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N6-methyladenosine (m6A) is a RNA modification that can regulate post-transcriptional processes including RNA stability, translation, splicing, and nuclear export. In CD4+lymphocytes, m6A modifications have been demonstrated to play a role in early differentiation processes. The role of m6A in CD4+T cell activation and effector function remains incompletely understood. To assess the role of m6A in CD4+T lymphocyte activation and function, we assessed the transcriptome-wide m6A landscape of human primary CD4+T cells by methylated RNA immunoprecipitation sequencing. Stimulation of the T cells impacted the m6A pattern of hundreds of transcripts including tumor necrosis factor (TNF). m6A methylation was increased on TNFmessenger RNA (mRNA) after activation, predominantly in the 3′ untranslated region of the transcript. Manipulation of m6A levels in primary human T cells, the directly affected the expression of TNF. Furthermore, we identified that the m6A reader protein YTHDF2 binds m6A-methylated TNFmRNA, and promotes its degradation. Taken together, this study demonstrates that TNF expression in CD4+T lymphocytes is regulated via m6A and YTHDF2, thereby providing novel insight into the regulation of T cell effector functions.This study demonstrates that tumor necrosis factor expression in CD4+ T lymphocytes is regulated via N6-methyladenosine and YTHDF2, thereby providing novel insight into the regulation of T cell effector functions.T helper cells are immune cells of the adaptive immune system. These cells are activated by antigen presenting cells that have engulfed invading pathogens. When the T helper cell is activated, it will produce and excrete signaling molecules (cytokines) that activate other immune cells in order to eradicate these pathogens. Cytokines are formed after translation of RNA molecules that encode for these cytokines. In this study it was found that a modification (N6-methyladenosine) on RNA molecules is involved in the regulation of the life cycle of these RNA molecules. It was found that the degradation of RNA encoding for cytokine tumor necrosis factor (TNF) was mediated through N6-methyladenosine and its “reader” protein YTHDF2 in activated T helper cells. As TNF promotes inflammation, reduction of TNF production through this mechanism dampens the immune response and therefore prevents chronic inflammation.

ABSTRACTIntroductionNeovascular age-related macular degeneration (nAMD) represents a leading cause of severe visual impairment in individuals over 50 years of age in developed nations. Intravitreal anti-vascular endothelial growth factor (VEGF) injections have become the standard of care for treating nAMD; however, monthly or bimonthly dosing represents significant time and cost burden due to the disease’s chronic nature and limited medication half-life.Areas coveredThis review summarizes innovative therapeutics and delivery methods for nAMD. Emerging methods for extended drug delivery include high molar concentration anti-VEGF drugs, intravitreal sustained-release polymers and devices, reservoirs for intravitreal delivery, suprachoroidal delivery of small molecular suspensions and gene therapy biofactories. In addition to VEGF-A, therapies targeting inhibition of VEGF-C and D, the angiopoetin-2 (Ang-2)/Tie-2 pathway, tyrosine kinases, and integrins are reviewed.Expert opinionThe evolving therapeutic landscape of nAMD is rapidly expanding our toolkit for effective and durable treatment. Recent FDA approvals of faricimab (Vabysmo) and high-dose aflibercept (Eylea HD) for nAMD with potential extension of injection intervals up to four months have been promising developments for patients and providers alike. Further research and innovation, including novel delivery techniques and pharmacologic targets, is necessary to validate the efficacy of developing therapeutics and characterize real-world outcomes, demonstrating promise in expanding treatment durability.

Herein we describe a series of synthetic efforts to prepare an advanced GPR40 agonist (compound 1), with focus on phase-appropriate processes that circumvented key reagents with short supply in the original synthesis. The key transformations refined for large-scale production were an asymmetric aldol reaction, O-alkylation of an unstable intermediate, selective (Z)-olefination, and reduction of a Weinreb amide to aldehyde. Additionally, the new route circumvented stability issues of the core pyrrolidine fragment through de novosynthesis, achieving high d.r. during ring formation. The new improved route was efficiently scaled up to prepare more than 100 g API for toxicology studies.

One concern with subsidies for low-carbon technologies is that they tend to go predominantly to high-income households. Previous research has shown, for example, that the top income quintile receives 60% of subsidies for rooftop solar and 90% of subsidies for electric vehicles. This paper finds that heat pumps are an important exception. Using newly available US nationally representative data, the paper finds that there is remarkably little correlation between heat pump adoption and household income. Nationwide, 14% of US households have a heat pump as their primary heating equipment, and adoption levels are essentially identical for all income levels ranging from the bottom of the income distribution (<$30,000 annually) to the top ($150,000+). Instead, the paper shows that heat pump adoption is strongly correlated with geography, climate, and electricity prices.

Medical image segmentation, or computing voxel-wise semantic masks, is a fundamental yet challenging task in medical imaging domain. To increase the ability of encoder-decoder neural networks to perform this task across large clinical cohorts, contrastive learning provides an opportunity to stabilize model initialization and enhances downstream tasks performance without ground-truth voxel-wise labels. However, multiple target objects with different semantic meanings and contrast level may exist in a single image, which poses a problem for adapting traditional contrastive learning methods from prevalent “image-level classification” to “pixel-level segmentation”. In this article, we propose a simple semantic-aware contrastive learning approach leveraging attention masks and image-wise labels to advance multi-object semantic segmentation. Briefly, we embed different semantic objects to different clusters rather than the traditional image-level embeddings. We evaluate our proposed method on a multi-organ medical image segmentation task with both in-house data and MICCAI Challenge 2015 BTCV datasets. Compared with current state-of-the-art training strategies, our proposed pipeline yields a substantial improvement of 5.53% and 6.09% on Dice score for both medical image segmentation cohorts respectively (p-value$&lt;$ 0.01). The performance of the proposed method is further assessed on external medical image cohort via MICCAI Challenge FLARE 2021 dataset, and achieves a substantial improvement from Dice 0.922 to 0.933 (p-value$&lt;$ 0.01).

ABSTRACT The environmental impact of Ordinary Portland Cement (OPC) production has driven substantial interest in the development of new types of 'green' concrete, one of which is geopolymer concrete. If [...]

The ability to tailor polymer brush coatings to the last nanometer has arguably placed them among the most powerful surface modification techniques currently available. Generally, the synthesis procedures for polymer brushes are designed for a specific surface type and monomer functionality and cannot be easily employed otherwise. Herein, we describe a modular and straightforward two-step grafting-to approach that allows introduction of polymer brushes of a desired functionality onto a large range of chemically different substrates. To illustrate the modularity of the procedure, gold, silicon oxide (SiO2), and polyester-coated glass substrates were modified with five different block copolymers. In short, the substrates were first modified with a universally applicable poly(dopamine) primer layer. Subsequently, a grafting-to reaction was performed on the poly(dopamine) films using five distinct block copolymers, all of which contained a short poly(glycidyl methacrylate) segment and longer segment of varying chemical functionality. Ellipsometry, X-ray photoelectron spectroscopy, and static water contact angle measurements confirmed successful grafting of all five block copolymers to the poly(dopamine)-modified gold, SiO2, and polyester-coated glass substrates. In addition, our method was used to provide direct access to binary brush coatings, by simultaneous grafting of two different polymer materials. The ability to synthesize binary brush coatings further adds to the versatility of our approach and paves the way toward production of novel multifunctional and responsive polymer coatings.

Imagine a transportation company operating out of Fort Riley, Kansas, that is required to deliver fuel to New York City, ammunition to Atlanta, and repair parts to California simultaneously. Now [...]

Placing the electrical and photonic chiplets in a single package leads to significant power reduction. Chiplets are connected by fine-line electrical routing over a length of a few millimeters and optical interconnects in the package connect photonic chips with optical fibers for off-package communication. A packaging substrate made of glass with optical waveguides, through glass vias and electrical redistribution layers inside a single-sided cavity enables lower-cost assembly. A single-sided 50 μm deep cavity was etched in glass, and electrical copper lines with 5 μm in height and width were deposited on the floor of the cavity. Ion-exchange (IOX) waveguides with propagation loss of &lt;0.1 dB/cm were fabricated below the glass surface. For flip-chip assembly of photonic chips and optical coupling with the IOX waveguides at the top surface of the glass, all electrical interconnects were located inside the cavity. Photonic chips with silicon nitride waveguides were optically coupled to glass waveguides with a minimum loss of 0.5 dB, achieved by fiducial-aligned flip-chip photonic assembly. A low-profile fiber connector with height of 4.4 mm connects the integrated ion-exchanged waveguides with the optical fibers. Average connector loss of 0.83 dB was demonstrated with physical contact between fibers and IOX glass waveguides.

This paper provides the first empirical analysis of the homeowner-renter gap for electric appliances. Using U.S. nationally representative data, the analysis shows that renters are significantly more likely than homeowners to have electric heat, electric hot water heating, an electric stove, and an electric dryer. The gap is highly statistically significant, prevalent across regions, and holds after controlling for the type, size, and age of the home, as well as for climate and household characteristics. The paper argues that this gap arises from the same split incentives that lead to the “landlord-tenant problem” and discusses the implications of the gap for an emerging set of policies aimed at reducing carbon dioxide emissions through building electrification.

The growing “electrify everything” movement aims to reduce carbon dioxide emissions by transitioning households and firms away from natural gas toward electricity. This paper considers what this transition means for the customers who are left behind. Using historical evidence from growing and shrinking US natural gas utilities, we show that utilities add pipelines but rarely remove them, even when the customer base from which to recover costs is shrinking. Correspondingly, we find that utility revenues decrease less than one for one when a customer base is shrinking, consistent with higher bills for remaining customers. We then use our empirical estimates to predict how customer bills might increase in the future for different levels of building electrification. We highlight the equity implications of our results and conclude by discussing alternative utility financing options such as recouping fixed costs through taxes rather than prices.

IMPORTANCE: Surgical complications associated with perioperative hyperglycemia are conventionally associated with diabetes, but, paradoxically, prior cohort studies have found that patients without diabetes have greater risk of complications at similar levels of hyperglycemia compared with patients with diabetes. OBJECTIVE: To describe the association between perioperative hyperglycemia and surgical complications in a population of surgical patients without diabetes receiving routine blood glucose testing and insulin administration and to evaluate the potential correlation of perioperative hyperglycemia. DESIGN, SETTING, AND PARTICIPANTS: This retrospective cohort study of National Surgical Quality Improvement Program–defined complications after operation took place at a single academic medical center hospital from January 2013 to October 2016. Consecutive patients undergoing general, vascular, and gynecologic operations who were expected to have at least a 48-hour admission were included. Hyperglycemia was defined as blood glucose level of 140 mg/dL or higher within 24 hours after surgery. Multivariate regression was used to assess the association of hyperglycemia and complications, stratified by hyperglycemia severity and adjusted for diabetes status. Analysis began in February 2022. EXPOSURES: Routine blood glucose testing and insulin administration. MAIN OUTCOMES AND MEASURES: The main outcomes are odds of experiencing perioperative hyperglycemia and postoperative complication, comparing patients with and without diabetes. RESULTS: A total of 7634 patients (mean [SD] age, 53.5 [15.1] years; 6664 patients without diabetes [83.3%] and 970 patients with diabetes [17.7%]) underwent general (6204 [81.3%]), vascular (208 [2.7%]), and gynecologic (1222 [16%]) operations. Of these, 5868 (77%) had blood glucose testing (4899 individuals without diabetes [73.5%] and 969 [99.9%] with diabetes). Hyperglycemia occurred in 882 patients with diabetes (91%) and 2484 patients without diabetes (50.7%). Of those with blood glucose level more than 180 mg/dL, 1388 (72.7%) received insulin (658 patients with diabetes who had hyperglycemia [91%] and 680 patients without diabetes who had hyperglycemia [61%]). Adjusted odds of experiencing a complication were 83% greater for patients without vs with diabetes at blood glucose level of 140 to 179 mg/dL (odds ratio, 1.83 [95% CI, 0.93-3.6]), 49% greater for blood glucose level of 180 to 249 mg/dL (odds ratio, 1.49 [95% CI, 1.06-2.11]), and 88% greater for blood glucose level more than 250 mg/dL (odds ratio, 1.88 [95% CI, 1.11-3.17]). A similar trend was observed for serious complications. Insulin may mitigate the association of hyperglycemia and complications in patients without diabetes. CONCLUSIONS AND RELEVANCE: In this study, with near universal blood glucose testing and frequent insulin use, patients without diabetes paradoxically had worse outcomes than patients with diabetes at similar levels of hyperglycemia. Insulin may mitigate this effect and broader use may improve outcomes.

Rare genetic variants in CDK13are responsible for CDK13-related disorder (CDK13-RD), with main clinical features being developmental delay or intellectual disability, facial features, behavioral problems, congenital heart defect, and seizures. In this paper, we report 18 novel individuals with CDK13-RD and provide characterization of genome-wide DNA methylation.

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The article discusses the author's experience as a gay medical student attending the AAOS 2024 Annual Meeting in San Francisco. The author highlights the significance of the inaugural Pride Ortho Annual Meeting, which promotes LGBTQ+ diversity and inclusion in orthopaedic surgery. The attendance and endorsement of AAOS president Kevin J. Bozic, as well as the recognition of several orthopaedic surgeons with Pride Ortho Ally Awards, demonstrate a cultural shift in the field. The author emphasizes the importance of mentorship and the need for greater visibility and research on LGBTQ+ topics in orthopaedics. [Extracted from the article]

Teju Cole’s Open Cityprovides a suitable springboard for insight into the dynamic ways in which Hans Ulrich Gumbrecht’s concept of a broad present might relate to the spatial-temporal configurations of a text. More specifically, Open Cityuses a combination of formal and stylistic approaches to illustrate the instability innate in modern, urban spaces to demonstrate the approaching apocalyptic visions of the future as well as the torrential multiplicity of histories that threaten to subsume the present. Stable notions of time are shown to be paralyzing, and alternatives ought to be sought out in presenting a sense of space-time that is free from the stagnation promised by dominant modes of spatial-temporal configurations.

The use of sodium dithionite with perfluoroalkyl iodides under basic conditions facilitates the direct perfluoroalkylation of arenes with pendant benzylic electron-withdrawing groups. This occurs via attack of the arene on the electrophilic perfluoroalkyl radical, through the donation of electron density from a benzylic anion. The substrate scope was expanded beyond benzylic nitriles with cyclic substrates bearing electron-withdrawing groups at the benzylic position—enforcing donation of electron density to the aromatic ring and enabling attack on the perfluoroalkyl radical.

The thermal stabilities of endogenous, intact proteins and protein assemblies in complex mixtures were characterized in parallel by means of variable-temperature electrospray ionization coupled to mass spectrometry (vT-ESI-MS). The method is demonstrated by directly measuring the melting transitions of seven proteins from a mixture of proteins derived from ribosomes. A proof-of-concept measurement of a fraction of an Escherichia colilysate is provided to extend this approach to characterize the thermal stability of a proteome. As the solution temperature is increased, proteins and protein complexes undergo structural and organizational transitions; for each species, the folded ↔ unfolded and assembled ↔ disassembled populations are monitored based on changes in vT-ESI-MS charge state distributions and masses. The robustness of the approach illustrates a step toward the proteome-wide characterization of thermal stabilities and structural transitions—the stabilitome.

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Insects have evolved unique structures that host a diversity of material and mechanical properties, and the mouthparts (proboscis) of butterflies and moths (Lepidoptera) are no exception. Here, we examined proboscis morphology and material properties from several previously unstudied moth lineages to determine if they relate to flower visiting and non-flower visiting feeding habits. Scanning electron microscopy and three-dimensional imaging were used to study proboscis morphology and assess surface roughness patterns on the galeal surface, respectively. Confocal laser scanning microscopy was used to study patterns of cuticular autofluorescence, which was quantified with colour analysis software. We found that moth proboscises display similar autofluorescent signals and morphological patterns in relation to feeding habits to those previously described for flower and non-flower visiting butterflies. The distal region of proboscises of non-flower visitors is brush-like for augmented capillarity and exhibited blue autofluorescence, indicating the possible presence of resilin and increased flexibility. Flower visitors have smoother proboscises and show red autofluorescence, an indicator of high sclerotization, which is adaptive for floral tube entry. We propose the lepidopteran proboscis as a model structure for understanding how insects have evolved a suite of morphological and material adaptations to overcome the challenges of acquiring fluids from diverse sources.

In this paper, we examine executive compensation data from 78 major U.S. oil and gas companies over a 24-year period. Perhaps in no other industry are the fortunes of so many executives so dependent on a single global commodity price. We find that a 10% increase in oil prices is associated with a 2% increase in executive compensation. This oil price effect holds for both CEOs and non-CEOs and separately for several different individual components of compensation, including bonuses.We find that the oil price effect is larger in companies with more insiders on the board, and asymmetric, with executive compensation rising with increasing oil prices more than it falls with decreasing oil prices. We then discuss potential mechanisms drawn from the broader existing literature on executive compensation.

Chiral phosphoric-acid-catalyzed asymmetric reductions of trans-chalcones have been investigated in this work. A BINOL-derived boro-phosphate-catalyzed asymmetric transfer hydrogenation of the carbon–carbon double bond of trans-chalcone derivatives employing borane as a hydride source was realized. This methodology provides a convenient procedure to access chiral dihydrochalone derivatives in high yields and with high enantioselectivities under mild conditions.

This work presents a new method for the synthesis of antifouling polymer brushes using surface-initiated photoinduced electron transfer-reversible addition–fragmentation chain-transfer polymerization with eosin Y and triethanolamine as catalysts. This method proceeds in an aqueous environment under atmospheric conditions without any prior degassing and without the use of heavy metal catalysts. The versatility of the method is shown by using three chemically different monomers: oligo(ethylene glycol) methacrylate, N-(2-hydroxypropyl)methacrylamide, and carboxybetaine methacrylamide. In addition, the light-triggered nature of the polymerization allows the creation of complex three-dimensional structures. The composition and topological structuring of the brushes are confirmed by X-ray photoelectron spectroscopy and atomic force microscopy. The kinetics of the polymerizations are followed by measuring the layer thickness with ellipsometry. The polymer brushes demonstrate excellent antifouling properties when exposed to single-protein solutions and complex biological matrices such as diluted bovine serum. This method thus presents a new simple approach for the manufacturing of antifouling coatings for biomedical and biotechnological applications.

In many countries, the revenue from gasoline taxes is used to fund highways and other transportation infrastructure. As the number of electric vehicles on the road increases, this raises questions about the effectiveness and equity of this financing mechanism. In this paper, we ask whether electric vehicle drivers should pay a mileage tax. Though the gasoline tax has been traditionally viewed as a benefits tax, we instead take the perspective of economic efficiency. We derive a condition for the optimal electric vehicle mileage tax that highlights a key trade-off. On the one hand, there are externalities from driving, including traffic congestion and accidents, that imply a mileage tax is efficient. On the other hand, gasoline tends to be underpriced, so a low (or even negative) mileage tax might have efficiency benefits in encouraging substitution away from gasoline-powered vehicles. We then turn to an empirical analysis aimed at better understanding the current policy landscape for electric vehicles in the United States. Using newly available, nationally representative microdata, we calculate that electric vehicles have reduced gasoline tax revenues by $250 million annually. We show that the forgone tax revenue is highly concentrated in a handful of states and is highly regressive, as most electric vehicles are driven by high-income households, and we discuss how this motivates and informs optimal policy.

Studies have confirmed that optic disc haemorrhage (ODH) is a significant risk factor for the development and progression of primary open-angle glaucoma (POAG). Various populations have differing risk factors for developing POAG. As such, a literature review was conducted examining seven studies published in India, China, Japan, Australia, Korea and the USA. The goal of this review was to better identify ODH risk factors and their relationship to development and progression of POAG. Ultimately, patients with ODH have a greater risk for developing POAG across all populations analysed in this review. However, some populations demonstrated additional risk factors for ODH, such as increasing age and female gender. Paradoxically, data from several studies show that people of African descent have a reduced risk of ODH despite having increased risk of open-angle glaucoma than their Caucasian counterparts. By parsing out the complex relations between ODH and open-angle glaucoma stratified by age, gender and race, we may gain a broader understanding of glaucoma pathogenesis and derive individualised treatment strategies.

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A full-dimension quasi-classical trajectory study of collisions between two NH radicals is presented. Interatomic interactions are represented by a previously reported global six-dimensional potential energy surface for singlet electronic state of the N2H2system. This study suggests that the formation of N2from the collision of two NH radicals may occur via a one-step (NH + NH → N2+ H + H) or two-step (NH + NH → N2H + H → N2+ H + H) microscopic reaction mechanism. A fast vibrational energy redistribution is observed in the four-body complex in the latter mechanism. Excitation functions are presented and discussed. A variant of the vibrational energy quantum mechanical threshold method was used to correct the zero-point energy leakage in the classical calculations. The influence of reactant’s rotational and vibrational energy on reactivity was investigated by state-specific calculations with one or both reactants excited. Reaction rate constants for the ground and some rotationally excited states are presented using an Arrhenius–Kooij-like functional form.

Ni-catalyzed C(sp3)–O bond activation provides a useful approach to synthesize enantioenriched products from readily available enantioenriched benzylic alcohol derivatives. The control of stereospecificity is key to the success of these transformations. To elucidate the reversed stereospecificity and chemoselectivity of Ni-catalyzed Kumada and cross-electrophile coupling reactions with benzylic ethers, a combined computational and experimental study is performed to reach a unified mechanistic understanding. Kumada coupling proceeds via a classic cross-coupling mechanism. Initial rate-determining oxidative addition occurs with stereoinversion of the benzylic stereogenic center. Subsequent transmetalation with the Grignard reagent and syn-reductive elimination produce the Kumada coupling product with overall stereoinversion at the benzylic position. The cross-electrophile coupling reaction initiates with the same benzylic C–O bond cleavage and transmetalation to form a common benzylnickel intermediate. However, the presence of the tethered alkyl chloride allows a facile intramolecular SN2 attack by the benzylnickel moiety. This step circumvents the competing Kumada coupling, leading to the excellent chemoselectivity of cross-electrophile coupling. These mechanisms account for the observed stereospecificity of the Kumada and cross-electrophile couplings, providing a rationale for double inversion of the benzylic stereogenic center in cross-electrophile coupling. The improved mechanistic understanding will enable design of stereoselective transformations involving Ni-catalyzed C(sp3)–O bond activation.

Despite widespread agreement that a carbon tax would be more efficient, many countries use fuel economy standards to reduce transportation-related carbon dioxide emissions. We pair a simple model of the automakers’ profit maximization problem with unusually rich nationally representative data on vehicle registrations to estimate the distributional impact of US fuel economy standards. The key insight from the model is that fuel economy standards impose a constraint on automakers that creates an implicit subsidy for fuel-efficient vehicles and an implicit tax for fuel-inefficient vehicles. Moreover, when these obligations are tradable, permit prices make it possible to quantify the exact magnitude of these implicit subsidies and taxes. We use the model to determine which vehicles are most subsidized and taxed, and we compare the pattern of ownership of these vehicles between high- and low-income census tracts. Finally, we compare these distributional impacts with existing estimates in the literature for a carbon tax.

Enantioselective total syntheses of the anticancer isocarbostyril alkaloids (+)-7-deoxypancratistatin, (+)-pancratistatin, (+)-lycoricidine, and (+)-narciclasine are described. Our strategy for accessing this unique class of natural products is based on the development of a Ni-catalyzed dearomative trans-1,2-carboamination of benzene. The effectiveness of this dearomatization approach is notable, as only two additional olefin functionalizations are needed to construct the fully decorated aminocyclitol cores of these alkaloids. Installation of the lactam ring has been achieved through several pathways and a direct interconversion between natural products was established via a late-stage C-7 cupration. Using this synthetic blueprint, we were able to produce natural products on a gram scale and provide tailored analogs with improved activity, solubility, and metabolic stability.

Additive manufacturing (AM) presents unique challenges to the nondestructive testing community, not least in that it requires inspection of parts with complex forms that are not possible using subtractive manufacturing.The drive to use AM for parts where design approaches include damage tolerance and retirement-for-causewithhigh quality and where safety criticality imposes new QA/QC requirements is growing.This article reviews the challenges faced to enable reliable inspection and characterization in metal powder-based AM processes,including issues due to geometric and microstructural features of interest, the limitation on existing and emerging NDT techniques, and remaining technology gaps. The article looks at inspection from powder to finished part, but focuses primarily on monitoring and characterization during the build. In-process, quantitative characterization and monitoring is anticipated to be transformational inadvancing adoption of metal AM parts,including offering the potential for in-process repair or early part rejection during part fabrication. [ABSTRACT FROM AUTHOR]

ABSTRACTDespite increasing calls for reform many countries continue to provide subsidies for gasoline and diesel. This paper quantifies the external costs from global fuel subsidies using the latest available data and estimates from the World Bank and International Monetary Fund. Under preferred assumptions about supply and demand elasticities, current subsidies cause $44 billion in external costs annually. This includes $8 billion from carbon dioxide emissions, $7 billion from local pollutants, $12 billion from traffic congestion, and $17 billion from accidents. These external costs are in addition to conventional deadweight loss, estimated to be $26 billion annually. Government incentives for alternative fuel vehicles are unlikely to cost-effectively reduce these externalities as they do little to address traffic congestion or accidents and only indirectly address carbon dioxide and local pollutants.

Organic glass films formed by physical vapor deposition exhibit enhanced stability relative to those formed by conventional liquid cooling and aging techniques. Recently, experimental and computational evidence has emerged indicating that the average molecular orientation can be tuned by controlling the substrate temperature at which these “stable glasses” are grown. In this work, we present a comprehensive all-atom simulation study of ethylbenzene, a canonical stable-glass former, using a computational film formation procedure that closely mimics the vapor deposition process. Atomistic studies of experimentally formed vapor-deposited glasses have not been performed before, and this study therefore begins by verifying that the model and method utilized here reproduces key structural features observed experimentally. Having established agreement between several simulated and experimental macroscopic observables, simulations are used to examine the substrate temperature dependence of molecular orientation. The results indicate that ethylbenzene glasses are anisotropic, depending upon substrate temperature, and that this dependence can be understood from the orientation present at the surface of the equilibrium liquid. By treating ethylbenzene as a simple model for molecular semiconducting materials, a quantum-chemical analysis is then used to show that the vapor-deposited glasses exhibit decreased energetic disorder and increased magnitude of the mean-squared transfer integral relative to isotropic, liquid-cooled films, an effect that is attributed to the anisotropic ordering of the molecular film. These results suggest a novel structure–function simulation strategy capable of tuning the electronic properties of organic semiconducting glasses prior to experimental deposition, which could have considerable potential for organic electronic materials design.