A Novel Experimental Approach to Understand the Transport of Nanodrugs.

Nanoparticle-based drugs offer attractive advantages like targeted delivery to the diseased site and size and shape-controlled properties. Therefore, understanding the particulate flow of the nanodrugs is important for effective delivery, accurate prediction of required dosage, and developing efficient drug delivery platforms for nanodrugs. In this study, the transport of nanodrugs including flow velocity and deposition is investigated using three model metal oxide nanodrugs of different sizes including iron oxide, zinc oxide, and combined Cu-Zn-Fe oxide synthesized via a modified polyol approach. The hydrodynamic size, size, morphology, chemical composition, crystal phase, and surface functional groups of the water-soluble nanodrugs were characterized via dynamic light scattering, transmission electron microscopy, scanning electron microscopy-energy dispersive X-ray, X-ray diffraction, and fourier transform infrared spectroscopy, respectively. Two different biomimetic flow channels with customized surfaces are developed via 3D printing to experimentally monitor the velocity and deposition of the different nanodrugs. A diffusion dominated mechanism of flow is seen in size ranges 92 nm to 110 nm of the nanodrugs, from the experimental velocity and mass loss profiles. The flow velocity analysis also shows that the transport of nanodrugs is controlled by sedimentation processes in the larger size ranges of 110-302 nm. However, the combined overview from experimental mass loss and velocity trends indicates presence of both diffusive and sedimentation forces in the 110-302 nm size ranges. It is also discovered that the nanodrugs with higher positive surface charges are transported faster through the two test channels, which also leads to lower deposition of these nanodrugs on the walls of the flow channels. The results from this study will be valuable in realizing reliable and cost-effective in vitro experimental approaches that can support in vivo methods to predict the flow of new nanodrugs.

Transition metal chalcogenides for next-generation energy storage.

Transition-metal chalcogenide nanostructures provide a unique material platform to engineer next-generation energy storage devices such as lithium-ion, sodium-ion, and potassium-ion batteries and flexible supercapacitors. The transition-metal chalcogenide nanocrystals and thin films have enhanced electroactive sites for redox reactions and hierarchical flexibility of structure and electronic properties in the multinary compositions. They also consist of more earth-abundant elements. These properties make them attractive and more viable new electrode materials for energy storage devices compared to the traditional materials. This review highlights the recent advances in chalcogenide-based electrodes for batteries and flexible supercapacitors. The viability and structure-property relation of these materials are explored. The use of various chalcogenide nanocrystals supported on carbonaceous substrates, two-dimensional transition metal chalcogenides, and novel MXene-based chalcogenide heterostructures as electrode materials to improve the electrochemical performance of lithium-ion batteries is discussed. The sodium-ion and potassium-ion batteries offer a more viable alternative to lithium-ion technology as they consist of readily available source materials. Application of various transition metal chalcogenides such as MoS2, MoSe2, VS2, and SnSx, composite materials, and heterojunction bimetallic nanosheets composed of multi-metals as electrodes to enhance the long-term cycling stability, rate capability, and structural strength to counteract the large volume expansion during the ion intercalation/deintercalation processes is highlighted. The promising performances of layered chalcogenides and various chalcogenide nanowire compositions as electrodes for flexible supercapacitors are also discussed in detail. The review also details the progress made in new chalcogenide nanostructures and layered mesostructures for energy storage applications.

Virtually the Same? Evaluating the Effectiveness of Remote Undergraduate Research Experiences.

In-person undergraduate research experiences (UREs) promote students' integration into careers in life science research. In 2020, the COVID-19 pandemic prompted institutions hosting summer URE programs to offer them remotely, raising questions about whether undergraduates who participate in remote research can experience scientific integration and whether they might perceive doing research less favorably (i.e., not beneficial or too costly). To address these questions, we examined indicators of scientific integration and perceptions of the benefits and costs of doing research among students who participated in remote life science URE programs in Summer 2020. We found that students experienced gains in scientific self-efficacy pre- to post-URE, similar to results reported for in-person UREs. We also found that students experienced gains in scientific identity, graduate and career intentions, and perceptions of the benefits of doing research only if they started their remote UREs at lower levels on these variables. Collectively, students did not change in their perceptions of the costs of doing research despite the challenges of working remotely. Yet students who started with low cost perceptions increased in these perceptions. These findings indicate that remote UREs can support students' self-efficacy development, but may otherwise be limited in their potential to promote scientific integration.

Dispersion and Aggregation Fate of Individual and Co-Existing Metal Nanoparticles under Environmental Aqueous Suspension Conditions.

The use of diverse metal nanoparticles (MNPs) in a wide range of commercial products has led to their co-existence in the aqueous environment. The current study explores the dispersion and aggregation fate of five prominent MNPs (silver, copper, iron, nickel, and titanium), in both their individual and co-existing forms. We address a knowledge gap regarding their environmental fate under turbulent condition akin to flowing rivers. We present tandem analytical techniques based on dynamic light scattering, ultraviolet-visible spectroscopy, and inductively coupled plasma atomic emission spectroscopy for discerning their dispersion behavior under residence times of turbulence, ranging from 0.25 to 4 h. The MNPs displayed a multimodal trend for dispersion and aggregation behavior with suspension time in aqueous samples. The extent of dispersion was variable and depended upon intrinsic properties of MNPs. However, the co-existing MNPs displayed a dominant hetero-aggregation effect, independent of the residence times. Further research with use of real-world environmental samples can provide additional insights on the effects of sample chemistry on MNPs fate.

"How Do We Do This at a Distance?!" A Descriptive Study of Remote Undergraduate Research Programs during COVID-19.

The COVID-19 pandemic shut down undergraduate research programs across the United States. A group of 23 colleges, universities, and research institutes hosted remote undergraduate research programs in the life sciences during Summer 2020. Given the unprecedented offering of remote programs, we carried out a study to describe and evaluate them. Using structured templates, we documented how programs were designed and implemented, including who participated. Through focus groups and surveys, we identified programmatic strengths and shortcomings as well as recommendations for improvements from students' perspectives. Strengths included the quality of mentorship, opportunities for learning and professional development, and a feeling of connection with a larger community. Weaknesses included limited cohort building, challenges with insufficient structure, and issues with technology. Although all programs had one or more activities related to diversity, equity, inclusion, and justice, these topics were largely absent from student reports even though programs coincided with a peak in national consciousness about racial inequities and structural racism. Our results provide evidence for designing remote Research Experiences for Undergraduates (REUs) that are experienced favorably by students. Our results also indicate that remote REUs are sufficiently positive to further investigate their affordances and constraints, including the potential to scale up offerings, with minimal concern about disenfranchising students.

Behavior of engineered nanoparticles in aquatic environmental samples: Current status and challenges.

The increasing use of engineered nanoparticles (ENPs) in consumer products has led to their increased presence in natural water systems. Here, we present a critical overview of the studies that analyzed the fate and transport behavior of ENPs using real environmental samples. We focused on cerium dioxide, titanium dioxide, silver, carbon nanotubes, and zinc oxide, the widely used ENPs in consumer products. Under field scale settings, the transformation rates of ENPs and subsequently their physicochemical properties (e.g., toxicity and bioavailability) are primarily influenced by the modes of interactions among ENPs and natural organic matter. Other typical parameters include factors related to water chemistry, hydrodynamics, and surface and electronic properties of ENPs. Overall, future nanomanufacturing processes should fully consider the health, safety, and environmental impacts without compromising the functionality of consumer products.

Understanding nanoparticle flow with a new in vitro experimental and computational approach using hydrogel channels.

Nanoparticles (NPs) are considered as one of the most promising drug delivery vehicles and a next-generation solution for current medical challenges. In this context, variables related to flow of NPs such as the quantity of NPs lost during transport and flow trajectory greatly affect the clinical efficiency of NP drug delivery systems. Currently, there is little knowledge of the physical mechanisms dominating NP flow inside the human body due to the limitations of available experimental tools for mimicking complex physiological environments at the preclinical stage. Here, we report a coupled experimental and computational fluid dynamics (CFD)-based novel in vitro approach to predict the flow velocity and binding of NP drug delivery systems during transport through vasculature. Poly(hydroxyethyl)methacrylate hydrogels were used to form soft cylindrical constructs mimicking vascular sections as flow channels for synthesized iron oxide NPs in these first-of-its-kind transport experiments. Brownian dynamics and material of the flow channels played key roles in NP flow, based on the measurements of NP flow velocity over seven different mass concentrations. A fully developed laminar flow of the NPs under these conditions was simultaneously predicted using CFD. Results from the mass loss of NPs during flow indicated a diffusion-dominated flow at higher particle concentrations but a flow controlled by the surrounding fluid and Brownian dynamics at the lowest NP concentrations. The CFD model predicted a mass loss of 1.341% and 6.253% for the 4.12 g·mL-1 and 2.008 g·mL-1 inlet mass concentrations of the NPs, in close confirmation with the experimental results. This further highlights the reliability of our new in vitro technique in providing mechanistic insights of NP flow for potential preclinical stage applications.

Multinary copper-based chalcogenide nanocrystal systems from the perspective of device applications.

Multinary chalcogenide semiconductor nanocrystals are a unique class of materials as they offer flexibility in composition, structure, and morphology for controlled band gap and optical properties. They offer a vast selection of materials for energy conversion, storage, and harvesting applications. Among the multinary chalcogenides, Cu-based compounds are the most attractive in terms of sustainability as many of them consist of earth-abundant elements. There has been immense progress in the field of Cu-based chalcogenides for device applications in the recent years. This paper reviews the state of the art synthetic strategies and application of multinary Cu-chalcogenide nanocrystals in photovoltaics, photocatalysis, light emitting diodes, supercapacitors, and luminescent solar concentrators. This includes the synthesis of ternary, quaternary, and quinary Cu-chalcogenide nanocrystals. The review also highlights some emerging experimental and computational characterization approaches for multinary Cu-chalcogenide semiconductor nanocrystals. It discusses the use of different multinary Cu-chalcogenide compounds, achievements in device performance, and the recent progress made with multinary Cu-chalcogenide nanocrystals in various energy conversion and energy storage devices. The review concludes with an outlook on some emerging and future device applications for multinary Cu-chalcogenides, such as scalable luminescent solar concentrators and wearable biomedical electronics.

Modifying Electrical and Magnetic Properties of Single-Walled Carbon Nanotubes by Decorating with Iron Oxide Nanoparticles.

In this work, we report a facile approach to modify the magnetic and electrical property of Hipco single-walled carbon nanotubes (SWCNTs) by attaching iron oxide nanoparticles (FeNPs). The Raman spectra of FeNP-SWCNTs revealed an apparent intensity reduction of metallic peaks in Radial breathing mode (RBM) region, which indicates the ratio change between the metallic and semiconducting component of SWCNTs after modification. Distinctive magnetic and electric resistance properties of FeNP-SWCNTs were found to be associated with the different shapes of FeNPs. The specific FeNP examples as showcased in this work can be applied to tune the electric and magnetic properties of other nanostructured materials in general and shed light on various electronic and magnetic applications.

Enhanced legume root growth with pre-soaking in α-Fe2O3 nanoparticle fertilizer.

The rising demand for food and energy crops has triggered interest in the use of nanoparticles for agronomy. Specifically, iron oxide-based engineered nanoparticles are promising candidates for next-generation iron-deficiency fertilizers. We used iron oxide and hybrid Pt-decorated iron oxide nanoparticles, at low and high concentrations, and at varied pHs, to model seed pre-soaking solutions for investigation of their effect on embryonic root growth in legumes. This is an environmentally friendly approach, as it uses less fertilizer, therefore less nanoparticles in contact with the soil. Analysis from varied material characterization techniques combined with a statistical analysis method found that iron oxide nanoparticles could enhance root growth by 88-366% at low concentrations (5.54 × 10-3 mg L-1 Fe). Hybrid Pt-decorated iron oxide nanoparticles and a higher concentration of iron oxide nanoparticles (27.7 mg L-1 Fe) showed reduced root growth. The combined materials characterization and statistical analysis used here can be applied to address many environmental factors to finely tune the development of vital nanofertilizers for high efficiency food production.

Pathways for Gold Nucleation and Growth over Protein Cages.

Proteins are widely utilized as templates in biomimetic synthesis of gold nanocrystals. However, the role of proteins in mediating the pathways for gold nucleation and growth is not well understood, in part because of the lack of spatial resolution in probing the complicated biomimetic mineralization process. Self-assembled protein cages, with larger size and symmetry, can facilitate in the visualization of both biological and inorganic components. We have utilized bacteriophage P22 protein cages of ∼60 nm diameter for investigating the nucleation and growth of gold nanocrystals. By adding a gold precursor into the solution with preexisting protein cages and a reducing agent, gold nuclei/prenucleation clusters form in solution, which then locate and attach to specific binding sites on protein cages and further grow to form gold nanocrystals. By contrast, addition of the reducing agent into the solution with incubated gold precursor and protein cages leads to the formation of gold nuclei/prenucleation clusters both in solution and on the surface of protein cages that then grow into gold nanocrystals. Because of the presence of cysteine (Cys) with strong gold-binding affinity, gold nanocrystals tend to bind at specific sites of Cys, irrespective of the binding sites of gold ions. Analyzing the results obtained using these alternate routes provide important insights into the pathways of protein-mediated biomimetic nucleation of gold that challenge the importance of incubation, which is widely utilized in the biotemplated synthesis of inorganic nanocrystals.

A new family of wurtzite-phase Cu2ZnAS4-x and CuZn2AS4 (A = Al, Ga, In) nanocrystals for solar energy conversion applications.

A new family of quaternary semiconductors Cu2ZnAS4-x and CuZn2AS4 (A = Al, Ga, In) has been synthesized in the form of wurtzite phase nanocrystals for the first time. The nanocrystals can be converted to the stannite phase via thermal annealing under a N2 atmosphere. A direct band gap in the visible wavelength region combined with a high absorption cross-section makes these materials promising for solar energy conversion applications.

Flexible and High Performance Supercapacitors Based on NiCo2O4for Wide Temperature Range Applications.

Binder free nanostructured NiCo2O4 were grown using a facile hydrothermal technique. X-ray diffraction patterns confirmed the phase purity of NiCo2O4. The surface morphology and microstructure of the NiCo2O4 analyzed by scanning electron microscopy (SEM) showed flower-like morphology composed of needle-like structures. The potential application of binder free NiCo2O4 as an electrode for supercapacitor devices was investigated using electrochemical methods. The cyclic voltammograms of NiCo2O4 electrode using alkaline aqueous electrolytes showed the presence of redox peaks suggesting pseudocapacitance behavior. Quasi-solid state supercapacitor device fabricated by sandwiching two NiCo2O4 electrodes and separating them by ion transporting layer. The performance of the device was tested using cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. The device showed excellent flexibility and cyclic stability. The temperature dependent charge storage capacity was measured for their variable temperature applications. Specific capacitance of the device was enhanced by ~150% on raising the temperature from 20 to 60 °C. Hence, the results suggest that NiCo2O4 grown under these conditions could be a suitable material for high performance supercapacitor devices that can be operated at variable temperatures.

A facile and cost-effective method for separation of oil-water mixtures using polymer-coated iron oxide nanoparticles.

Catastrophic oil spills and oil from waste waters such as bilge and fracking waters pose major environmental concerns. The limitations of existing cleanup techniques for benign oil remediation has inspired a recent scientific impetus to develop oil-absorbing smart nanomaterials. Magnetic nanocomposites were here designed to allow easy recovery from various systems. In this study, sorption of reference MC252 oil with easy-to-synthesize and low-cost hydrophilic polyvinylpyrrolidone-coated iron oxide nanoparticles is reported for the first time. The one-step modified polyol synthesis in air directly generates water-soluble nanoparticles. Stable polyvinylpyrrolidone-coatings are known to minimize environmental alterations of nanoparticles from aggregation and other processes. Iron oxide provides effective magnetic actuation, while both PVP and iron oxide have low toxicity. These nanoparticles gave quantitative (near 100%) oil removal under optimized conditions. The facile synthesis and ease of use represents a significant improvement over existing techniques.

Controlled synthesis of iron oxide nanoplates and nanoflowers.

An effective approach to synthesizing crystalline iron oxide nanoplates (~3 nm thick) and nanoflowers composed of ~5 nm small grains was reported. The formation of different-shaped nanoparticles in a similar system was achieved by controlling the nucleus concentration and growth rate.

Make conjugation simple: a facile approach to integrated nanostructures.

We report a facile approach to the conjugation of protein-encapsulated gold fluorescent nanoclusters to the iron oxide nanoparticles through catechol reaction. This method eliminates the use of chemical linkers and can be readily extended to the conjugation of biological molecules and other nanomaterials onto nanoparticle surfaces. The key to the success was producing water-soluble iron oxide nanoparticles with active catechol groups. Further, advanced electron microscopy analysis of the integrated gold nanoclusters and iron oxide nanoparticles provided direct evidence of the presence of a single fluorescent nanocluster per protein template. Interestingly, the integrated nanoparticles exhibited enhanced fluorescent emission in biological media. These studies will provide significantly practical value in chemical conjugation, the development of multifunctional nanostructures, and exploration of multifunctional nanoparticles for biological applications.

Water-soluble iron oxide nanoparticles with high stability and selective surface functionality.

The water dispensability and stability of high quality iron oxide nanoparticles synthesized in organic solvents are major issues for biomedical and biological applications. In this paper, a versatile approach for preparing water-soluble iron oxide nanoparticles with great stability and selective surface functionality (-COOH, -NH(2), or -SH) was demonstrated. The hydrophobic nanoparticles were first synthesized by the thermal decomposition of an iron oleate complex in organic solvent. Subsequently, the hydrophobic coatings of nanoparticles were replaced with poly(acrylic acid) , polyethylenimine, or glutathione, yielding charged nanoparticles in aqueous solution. Two parameters were found to be critical for obtaining highly stable nanoparticle dispersions: the original coating and the surfactant-to-nanoparticle ratio. These charged nanoparticles exhibited different stabilities in biological buffers, which were directly influenced by the surface coatings. This report will provide significant practical value in exploring the biological or biomedical applications of iron oxide nanoparticles.

Synthesis and growth mechanism of iron oxide nanowhiskers.

Iron oxide nanowhiskers with dimensions of approximately 2 × 20 nm were successfully synthesized by selectively heating an iron oleate complex. Such nanostructures resulted from the difference in the ligand coordination microenvironments of the Fe(III) oleate complex, according to our electronic structure calculations and thermogravimetric analysis. A ligand-directed growth mechanism was subsequently proposed to rationalize the growth process. The formation of the nanowhiskers provides a unique example of shape-controlled nanostructures, offering additional insights into nanoparticle synthesis.