Low Reactivity Research Articles

Analysis of spontaneous cytomegalovirus clearance after low level reactivation using a pre-emptive treatment threshold of 4,000 IU/mL in allogeneic hematopoietic cell transplant recipients

BackgroundCytomegalovirus (CMV) can be a serious complication after allogeneic hematopoietic cell transplant (HCT). CMV viral load is routinely monitored, and pre-emptive therapy is initiated to prevent CMV viremia from developing into CMV organ disease based on institutional thresholds. There is no established universal threshold for pre-emptive therapy and many centers utilize different strategies. MethodsAllogeneic HCT recipients at WVU Medicine from 2009 to 2021 were routinely initiated on pre-emptive CMV treatment for a PCR viral threshold above 4000 IU/mL. Adult patients with quantifiable values below this threshold, were analyzed to evaluate the rate of spontaneous clearance without initiation of CMV-directed therapy, during their first episode of CMV reactivation. This study excluded any patients that received letermovir prophylaxis. ResultsSixty patients were included in the analysis. The spontaneous clearance rate was 60 %. The risk factors that were associated with a lower spontaneous clearance rate were reactivation within thirty days after transplant (p = 0.031), presence of graft-versus-host-disease (p = 0.031), and CMV PCR values of 2500–4000 IU/mL (p = 0.02). Although these patients had lower rates of spontaneous clearance, they still spontaneously cleared in 42 %, 42 %, and 43 % of the cases, respectively. ConclusionDelaying pre-emptive treatment until a CMV PCR value of 4000 IU/mL is reached appears appropriate and decreases unnecessary treatment toxicity and resistance.

Iodide enhances degradation of histidine sidechain and imidazoles and forms new iodinated aromatic disinfection byproducts during chlorination

Peptide-bound histidines and imidazoles are important constituents of dissolved organic matter in water, and understanding the formation of halogenated disinfection byproduct (DBP) formation from these compounds during disinfection is important for ensuring a safe drinking water supply. Previous studies suggested that histidine has low reactivity with chlorine only; this study indicates that iodide substantially enhances histidine reactivity with the disinfectant at a time scale from days to hours. Mono- and di-iodinated histidines were identified as dominant transformation products with cumulative molar yields of 3.3 % at 6 h and they were stable in water over 7 days. These products were formed via electrophilic substitution of iodine to imidazole ring when hypoiodous acid reacted with histidine sidechain. Bromide minimally influenced the formation yields of these iodinated products, and higher pH increased yields up to 12 % for pH in the range 5–9. The cumulative concentration of low-molecular-weight DBPs, such as trihalomethanes and haloacetic acids, was less than 0.3 % under the same conditions. Similar iodinated imidazole analogs were also identified from other imidazoles (i.e., imidazole-carboxylic and phenyl-imidazole-carboxylic acids). This study demonstrated that peptide-bound histidine and imidazoles can serve as important precursors to iodinated aromatic DBPs, facilitating the identification of less-known iodinated DBPs.

Strength and durability performance of acid-mechanically treated recycled aggregate concrete with metakaolin, lime powder, and A-fine

This study examines the effectiveness of lime powder (LP) and metakaolin (MK) in concrete containing acid-mechanically treated recycled concrete aggregate (RCA). The acid-mechanically produced recycled fine, i.e., A-Fine (AF), is also evaluated as a supplementary cementitious material (SCM). According to the strength activity index (SAI) for AF, it has a low pozzolanic reactivity in comparison to MK and a higher pozzolanic reactivity in comparison to LP. An optimal dosage of AF (15 %), LP (17 %), and MK (22 %) improves the physical properties of recycled aggregate concrete (RAC). The compressive strength of RAC with AF (RAC-AF) is closer to that of RAC with LP (RAC-LP), and RAC with MK (RAC-MK). As a result of their partial or complete chemical inertness, AF, LP, or MK decrease the self-cementing capability of RCA and reduce the mechanical properties and fracture energy of RAC. While the split tensile and flexural strength of RAC-AF is greater than that of RAC-LP, it is smaller than that of RAC-MK. As a result of their higher elastic modulus, RAC-AF and RAC-MK are more ductile than RAC and RAC-LP. As a result of low ion penetration and high electrical resistance, RAC, RAC-AF, RAC-LP, and RAC-MK are classified as low permeability materials. AF or MK as a cement substitute does not alter the sorptivity of RAC despite improvement. In contrast, RAC has higher initial and final absorption when LP substitutes for cement. According to their pozzolanic reactivity and filler effect, RAC sorptivity varies with these SCMs. There is a strong correlation between the compressive strength and UPV of RAC, RAC-AF, RAC-LP, and RAC-MK with R2 = 0.94. The sorptivity and electrical resistivity are also correlated with R2 = 0.94. Due to the formation of Si-rich C-S-H gels, SEM and EDS show a more uniform and denser microstructure in RAC-AF, RAC-LP, and RAC-MK.

Oxygen donation of alkali earth metal ferrites for biomass chemical looping gasification: A comparative study

This study objectives to compare the oxygen donation properties among a series of alkali earth metal (AEM) ferrites as oxygen carriers (OCs), including MgFe2O4, CaFe2O4, SrFe2O4 and BaFe2O4, in biomass chemical looping gasification (CLG), through fixed bed reactivity tests and several characterizations, including XRD, XPS, TPR and thermogravimetric analysis. It was found that BaFe2O4 possessed the best syngas production performance, owing to its highest reactivity with char and lowest reactivity with CO/H2. Thermogravimetry analysis and TPR tests show that heavier AEM ferrites exhibited higher reactivity with char and lower reactivity with syngas, except for the relationship between SrFe2O4 and CaFe2O4. Fixed bed tests show that the AEM ferrites could be ranked as BaFe2O4 > CaFe2O4 > SrFe2O4 > MgFe2O4 according to their syngas production performance. Other than reactivity, 20-cycle tests demonstrate that BaFe2O4 had the best stability on H2 production compared to other OCs. The advantage of BaFe2O4 may be related to its more sufficient oxygen vacancy and crystal structure. Therefore, BaFe2O4-based OCs were found the most suitable for biomass CLG. The current study filled the gap in screening of AEM ferrite OCs and provided guidance for future OC development, achieving cleaner biomass conversion and enhanced sustainability.

Coconstruction of Supramolecular Lithium-Conducting Cross-Linked Networks Based on PVDF and Triblock Polymer Nanomicrosphere Solid-State Polymer Electrolytes for Lithium-Metal Batteries.

Uneven lithium plating and low ionic conductivity currently impede the realization of high-capacity rechargeable lithium metal batteries. And the conventional poly(ethylene oxide) (PEO) solid-state electrolytes are unsuitable for high-energy-density Li anode applications due to their low lithium-ion transference number and high reactivity with Li metal, leading to detrimental dendrite formation and potentially hazardous exothermic reactions with the electrolyte. In this study, we employ a supramolecular approach to develop a novel polymer solid-state electrolyte based on poly(vinylidene fluoride) (PVDF) and a novel triblock polymer nanomicrosphere, (poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone), (PCL-PEG-PCL). The abundance of carbonyl and ether-oxygen functional groups in PCL-PEG-PCL enhances the lithium coordination environment within the polymer solid-state electrolyte. Additionally, the original C-F moieties of PVDF form hydrogen bonds with C-H and terminal hydroxyl groups in PCL-PEG-PCL, collectively creating a multichannel fast Li+-conducting supramolecular cross-linked network. The resulting electrolyte demonstrates a high ionic conductivity of 1.4 × 10-3 S cm-1 and an extended electrochemical window of 5.2 V. Moreover, the electrolyte exhibits a high lithium-ion transference number (tLi+ = 0.63) at room temperature and exhibits excellent interfacial compatibility with the lithium metal anode. For the resulting electrolyte utilized in LiFePO4 batteries, the capacity retention of the cells assembled with this electrolyte exceeds 91.3% after 1000 cycles at 25 °C and 2 C (0.281 mA cm-2).

Effect of ultra-low dosage graphene oxide on the properties of recycled cement-based materials

The utilization of recycled fine powder (RFP) from crushed concrete waste as partial cement replacement is limited by its low reactivity. Graphene Oxide (GO) is a two-dimensional amphiphilic conjugated polymer that can effectively improve the properties of cement-based materials, but its application is limited due to its high cost. This study investigates the ultra-low dosage GO on the properties of recycled cement-based materials. GO was dispersed using polycarboxylate superplasticizers (PCE) before incorporation in the pastes containing 25 % RFP as the binder. The results show that PCE can effectively improve the dispersion of GO in cement-based materials. The improvement effect of well-dispersed ultra-low dosage GO on the strength of recycled cement-based materials in the early stage was better than that in the later stage, and the improvement effect on the flexural strength was better than that on the compressive strength. The GO dosage was optimized at 0.004 % which improved the 3 days flexural strength by 52 % compared to the control sample without GO. Results showed that well-dispersed ultra-low dosage GO accelerated the hydration of recycled cement-based materials due to the nucleation effect and template effect, promoted the formation of additional C–S–H gels, and facilitated the development of C–S–H gels more orderly, reduced the porosity of the hardened pastes, and refined the microstructure. However, excessive GO reduced strength due to agglomeration. The improvement in strength and microstructure refinement demonstrates the positive role of GO in enhancing the reactivity of recycled cement-based materials. This process successfully reduced the dosage of GO in cement-based materials by about 90 % and provided an approach to utilizing recycled fine powder.

Impacts of pine oil and hydrogen induction with hemp oil methyl ester on dual fuel reactivity controlled compression ignition combustion in diesel engine

AbstractThe current research focuses on the impacts of pine oil injection and hydrogen induction separately with hemp oil methyl ester (HOME) in the single cylinder diesel engine in dual fuel‐reactivity controlled compression ignition (DF‐RCCI) combustion mode. The engine was tested under a DF‐RCCI mode for the different energy shares of 10% pine oil with HOME (10P‐HOME), 30% pine oil with HOME (30P‐HOME), 3‐lpm hydrogen with HOME (3‐lpmH2‐HOME), and 6‐lpm hydrogen with HOME (6‐lpmH2‐HOME) separately at 345 °CA bTDC of low reactivity fuel (pine oil and hydrogen) and 23°C bTDC injection timing of high reactivity fuel (HOME). The results showed a higher Brake Thermal Efficiency (BTE) of 7.44%, 5.32%, 5.72%, and 2.46% for 6‐lpmH2‐HOME, 3‐lpmH2‐HOME, 30P‐HOME, and 10P‐HOME fuel shares, respectively, over the conventional diesel combustion (CDC) at full load. 30P‐HOME, 3‐lpmH2‐HOME, and 6‐lpmH2‐HOME fuel combinations recorded 4.08% 4.42%, and 5.69% lower brake specific fuel consumption (BSFC), respectively, at full load. When comparing DF‐RCCI combustion to CDC, an increase in the heat release rate (HRR) of 2.89%–26.50% and a rise in peak cylinder pressure of 0.77%–12.99% were observed. The 30P‐HOME, 3‐lpmH2‐HOME, and 6‐lpmH2‐HOME emit less smoke in DF‐RCCI combustion mode by 13.06%, 4.84%, and 7.26%, respectively at full load condition. When using 30P‐HOME the exhaust gas temperature (EGT) decreased by 3.50% at full load condition. At part and full load conditions, the 30P‐HOME fuel share reduced oxides of nitrogen (NOX) emissions by 3.93% and 5.26%, respectively.

Preparation and Hydration Properties of Sodium Silicate-Activated Municipal Solid Waste Incineration Bottom Ash Composite Ground-Granulated Blast Furnace Slag Cementitious Materials.

The production of municipal solid waste incineration bottom ash (MSWIBA) is substantial and has the potential to replace cement, despite challenges such as complex composition, uneven particle size distribution, and low reactivity. This paper employs sodium silicate activation of MSWIBA composite Ground-granulated Blast Furnace slag (GGBS) to improve the reactivity in preparing composite cementitious materials. It explores the hydration performance of the composite cementitious materials using isothermal calorimetric analysis, Fourier-transform infrared (FTIR) spectroscopy, XRD physical diffraction analysis, and SEM tests. SEM tests were used to explore the hydration properties of the composite gelling. The results show that with an increase in MSWIBA doping, the porosity between the materials increased, the degree of hydration decreased, and the compressive strength decreased. When the sodium silicate concentration increased from 25% to 35%, excessive alkaline material occurred, impacting the alkaline effect. This inhibited particle hydration, leading to a decrease in the degree of hydration and, consequently, the compressive strength. The exothermic process of hydration can be divided into five main stages; quartz and calcite did not fully participate in the hydration reaction, while aluminum did. The vibrational peaks of Si-O-Ti (T = Si and Al) were present in the material. The vibrational peaks of XRD, FTIR, and SEM all indicate the presence of alumosilicate network structures in the hydration products, mainly N-A-S-H and C-A-S-H gels.

Selection of viral variants with enhanced transmission and reduced neutralization susceptibility alongside lateral introductions may explain the persistence of porcine reproductive and respiratory syndrome virus in vaccinated breeding herds.

This study investigates the long-term evolutionary dynamics of porcine reproductive and respiratory syndrome virus (PRRSV-1) in an endemically infected and vaccinated pig herd. Over a one year and a half period, piglets from seven farrowing batches in a 300-sow PRRSV-vaccinated farm were monitored from birth to nine weeks of age by reverse transcription-quantitative polymerase chain reaction (RT-qPCR). Eighty-five PRRSV-positive samples were subjected to whole genome sequencing (Illumina Miseq), and 251 samples to open reading frame 5 (ORF5) sequencing. Farm-specific PRRSV variants' impact on anti-PRRSV antibodies was evaluated using enzyme-linked immunosorbent and neutralizing antibody assays. The replication kinetics and cytokine inhibition capabilities (IFN-α and TNF-α) of these variants were assessed in porcine alveolar macrophages. The study revealed fluctuating PRRSV-1 incidences in farrowing units and nurseries, attributed to two key evolutionary events: an escape variant emergence and a lateral introduction of a new strain. Initially, strain 1 variant α was swiftly replaced within weeks by variant 1β (99.5 per cent genomic similarity), with twenty-five amino acid mutations, primarily in nsp1α, GP2, GP3, and GP5, including an additional glycosylation site and a deletion downstream the neutralization epitope of GP5. This shift to 1β correlated with increased incidence in nurseries and higher viral loads, with sera from 1α-exposed animals showing reduced neutralization against 1β. Consistently for in vitro assays, variant 1β demonstrated enhanced replication in porcine alveolar macrophages but no difference regarding IFN-α or TNF-α responses. Later, a new strain (strain 2, 83.3 per cent similarity to strain 1) emerged and led to incidence resurgence because of the low cross reactivity with the previous antibodies. The study highlights PRRSV's rapid adaptability and challenges in controlling its spread, underscoring the necessity for more effective vaccines and eradication approaches.

Unlocking the potential of phenolated kraft lignin as a versatile feed additive

Lignin, a renewable natural antioxidant and bacteriostat, holds promise as a versatile, cost-effective feed additive. However, traditional industrial lignin faces limitations, including low reactivity, poor uniformity, and unstable properties, necessitating chemical modification. Complex modification methods pose economic and toxicity challenges, so this study adopted a relatively simple alkali-catalyzed phenolization approach, using phenol, catechol, and pyrogallol to modify kraft lignin, and characterized the resulting products using various techniques. Subsequently, their antioxidant, antibacterial, adsorption properties for heavy metal ions and mycotoxins, growth-promoting properties, and antiviral abilities were assessed. The phenolation process led to lignin depolymerization and a notable increase in phenolic hydroxyl content, particularly in pyrogallol-phenolated lignin (Py-L), rising from 3.08 to 4.68 mmol/g. These modified lignins exhibited enhanced antioxidant activity, with over 99 % inhibition against E. coli and S. aureus, and remarkable adsorption capacities for heavy metal ions and mycotoxins. Importantly, Py-L improved the growth performance of mice and reduced influenza mortality. Furthermore, density functional theory calculations elucidated the mechanism behind the enhanced antioxidant properties. This study presents a promising avenue for developing versatile feed additives to address challenges related to animal feed antioxidant supplementation, bacterial control, and growth promotion.

Molybdenum single-atoms decorated multi-channel carbon nanofibers for advanced lithium-selenium batteries.

The cathode in lithium-selenium (Li-Se) batteries has garnered extensive attention owing to its superior specific capacity and enhanced conductivity compared to sulfur. Nonetheless, the adoption and advancement of Li-Se batteries face significant challenges due to selenium's low reactivity, substantial volume fluctuations, and the shuttle effect associated with polyselenides. Single-atom catalysts (SACs) are under the spotlight for their outstanding catalytic efficiency and optimal atomic utilization. To address the challenges of selenium's low chemical activity and volume expansion in Li-Se batteries, through electrospun, we have developed a lotus root-inspired carbon nanofiber (CNF) material, featured internal multi-channels and anchored with molybdenum (Mo) single atoms (Mo@CNFs). Mo single atoms significantly enhance the conversion kinetics of selenium (Se), facilitating rapid formation of Li2Se. The internally structured multi-channel CNF serves as an effective host matrix for Se, mitigating its volume expansion during the electrochemical process. The resulting cathode, Se/Mo@CNF composite, exhibits a high discharge specific capacity, superior rate performance, and impressive cycle stability in Li-Se batteries. After 500 cycles at a current density of 1 C, it maintains a capacity retention rate of 82% and nearly 100% coulombic efficiency (CE). This research offers a new avenue for the application of single-atom materials in enhancing advanced Li-Se battery performance.

Hydroxyl‐terminated polybutadiene(HTPB) propellants cross‐linked by dimer acid diisocyanate (DDI): Cross‐linking network and properties

AbstractConsidering the high toxicity of toluene diisocyanate (TDI) and the low reactivity of isophorone diisocyanate (IPDI), a low‐toxicity curing agent, dimer acid diisocyanate (DDI), was used to cross‐link HTPB elastomers and propellants. The unique long‐chain structure of DDI not only ensures the elastic modulus and tensile strength of the elastomer, but also improves the flexibility to some extent. The long flexible chains promote the segment movement, which is very important for the formation of hydrogen bonds between segments. The chemical cross‐linking network and hydrogen bonding association play a significant role in the mechanical properties of the HTPB/DDI system. The relationship between the mole ratio of ‐NCO to ‐OH (R‐value) and the mechanical properties of HTPB/DDI elastomers were also investigated. In the range of R‐value from 0.85 to 1.2, the elastic modulus and tensile strength first increase and then decrease, and the elongation at break first decreases and then increases. Under the same curing conditions, the elastic modulus and tensile strength of the HTPB/DDI propellant are similar to the HTPB/TDI propellant. For the HTPB/AP/Al propellants and HTPB/AP/RDX/Al propellants, the HTPB/DDI system has lower burning rates in the range of 5–19 MPa than the HTPB/TDI system and HTPB/IPDI system. The application of DDI can reduce the burning rates of the propellant without adding any burning rate modifiers. It is considered that DDI can replace TDI and IPDI as a new curing agent with low toxicity and moderate reactivity for HTPB systems.

Co-pyrolysis of coal with biomass residues and coke breeze for superior quality coke via hot pressing technology

Superior quality coke is essential in the metallurgical industry. However, the coking coal source is limited. The biomass or breeze could be blended into the coking coal to produce high-standard cokes by hot pressing technology. High-standard cokes should have low reactivity (chemical reaction intensity of coke and CO2 at high temperature) and high strength. The influences of biomass category and blending ratio on pore structure, reactivity and crushing strength of cokes were explored. Pore evolution during the coking process was studied by experiments and simulations to reveal the mechanism of producing high-quality cokes with biomass and breeze blended into coking coal via hot pressing technology. Results show that hot pressing technology can make high-quality cokes when the blending ratio of biomass or breeze is appropriate. When 5% bamboo, wood or straw is blended to produce hot-pressed coke, the coke reactivity decreases by 6.58%, 7.66% and 6.41% and the crushing strength increases to 1.15, 1.19 and 1.12 times when compared with coke in case of no blending and no pressing, respectively. The proper blending ratio of the three biomasses should be less than 15% because the coke quality deteriorates greatly when the blending ratio increases to 15%. If the breeze is mixed with coal to produce high-standard cokes under hot pressing conditions, the blending ratio should not exceed 30%. Hot pressing technology can reduce the coke pores when the biomass or breeze is blended into the coal with a low ratio. When 5% bamboo or 10% breeze is blended, the porosity of hot-pressed coke in the center region decreases by 5.69% and 4.02% than coke with no blending and no pressing, respectively. The low porosity contributes to the reduction of coke reactivity. The fewer pores, thicker pore walls and higher carbon matrix strength impede the growth of cracks, resulting in a higher coke crushing strength. Therefore, hot pressing technology can effectively enhance coke quality if the biomass or breeze is mixed with the coking coal with an appropriate blending ratio.

Insight into the structural variation mechanism of highly spinnable isotropic pitch prepared by halogenated model aromatic compounds

This study developed a novel method for synthesis highly spinnable pitch through thermal polymerization of halogenated polycyclic aromatic hydrocarbons (PAH-X) and anthracene oil (AO). The characteristics, average molecular model, and polymerization mechanism of the as-prepared pitches were systematically elucidated. Results show that the thermal cleavage of C-X bonds of the PAHs-X could generate large number of free radicals that greatly facilitate the cross-linking reaction of the active fragments. Namely, the formation of benzyl radicals with high reactivity of the raw materials made it possible to synthesize pitches at lower temperature. The softening point of the as-prepared pitches showed a decreasing trend with increasing of AO proportion due to the abundant carbon content and lower reactivity of AO. Higher temperature could elevate the polymerization activity of aromatic fragments, thus significantly promoted the formation of macromolecular aromatic structures to obtain the spinnable pitch with suitable softening point. The average models validated by calculating the NMR spectra was successfully constructed to demonstrate the condensation degree, which was found be conducive to probe the spinnability of the pitches. Further, the average molecular models could well describe the correlation of the molecular structure, spinnability of pitches, as well as the mechanical properties of carbon fiber.

Boosting Zn2+ intercalation in manganese oxides for aqueous zinc ion batteries via delocalizing the d-electrons spin states of Mn site

Rechargeable aqueous zinc-ion batteries (AZIBs) have received increasing attention on account of their eco-friendliness and low cost. However, the limited capacity and poor rate properties of cathodes remain a major challenge due to the low electrochemical reactivity of cathode materials and sluggish Zn2+ transport kinetics. Herein, we design a 1,5-naphthalenediamine (NAPD) pre-intercalate potassium manganese dioxide (KMO-NAPD) with high capacity and rate capability for AZIBs. The introduction of NAPD can delocalize the d-electrons spin states of the Mn site and activate the reactivity of KMO-NAPD for Zn2+ intercalation. Moreover, the interaction between intercalated Zn2+ and KMO-NAPD is weakened due to the decreased electrostatic interaction force, which promotes the diffusion of Zn2+. Consequently, the KMO-NAPD cathode exhibits high specific capacity (237 mAh g−1 at 1 A g−1) satisfying rate capability (129 mAh g−1 at 4 A g−1), and excellent cycling stability (85 % capacity retention after 1000 cycles). Furthermore, the fabricated AZIBs based on the KMO-NAPD exhibit a high energy density of 294.3 Wh kg−1 and a peak power density of 8.6 kW kg−1. This study opens up a new path for the development of high-energy organic-inorganic hybrid cathode materials with modulated electronic structures for advanced AZIBs.

Clinicoradiological Parameters and Biochemical and Molecular Alterations Predicting Remission and Recurrence After Surgical Treatment of Corticotroph Adenomas—Cushing Disease

ObjectivesEndonasal endoscopic transsphenoidal surgery (TSS) and resection of pituitary adenomas is considered to be the gold standard treatment for Cushing’s Disease (CD). Even with various recent advances in management, disease persistence and recurrences are common in these patients. The remission rate in the global population after surgery has been reported to vary widely from 64 to 93%. This study aims to determine various clinical, biochemical, radiological and histological factors that correlate with persistence and recurrence in patients with CD. This study also aims to understand the clinicopathological significance of EGFR-MAPK, NF-kB and SHH pathway activation and to study the protein expression levels of activation markers of these pathways viz. c-Fos , c-Jun, GLI-1 , pMEK, NR4A1 and p44 in functioning corticotroph pituitary adenomas. MethodsFrom January 2009 to September 2022, the clinical data of 167 patients who underwent surgical treatment (n=174 surgeries) for Cushing’s disease was ambispectively analysed with a median follow up of 8.1 years (1-13.29 years). The preoperative clinical, biochemical, radiological features, operative findings, postoperative clinical and biochemical data, histopathological and molecular profile, were retrieved from electronic records. The patients were followed up to assess the remission status. ResultsAmong the 174 surgeries performed, 140 were primary surgeries, 22 were revision surgeries, 24 surgeries were for paediatric patients and 12 surgeries were performed in patients with Nelson syndrome. In the primary surgery cohort, 74.3% were females and the average age was 28.73 years (SD 10.15). 75% of the patients experienced remission after primary surgery compared to 47.4% in revision surgery. The remission rate in paediatric patients was 55.5%. Post-operative day 1 plasma cortisol (p<0.001; AUC 0.8894 [0.8087-0.9701]) and ACTH (p<0.001; AUC 0.9 [0.7386-1]) levels were seen to be strong independent predictors of remission in the primary surgery cohort. Remission rates after Endoscopic TSS were more than that after microscopic TSS, in patients undergoing primary surgery (81.08% vs 57.14%; p=0.008). Presence of adenoma on histopathological examination (HPE) was also a strong predictor of disease remission (p=0.020). On categorising based on surgical approach and HPE, microscopically operated patients without histopathological evidence of adenoma had significantly higher odds of non-remission (OR 38.1 95% CI 4.2-348.3) compared to endoscopically operated patients with adenoma on HPE. Lower immune reactivity score (IRS) of NR4A1 was found to correlate with higher remission rates (p=0.074). However, none of the molecular markers studied viz. c-Fos , c-Jun, GLI-1, pMEK and p44 showed a significant correlation with the preoperative cortisol values. ConclusionRemission rate after primary surgery is higher as compared to that after revision surgery, and that in paediatric patients is lower as compared to adults. Post-operative day 1 plasma cortisol and ACTH levels are strong independent predictors of remission in the primary surgery cohort. Endoscopic approach with histopathological evidence of adenoma is associated with a higher remission rate and thus endoscopy should be the approach of choice in these patients with the goal of identification of an adenoma on histopathological analysis.

Constraints on the emergence of RNA through non-templated primer extension with mixtures of potentially prebiotic nucleotides.

The emergence of RNA on the early Earth is likely to have been influenced by chemical and physical processes that acted to filter out various alternative nucleic acids. For example, UV photostability is thought to have favored the survival of the canonical nucleotides. In a recent proposal for the prebiotic synthesis of the building blocks of RNA, ribonucleotides share a common pathway with arabino- and threo-nucleotides. We have therefore investigated non-templated primer extension with 2-aminoimidazole-activated forms of these alternative nucleotides to see if the synthesis of the first oligonucleotides might have been biased in favor of RNA. We show that non-templated primer extension occurs predominantly through 5'-5' imidazolium-bridged dinucleotides, echoing the mechanism of template-directed primer extension. Ribo- and arabino-nucleotides exhibited comparable rates and yields of non-templated primer extension, whereas threo-nucleotides showed lower reactivity. Competition experiments confirmed the bias against the incorporation of threo-nucleotides. The incorporation of an arabino-nucleotide at the end of the primer acts as a chain terminator and blocks subsequent extension. These biases, coupled with potentially selective prebiotic synthesis, and the templated copying that is known to favour the incorporation of ribonucleotides, provide a plausible model for the effective exclusion of arabino- and threo-nucleotides from primordial oligonucleotides.

Volatility and chemical composition of secondary organic aerosol derived from acenaphthylene and acenaphthene under various oxidant conditions

Acenaphthene (ACE) and acenaphthylene (ACY), distinguished by their unique structures, exhibit high reactivity among polycyclic aromatic hydrocarbons (PAHs). Particularly, the rapid ozonolysis of the carbon-carbon double bond in ACY and the swift oxidation of the fused cyclopenta ring in both ACE and ACY by NO3 underscore their distinct atmospheric fate. Through the utilization of a thermo denuder and high-resolution mass spectrometry, the chemical composition and volatility of four types of secondary organic aerosols (SOA) derived from ACE and ACY are investigated. The chemical composition of SOA formed by ACY ozonolysis is characterized by low O: C ratios and high unsaturation, suggesting the retention of aromatic structures. This leads to measured high SOA volatility and is consistent with the low reactivity of O3 with aromatic compounds. In contrast to ozonolysis, the reaction of NO3 with ACY could yield SOA with very low volatility, characterized by abundant dimers and highly oxidized products. Furthermore, the prevalence of compounds with 11 carbon atoms suggests the presence of complex mechanisms in the ACY oxidation process initiated by NO3, where dealkylation reactions and cleavage reactions may be pivotal. The diverse chemical composition and volatility of SOA from ACE and ACY reacting with NO3 radicals highlight the substantial impact of precursor structure on SOA chemical composition, particularly concerning the presence of active carbon-carbon double bonds. The higher O: C ratio of SOA from OH-initiated oxidation of ACE indicates the significant role of OH in the oxidation of PAHs. These findings offer valuable insights into the atmospheric fate of these PAHs, underscoring the necessity for a comprehensive understanding of their degradation processes and the formation of SOA.

Detonation properties and nitrogen oxide production in ammonia–hydrogen–air mixtures

Ammonia is a promising compound for chemical storage of renewable energy produced from non-continuous sources. However, the low reactivity of ammonia requires to use ammonia–hydrogen blends as a fuel for combustion applications. The present study corresponds to a first numerical assessment of the potential of ammonia–hydrogen–air mixtures as reactive mixtures for detonation engine applications. Both ideal and curved detonation models were employed to calculate the detonation properties, entropy production, and NOx production for mixtures with varying amounts of ammonia and hydrogen under a wide range of initial thermodynamics conditions. Interestingly, our calculations show that the entropy production and the amount of nitrogen oxides produced at the Chapman–Jouguet state respectively decreases and increases with the proportion of hydrogen in the ammonia–hydrogen blend. These aspects could have a great impact on engine efficiency and air pollution and should be considered with care. Our results also demonstrate that only mixtures with relatively low amounts of ammonia, i.e., XNH3 lower than 0.25 of the fuel blend, can be employed for detonation engine applications.

Effects of operating parameters on start performance of compression ignition engine by using high-pressure direct-injection pure methanol fuel

Methanol was one of the research hotspots in internal combustion engines over recent years. The application of methanol is a promising approach to transport decarbonization due to low carbon content. However, the utilization of methanol in compression ignition (CI) engines faces some challenges as a result of low reactivity and high latent heat of vaporization, such as cold start and operation stability. Furthermore, the impact mechanisms of operating parameters on cold start and operation stability in CI engine have not been understood deeply. In this work, the effects of operating parameters on average cycle of start and coefficient of speed variation (CoVspeed) of idle were studied on a CI engine fueled by pure methanol fuel. Results show that the injection strategy of the minimum average starting cycle number is the pre-main injection, which includes lower injection pressure, −4 °CA ATDC (degree crank angle after top dead center) main timing, smaller pre mass, and larger pre-main interval. The injection strategy of the minimum CoVspeed of idle is the pilot-pre-main injection, which includes lower injection pressure, −4 °CA ATDC main timing, smaller pre mass, larger pre-main interval, smaller pilot mass, and shorter pilot-main interval. Under the same operating conditions, the average cycle of start is 12 and 5 for methanol and diesel respectively. The CoVspeed of idle is 6.72% and 0.53% for methanol and diesel respectively. When coolant temperature is 30 °C, the minimum intake temperature is 120 °C. Upon adjusting the coolant temperature to 80 °C, the minimum intake temperature decreases to 80 °C.