Photochemical Acceleration of Ammonia Production by Pt1-Ptn-TiN Reduction and N2 Activation.

Stable metal nitrides (MN) are promising materials to fit the future "green" ammonia-hydrogen nexus. Either through catalysis or chemical looping, the reductive hydrogenation of MN to MN1-x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt1-Ptn) under N2-H2 conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt1-Ptn effectively transformed any formed Ti-NH into free ammonia. The generated ammonia was found to originate mainly from TiN reduction with a minor contribution from N2 activation. The knowledge accrued from this fundamental study could serve as a springboard for the development of MN materials for more efficient ammonia production to potentially disrupt the century-old fossil-powered Haber-Bosch process.

Sideways maneuvers enable narrow aperture negotiation by free-flying hummingbirds.

Many birds routinely fly fast through dense vegetation characterized by variably sized structures and voids. Successfully negotiating these cluttered environments requires maneuvering through narrow constrictions between obstacles. We show that Anna's hummingbirds (Calypte anna) can negotiate apertures less than one wingspan in diameter using a novel sideways maneuver that incorporates continuous, bilaterally asymmetric wing motions. Crucially, this maneuver allows hummingbirds to continue flapping as they negotiate the constriction. Even smaller openings are negotiated via a faster ballistic trajectory characterized by tucked and thus non-flapping wings, which reduces force production and increases descent rate relative to the asymmetric technique. Hummingbirds progressively shift to the swept method as they perform hundreds of consecutive transits, suggesting increased locomotor performance with task familiarity. Initial use of the slower asymmetric transit technique may allow birds to better assess upcoming obstacles and voids, thereby reducing the likelihood of subsequent collisions. Repeated disruptions of normal wing kinematics as birds negotiate tight apertures may determine the limits of flight performance in structurally complex environments. These strategies for aperture transit and associated flight trajectories can inform designs and algorithms for small aerial vehicles flying within cluttered environments.

Adiponectin and related C1q/TNF-related proteins bind selectively to anionic phospholipids and sphingolipids.

Adiponectin (Acrp30) is an adipokine associated with protection from cardiovascular disease, insulin resistance, and inflammation. Although its effects are conventionally attributed to binding Adipor1/2 and T-cadherin, its abundance in circulation, role in ceramide metabolism, and homology to C1q suggest an overlooked role as a lipid-binding protein, possibly generalizable to other C1q/TNF-related proteins (CTRPs) and C1q family members. To investigate this, adiponectin, representative family members, and variants were expressed in Expi293 cells and tested for binding to lipids in liposomes using density centrifugation. Binding to physiological lipids were also analyzed using gradient ultracentrifugation, liquid chromatography-mass spectrometry, and shotgun lipidomics. Interestingly, adiponectin selectively bound several anionic phospholipids and sphingolipids, including phosphatidylserine, ceramide-1-phosphate, glucosylceramide, and sulfatide, via the C1q domain in an oligomerization-dependent fashion. Binding to lipids was observed in liposomes, low-density lipoproteins, cell membranes, and plasma. Other CTRPs and C1q family members (Cbln1, CTRP1, CTRP5, and CTRP13) also bound similar lipids. These findings suggest that adiponectin and CTRPs function not only as hormones, but also as lipid opsonins, as may other C1q family proteins.

Patient survey superior to EMR extraction for eliciting positive symptoms at COVID-19 illness onset.

Context: COVID-19 has ravaged nations around the world, with New York City (NYC) and the NYC suburbs being particular epicenters of COVID-19 infection. Suffolk County, NY, has reported over 200,000 cases and 3,000 deaths to date. Most initial COVID-19 research concerned hospitalized patients. Presenting symptomology in the outpatient setting was poorly characterized, as were the implications of specific presenting symptoms, beyond respiratory distress or hypoxia, for eventual disease severity. This made it difficult for primary care physicians to predict which patients would require hospitalization for COVID-19 disease or decompensate while being managed at home during a time when hospital and ICU beds were limited. Objective: To characterize presenting symptoms of COVID-19 infection in the outpatient setting and evaluate for correlation with severity, duration, and chronicity of disease. Study Design and Analysis: We collected survey data from both patient telephone interviews and electronic medical record (EMR) extraction. Patient characteristics were described using means and percentages when appropriate. Percentage of symptoms by severity level, symptom duration, COVID-19 testing and escalating medical care were calculated. To evaluate association of risk factors with positive testing, severity, duration and chronicity of symptoms, logistic regression was used. Patient characteristics, medications and repeat measures were evaluated as risk factors in logistic regression. Setting or Dataset: 107 patients with suspected and confirmed COVID-19 cases at the 3 primary care practices of Stony Brook University Hospital between March and December, 2020. Population Studied: adult, English speaking primary care patients with suspected or confirmed COVID-19 Intervention/Instrument: patient self report telephone survey, EMR data extraction survey Outcome Measures: symptom duration, symptom severity, persistence of symptoms at 3 month time point Significant Results: Patient self-report survey elicited nearly twice as many symptoms described at illness onset vs. those recorded in the EMR. Conclusions: Early in the setting of newly emerging infectious diseases, particularly those such as COVID-19 which involve multiple organ systems, patient self report of symptoms of illness rather than EMR extraction alone may be crucial both for identifying cases and in order to characterize pathophysiology of disease in real time.

Solar Urea: Towards a Sustainable Fertilizer Industry.

Urea, an agricultural fertilizer, nourishes humanity. The century-old Bosch-Meiser process provides the world's urea. It is multi-step, consumes enormous amounts of non-renewable energy, and has a large CO2 footprint. Thus, developing an eco-friendly synthesis for urea is a priority. Herein we report a single-step Pd/LTA-3A catalyzed synthesis of urea from CO2 and NH3 under ambient conditions powered solely by solar energy. Pd nanoparticles serve the dual function of catalyzing the dissociation of NH3 and providing the photothermal driving force for urea formation, while the absorption capacity of LTA-3A removes by-product H2 O to shift the equilibrium towards urea production. The solar urea conversion rate from NH3 and CO2 is 87 µmol g-1 h-1 . This advance represents a first step towards the use of solar energy in urea production. It provides insights into green fertilizer production, and inspires the vision of sustainable, modular plants for distributed production of urea on farms.

Tetramers reveal IL-17-secreting CD4+ T cells that are specific for U1-70 in lupus and mixed connective tissue disease.

Antigen-specific CD4(+) T cells are implicated in the autoimmune disease systemic lupus erythematosus (SLE), but little is known about the peptide antigens that they recognize and their precise function in disease. We generated a series of MHC class II tetramers of I-E(k)-containing peptides from the spliceosomal protein U1-70 that specifically stain distinct CD4(+) T-cell populations in MRL/lpr mice. The T-cell populations recognize an epitope differing only by the presence or absence of a single phosphate residue at position serine(140). The frequency of CD4(+) T cells specific for U1-70(131-150):I-E(k) (without phosphorylation) correlates with disease severity and anti-U1-70 autoantibody production. These T cells also express RORγt and produce IL-17A. Furthermore, the U1-70-specific CD4(+) T cells that produce IL-17A are detected in a subset of patients with SLE and are significantly increased in patients with mixed connective tissue disease. These studies provide tools for studying antigen-specific CD4(+) T cells in lupus, and demonstrate an antigen-specific source of IL-17A in autoimmune disease.

Understanding the role of transition metal single-atom electronic structure in oxysulfur radical-mediated oxidative degradation.

The ubiquity of refractory organic matter in aquatic environments necessitates innovative removal strategies. Sulfate radical-based advanced oxidation has emerged as an attractive solution, offering high selectivity, enduring efficacy, and anti-interference ability. Among many technologies, sulfite activation, leveraging its cost-effectiveness and lower toxicity compared to conventional persulfates, stands out. Yet, the activation process often relies on transition metals, suffering from low atom utilization. Here we introduce a series of single-atom catalysts (SACs) employing transition metals on g-C3N4 substrates, effectively activating sulfite for acetaminophen degradation. We highlight the superior performance of Fe/CN, which demonstrates a degradation rate constant significantly surpassing those of Ni/CN and Cu/CN. Our investigation into the electronic and spin polarization characteristics of these catalysts reveals their critical role in catalytic efficiency, with oxysulfur radical-mediated reactions predominating. Notably, under visible light, the catalytic activity is enhanced, attributed to an increased generation of oxysulfur radicals and a strengthened electron donation-back donation dynamic. The proximity of Fe/CN's d-band center to the Fermi level, alongside its high spin polarization, is shown to improve sulfite adsorption and reduce the HOMO-LUMO gap, thereby accelerating photo-assisted sulfite activation. This work advances the understanding of SACs in environmental applications and lays the groundwork for future water treatment technologies.

Giant Cell Arteritis Presenting With Multiple Cranial Neuropathies - Case Report.

Background: Vision loss accounts for most ophthalmic presentations of giant cell arteritis (GCA), but an important minority of patients present with diplopia and other cranial neuropathies. Case study: Here we present the case of an 84-year-old woman with a prior history of multiple cancers who was admitted to our hospital after developing double vision. She was found to have mydriasis, ptosis, and ophthalmoplegia in the right eye (OD) consistent with a combined R CNIII/CNVI neuropathy, as well as highly elevated inflammatory markers. Given her cancer history, the patient was initially worked up for various neoplastic, paraneoplastic, inflammatory, and infectious causes of multiple cranial neuropathies; however, as these results were negative, GCA became a more likely contender as a possible rare cause of multiple cranial neuropathies. The patient underwent temporal artery biopsy which showed pathology consistent with giant cell arteritis, and she was treated with steroids with eventual improvement in ophthalmoplegia and ptosis. Conclusions: This case illustrates the importance of recognizing GCA as a rare possible cause of multiple cranial neuropathies, including the indispensable role of temporal artery biopsy.

Association of Presenting Symptoms With Abnormal Laboratory Values for Vector-Borne Illness - Experience in an Urban Gastroenterology Practice.

PURPOSE: In the clinical setting, it is not common practice to consider a vector bite, such as from a tick or flea, to be a contributing factor to chronic digestive symptoms. This article investigates associations we have observed among symptomatic patients and positive blood tests for vector-borne illness (VBI). METHODS: Patients who visited an urban gastroenterology clinic over a 3-year period were retrospectively reviewed. A total of 270 patients presenting with a constellation of digestive symptoms - and who had no apparent digestive pathology and reported no prior diagnosis or treatments for VBI - were analyzed. Before the initial visit, all patients completed a review of systems medical history form, which comprised 19 gastrointestinal (GI) symptoms and 73 non-GI-related symptoms and conditions. Patients were tested for small intestinal bacterial overgrowth (SIBO) by lactulose breath test. VBI (babesiosis, ehrlichiosis, anaplasmosis, bartonellosis, borreliosis) was established using 1 or more of several blood tests. Odds ratio (OR) analysis determined associations between exposure to VBI, SIBO, and presenting symptoms/conditions. Two age groups (≤35 years and ≥36 years) were studied using Cochran-Mantel-Haenszel stratum-based test. RESULTS: A higher OR (2.03, 95% CI: 1.5-3.6) was found between patients with ≥3 digestive symptoms and positive blood tests for ≥1 VBI. Five of the 19 GI symptoms were independently associated with VBI-positive samples: food intolerance, indigestion, nausea/vomiting, constipation, and heartburn. A similar association in patients with ≥3 non-GI symptoms (OR: 2.83, 95% CI: 1.3-6.4) was observed. Five of the 73 non-GI symptoms/conditions were independently associated with VBI-positive samples: chest pain, shortness of breath, extremity or joint pain, anxiety, and night sweats. Having ≥3 of any digestive or nondigestive symptoms generated significant relative risk of being VBI-positive. Presence of SIBO alone did not identify significant relative risk for a VBI, and age was not a confounder. CONCLUSIONS: Findings revealed an association between positive blood tests for vector-borne illness and chronically symptomatic patients regardless of whether symptoms were digestive or nondigestive. The manifestation of 3 or more gastrointestinal and/or extraintestinal symptoms should raise suspicion for a VBI.

Regulation of human Th9 differentiation by type I interferons and IL-21.

Interleukin (IL)-9-producing CD4(+) T cells are a novel subset of T helper (Th) cells that develops independently of the Th1, Th2, Th17 and regulatory T-cell lineages. Similar to the murine model, transforming growth factor (TGF)-beta and IL-4 directed human naive CD4(+) T cells to produce IL-9. Whereas IL-4 suppressed TGF-beta-induced Foxp3 expression, TGF-beta failed to inhibit IL-4-mediated upregulation of the Th2 transcription factor GATA-3. Addition of IL-1 beta, IL-6, IL-10, interferon (IFN)-alpha, IFN-beta or IL-21 to Th9-polarizing conditions augmented Th9 differentiation, while the Th1-associated cytokines IFN-gamma and IL-27 partially suppressed IL-9 production. Given that T cells are a primary source of IL-21, IL-21 expression was analyzed under Th9-polarizing conditions in the context of inflammatory cytokines. Surprisingly, type I IFNs induced elevated levels of IL-21, and blockade of IL-21 abrogated their ability to enhance Th9 differentiation. Taken together, these data indicate a complex cytokine network in the regulation of human IL-9-producing CD4(+) T cells.

Control strategies in systemic metabolism.

Metabolic control systems coordinate myriad processes across the cellular, tissue and organismal levels to optimize the allocation of limited supplies across multiple, often competing, metabolic demands. As such, the regulation of metabolism can be analysed from the perspective of the economic theory of supply and demand. Here, we discuss how such analyses can provide new insights into the logic of metabolic control. In particular, we suggest that, in addition to being subject to well-appreciated homeostatic control, metabolism is subject to supply-driven and demand-driven controls, each operated by a dedicated set of signals throughout various physiological states, including inflammation. Furthermore, we argue that systemic homeostasis is a derived feature that evolved from the control systems that monitor metabolic supply and demand.

Evaluation of antiviral effect and toxicity of total flavonoids extracted from Robinia pseudoacacia cv. idaho.

In this study, we aimed to evaluate the antiviral effect of total flavonoids extracted from Robinia pseudoacacia cv. idaho (RPTF) in vivo and its toxicity on rats with oral gavage. RPTF was prepared by percolation with 70% ethanol for 24 h and its antiviral effect on different kinds of viruses was evaluated in vitro by MTT staining. The long-term toxicity of RPTF on rats was evaluated through the detection of general behavior, body weight, food intake and related organ tissue sections of experimental animals. We found that RPTF produced significantly inhibitory effects on HSV-1 and EV-71 viruses with the therapeutic index TI values 113.8 and 46.2, respectively. Moreover, toxicity evaluation in vivo showed no significantly adverse effects in rats, indicating that RPTF was safe in use. In conclusion, we demonstrated that RPTF, natural compounds in the Chinese traditional medicine, could act as promising and effective antiviral therapeutics with relative safety in use.

Multivalent DNA-based vectors for DNA vaccine delivery.

DNA can be utilized as a generic delivery vector as well as a traditional biological material for DNA vaccination. Although the use of DNA as an antigen expression vector or a vaccine adjuvant has been intensively studied for several decades, the use of DNA molecules as a delivery carrier has not been explored until recently. This issue is probably due to the topological limitation of DNA in its natural linear or circular structure form. Multivalent DNA-based vector delivery platforms overcome this structural barrier and are particularly suited for DNA vaccine delivery because of their multifunctionality, monodispersity, anisotropicity, and bioconjugation ability with numerous functional moieties. In this chapter, we mainly describe the construction of multivalent DNA-based delivery vectors using DNA engineering methods. Specifically, the synthesis strategies for highly branched dendrimer-like DNA structures in general and methods for their application to DNA vaccine delivery are introduced.

Coinhibitory receptor PD-1H preferentially suppresses CD4⁺ T cell-mediated immunity.

T cell activation is regulated by the interactions of surface receptors with stimulatory and inhibitory ligands. Programmed death-1 homolog (PD-1H, also called VISTA) is a member of the CD28 family of proteins and has been shown to act as a coinhibitory ligand on APCs that suppress T cell responses. Here, we determined that PD-1H functions as a coinhibitory receptor for CD4⁺ T cells. CD4⁺ T cells in mice lacking PD-1H exhibited a dramatically increased response to antigen stimulation. Furthermore, delivery of a PD-1H-specific agonist mAb directly inhibited CD4⁺ T cell activation both in vitro and in vivo, validating a coinhibitory function of PD-1H. In a murine model of acute hepatitis, administration of a PD-1H agonist mAb suppressed CD4⁺ T cell-mediated acute inflammation. PD-1H-deficient animals were highly resistant to tumor induction in a murine brain glioma model, and depletion of CD4⁺ T cells, but not CD8⁺ T cells, promoted tumor formation. Together, our findings suggest that PD-1H has potential as a target of immune modulation in the treatment of human inflammation and malignancies.