Under the CTAP Statement of Work, Sandia was tasked with providing technical assistance to Dine College to create a testing program to determine hazardous contaminant levels in donated hand sanitizer. Sandia will loan instrumentation, provide a procedure, and act as technical advisor. The challenge for on-site testing lies in a balance of testing capability/speed, complexity, and cost of operations. Instruments that allow fastest and least expensive operation will be validated for performance for this sample problem (hand sanitizer w/ poisonous methanol or 1-propanol). The objective of this project is to enable Dine College personnel to perform on-site testing.
Although mass spectrometry is a widely used analytical tool, age-appropriate, interactive outreach activities for laboratory visitors, especially children, are lacking. The presented interactive demonstration, "Did you eat a MOLEcule today?", introduces all ages to molecular weight concepts and mass spectrometry in a research laboratory, while connecting the concepts to real-world applications. Through real-time breath analysis, participants explore the concepts of molecular weight, electrostatic field manipulation of charged molecules, and analyte identification by mass analysis. This module is rapid and highly adaptable for outreach activities but also includes age- or classroom-appropriate variations to decrease or increase difficulty levels. The presented interactive demonstration has repeatedly been implemented, with over 2300 participants during six annual "Take Our Daughters & Sons to Work Day" and two corporate "Family Day" outreach activities, successfully engaging, exciting, and educating both kids and parents.
Alkali metals, such as lithium, sodium, potassium, etc., are highly reactive elements. While researchers generally handle these metals with caution, less caution is taken when these elements have been “reacted”. In this work, a recent incident is examined in which a pair of researchers ignited a lithium silicide alloy sample that was assumed to be fully hydrated to lithium hydroxide and, thereby, no longer water-reactive. However, variations in the original chemical composition of the lithium compounds examined resulted in select mixtures failing to hydrate and react completely to lithium hydroxide in the time frame allowed. This gave rise to residual unreacted, water-sensitive lithium silicide which resulted in a violent exothermic reaction with water and autoignition of the produced hydrogen gas. This Article describes this incident and improvements that can be implemented to prevent similar incidents from occurring.
Laboratory research can expose workers to a wide variety of chemical hazards. Researchers must not only take personal responsibility for their safety but also inevitably rely on coworkers to also work safely. The foundations for protocols, requirements, and behaviors come from our history and lessons learned from others. For that reason, here, a recent incident is examined in which a researcher suffered hydrofluoric acid (HF) burns while working with an inorganic digestion mixture of aqueous HF (8%) and nitric acid (HNO3, 58%). HF education is critical for workers because delays in treatment, improper treatment, and delay of symptoms are all factors in unfavorable outcomes in case reports. While the potential severity of the incident was elevated due to bypassed engineered controls and lack of proper personal protective equipment, only minor injuries were sustained. We discuss the results of a causal analysis of the incident that revealed areas of improvement in protocols, personal protective equipment, and emergency response that could help prevent similar accidents from occurring. We also present simple improvements that anyone can implement to reduce the potential consequences of an accident, based upon our lessons learned.
This communication describes a novel series of linear and crosslinked polyurethanes (PUs) and their selective depolymerization under mild conditions. Two unique polyols are synthesized bearing unsaturated units in a configuration designed to favor ring-closing metathesis (RCM) to five- and six-membered cycloalkenes. These polyols are co-polymerized with toluene diisocyanate to generate linear PUs and trifunctional hexamethylene- and diphenylmethane-based isocyanates to generate crosslinked PUs. The polyol design is such that the RCM reaction cleaves the backbone of the polymer chain. Upon exposure to dilute solutions of Grubbs’ catalyst under ambient conditions, the PUs are rapidly depolymerized to low molecular weight, soluble products bearing vinyl and cycloalkene functionalities. These functionalities enable further re-polymerization by traditional strategies for polymerization of double bonds. It is anticipated that this general approach can be expanded to develop a range of chemically recyclable condensation polymers that are readily depolymerized by orthogonal metathesis chemistry.
Kustas, Jessica K.; Hoffman, Jacob B.; Alonso, David; Reed, Julian H.; Gonsalves, Andrew E.; Oh, Junho; Hong, Sungmin; Jo, Kyoo D.; Dana, Catherine E.; Alleyne, Marianne; Miljkovic, Nenad; Cropek, Donald M.
Cicada wings exhibit several intriguing properties that arise from a combination of nanopillar structures and chemical constituents, including superhydrophobicity, as well as antimicrobial, antireflective, and self-cleaning functions. While the physical dimensions of the nanofeatures are relatively simple to characterize through microscopy, the chemicals that cover these pillars are more difficult to characterize due to the variety and complexity of the mixture. Here, we compared the extractable chemicals from the wing surfaces of two different cicada species using both gas chromatography time-of-flight mass spectrometry (GC-TOFMS) and two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOFMS) platforms. Chemical extracts from Neotibicen pruinosus and Magicicada septendecim cicada wings were separated and analyzed. The GC × GC-TOFMS platform was able to isolate and identified roughly three times the number of constituents as the GC-TOFMS platform at a signal-to-noise ratio (SNR) ≥10.0 and spectral similarity ≥800. When comparing the two cicada species wing extracts, the two-dimensional platform was able to expose differences in the chemical composition that were undetectable by the one-dimensional technique. GC × GC-TOFMS revealed nearly four times the number of unique species-specific compounds as compared to the number identified by GC-TOFMS. Further, surface chemicals were identified that are likely xenobiotics and can pinpoint location and contamination from where the cicada was collected. While the advantages of GC × GC-TOFMS over GC-TOFMS have been documented in the past, our work presents a powerful biological application of GC × GC-TOFMS with promise to reveal both organism species-specific biomarkers while providing insight into the environmental conditions of individual organisms.
Oh, Junho; Hoffman, Jacob B.; Hong, Sungmin; Jo, Kyoo D.; Kustas, Jessica K.; Reed, Julian H.; Dana, Catherine E.; Cropek, Donald M.; Alleyne, Marianne; Miljkovic, Nenad
Nanoimprinting lithography (NIL) is a next-generation nanofabrication method, capable of replicating nanostructures from original master surfaces. Here, we develop highly scalable, simple, and nondestructive NIL using a dissolvable template. Termed dissolvable template nanoimprinting lithography (DT-NIL), our method utilizes an economic thermoplastic resin to fabricate nanoimprinting templates, which can be easily dissolved in simple organic solvents. We used the DT-NIL method to replicate cicada wings which have surface nanofeatures of ∼100 nm in height. The master, template, and replica surfaces showed a >∼94% similarity based on the measured diameter and height of the nanofeatures. The versatility of DT-NIL was also demonstrated with the replication of re-entrant, multiscale, and hierarchical features on fly wings, as well as hard silicon wafer-based artificial nanostructures. The DT-NIL method can be performed under ambient conditions with inexpensive materials and equipment. Our work opens the door to opportunities for economical and high-throughput nanofabrication processes.
Kustas, Jessica K.; Hoffman, Jacob B.; Reed, Julian H.; Gonsalves, Andrew E.; Oh, Junho; Li, Longnan; Hong, Sungmin; Jo, Kyoo D.; Dana, Catherine E.; Miljkovic, Nenad; Cropek, Donald M.; Alleyne, Marianne
Numerous natural surfaces have micro/nanostructures that result in extraordinary functionality, such as superhydrophobicity, self-cleaning, antifogging, and antimicrobial properties. One such example is the cicada wing, where differences in nanopillar geometry and composition among species can impact and influence the degree of exhibited properties. To understand the relationships between surface topography and chemical composition with multifunctionality, the wing properties of Neotibicen pruinosus (superhydrophobic) and Magicicada cassinii (hydrophobic) cicadas are investigated at time points after microwave-assisted extraction of surface molecules to characterize the chemical contribution to nanopillar functionality. Electron microscopy of the wings throughout the extraction process illustrates nanoscale topographical changes, while concomitant changes in hydrophobicity, bacterial fouling, and bactericidal properties are also measured. Extract analysis reveals the major components of the nanostructures to be fatty acids and saturated hydrocarbons ranging from C17 to C44. Effects on the antimicrobial character of a wing surface with respect to the extracted chemicals suggest that the molecular composition of the nanopillars plays both a direct and an indirect role in concert with nanopillar geometry. The data presented not only correlates the nanopillar molecular organization to macroscale functional properties, but it also presents design guidelines to consider during the replication of natural nanostructures onto engineered substrates to induce desired properties.
Energy storage systems with Li-ion batteries are increasingly deployed to maintain a robust and resilient grid and facilitate the integration of renewable energy resources. However, appropriate selection of cells for different applications is difficult due to limited public data comparing the most commonly used off-the-shelf Li-ion chemistries under the same operating conditions. This article details a multi-year cycling study of commercial LiFePO4 (LFP), LiNixCoyAl1-x-yO2 (NCA), and LiNixMnyCo1-x-yO2 (NMC) cells, varying the discharge rate, depth of discharge (DOD), and environment temperature. The capacity and discharge energy retention, as well as the round-trip efficiency, were compared. Even when operated within manufacturer specifications, the range of cycling conditions had a profound effect on cell degradation, with time to reach 80% capacity varying by thousands of hours and cycle counts among cells of each chemistry. The degradation of cells in this study was compared to that of similar cells in previous studies to identify universal trends and to provide a standard deviation for performance. All cycling files have been made publicly available at batteryarchive.org, a recently developed repository for visualization and comparison of battery data, to facilitate future experimental and modeling efforts.
Reed, Julian H.; Gonsalves, Andrew E.; Kustas, Jessica K.; Oh, Junho O.; Cha, Hyeongyun C.; Dana, Catherine E.; Toc, Marco T.; Hong, Sungmin H.; Hoffman, Jacob B.; Andrade, Juan A.; Jo, Kyoo J.; Alleyne, Marianne A.; Miljkovic, Nenad M.; Cropek, Donald C.
Biofouling disrupts surface functionality and integrity of engineered substrates. A variety of natural materials such as plant leaves and insect wings have evolved sophisticated physical mechanisms capable of preventing biofouling. Over the past decade, several reports have pinpointed nanoscale surface topography as an important regulator of the surface adhesion and growth of bacteria. Although artificial nanoengineered features have been used to create bactericidal materials that kill adhered bacteria, functional surfaces capable of synergistically providing anti-biofouling and bactericidal properties remain to be developed. Furthermore,fundamental questions pertaining to the need for intrinsic hydrophobicity to achieve bactericidal performance or the crucial role played by structure length scale (nano vs. micro), remain to be answered. Here, we demonstrate highly scalable, cost effective, and efficient nanoengineered multifunctional surfaces that possess both anti-biofouling and bactericidal properties on industrially relevant copper (Cu) and aluminum (A1) substrates. We characterize biofouling and bactericidal performance using a combination of scanning electron microscopy (SEM), atomic force microscopy (AFM), live-dead bacterial staining and imaging, as well as solution phase measurements of bacterial viability. SEM results showed that nanostructures created on both Cuand Al were capable of physical deformation of adhered E. coli. Bacterial viability measurements on both Cu and Al indicated a complex interaction between the anti-biofouling and bactericidal nature of these materials and their surface topography, chemistry, and structure. We found that nano-length structures, as compared to micro-length, provide improved bactericidal properties,and that increased hydrophobicity greatly decreased the of adhered bacteria while also modestly increasing the surfaces killing capacity. This study provides additional insights into design guidelines for materials that are not only bactericidal, but also anti-biofouling, using a simple and economic method.