphiphile. The carbon dot-to-amphiphile ratio dictates the gel stiffness. Moreover, this hydrogel can be used as a prominent fluorescent ink and the dried gel shows a remarkable, unusual green fluorescence in the solid state.

Luminescent Naphthalene Diimide-Based Peptide in Aqueous Medium and in Solid State: Rewritable Fluorescent Color Code.

This study convincingly demonstrates a unique example of the self-assembly of a naphthalene diimide (NDI)-appended peptide into a fluorescent J-aggregate in aqueous media. Moreover, this aggregated species shows a remarkable yellow fluorescence in solid state, an unusual phenomenon for NDI-based compounds. The aggregated species has been characterized using transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy, X-ray diffraction, time-correlated single proton counting (TCSPC), UV-vis, and photoluminescence studies. TEM images reveal cross-linked nanofibrillar morphology of this aggregated species in water (pH 7.4). TCSPC study clearly indicates that the aggregated species in water has a higher average lifetime compared to that of the non-aggregated species. Interestingly, this NDI-based peptide shows H+ ion concentration-dependent change in the emission property in water. The fluorescence output is erased completely in the presence of an alkali, and it reappears in the presence of an acid, indicating its erasing and rewritable property. This indicates its probable use in authentication tools for security purposes as a rewritable fluorescence color code. This NDI-appended peptide-based molecule can be used for encryption of information due to erasing and rewritable property of the molecule in the aggregated state in aqueous medium.

A tripeptide-based self-shrinking hydrogel for waste-water treatment: removal of toxic organic dyes and lead (Pb2+) ions.

A triphenylalanine-based superhydrogel shows automatic syneresis (self-compressing properties) with time and this self-shrinking behavior has been successfully utilized to remove toxic lead ions and organic dyes from waste-water efficiently with the ability to re-use for a few times.