Optimization of HS-SPME/GC-MS Method for Determining Volatile Organic Compounds and Sensory Profile in Cocoa Honey from Different Cocoa Varieties (Theobroma cacao L.).

This study aimed to develop an analytical method using HS-SPME/GC-MS to determine the volatile organic compound (VOC) profiles and evaluate the sensory attributes of cocoa honey from four cocoa varieties (CCN51, PS1319, SJ02, and Parazinho). Using a multivariate factorial experimental design, the HS-SPME/GC-MS method was optimized to determine the VOC profiles. Twenty previously trained tasters participated in the ranking descriptive analysis, while 108 consumers participated in the acceptance and purchase intention tests. A total of 84 volatile organic compounds were identified from various chemical classes, including acids, alcohols, aldehydes, esters, ketones, monoterpenes, oxygenated monoterpenoids, sesquiterpenes, and oxygenated sesquiterpenoids. Palmitic acid was the compound found in the highest concentration in all varieties (5.13-13.10%). Multivariate analysis tools identified key compounds for differentiation and grouping of the samples. The results revealed that the variety significantly influenced both the VOCs' concentrations and sensory profiles. The CCN51, PS1319, and SJ02 varieties exhibited the highest diversity of VOCs and sensory attributes. Notably, the SJ02 and CCN51 varieties demonstrated superior acceptability and purchase intention, with means ranging from 7.21 and 7.08 to 3.71 and 3.56, respectively. These results indicate their potential as promising sources of cocoa honey for the food industry.

Dynamics of Corneal Swelling With Hypoosmolar Riboflavin After Induction During Corneal Collagen Crosslinking in Patients With Progressive Keratoconus.

PURPOSE: To evaluate the rate of corneal swelling induced by hypoosmolar riboflavin in patients with progressive keratoconus (KCN) with corneal thickness <400 µm after the induction phase using riboflavin with 20% dextran during epithelium-off corneal crosslinking (CXL). METHODS: Prospective, nonrandomized, single-center consecutive case series. Preoperative assessments included tomography, specular microscopy, and hysteresis. After epithelial debridement, riboflavin with 20% dextran (Photrexa Viscous; Glaukos, Burlington, MA) was applied at 2-min intervals during a 30-min induction phase. Eyes that dehydrated to a minimum corneal thickness (MCT) of <400 µm after induction (postinduction pachymetry) were recruited. Hypoosmolar riboflavin 0.146% (Photrexa; Glaukos) was used every 10 s to induce stromal swelling, with pachymetry performed every 30 s until the MCT was ≥400 µm (postswelling pachymetry). Corneal swelling rate was compared with variables using regression analysis. RESULTS: In 31 eyes of 31 patients, mean postinduction pachymetry was 338.4 ± 28.7 µm. Hypoosmolar riboflavin induced a postswelling pachymetry of 413.4 ± 15.0 µm over a mean of 5.2 ± 3.2 min, and the average stromal swelling rate was 10.3 ± 8.7 µm/30 s. All eyes reached a postswelling pachymetry MCT ≥400 µm and no cases were aborted. Eyes with highly severe KCN (Kmax >70 and Belin/Ambrosio enhanced ectasia display final D score >17) experienced quicker swelling (14.4 ± 12.8 µm/30 s and 14.9 ± 12.4 µm/30 s, respectively; P < 0.05 for both). A thicker postinduction pachymetry was moderately associated with a faster rate of swelling (rs = 0.389; P = 0.030). CONCLUSIONS: Hypoosmolar riboflavin 0.146% can be safely employed in thinner corneas, allowing for swelling to ≥400 µm for epithelium-off CXL. Associations between swelling rate, KCN severity, and postinduction pachymetry were determined, allowing for a more accurate prediction of procedure time during CXL.

Nonterpenoid Chemical Diversity of Cannabis Phenotypes Predicts Differentiated Aroma Characteristics.

The recent increase in legality of Cannabis Sativa L. has led to interest in developing new varieties with unique aromatic or effect-driven traits. Selectively breeding plants for the genetic stability and consistency of their secondary metabolite profiles is one application of phenotyping. While this horticultural process is used extensively in the cannabis industry, few studies exist examining the chemical data that may differentiate phenotypes aromatically. To gain insight into the diversity of secondary metabolite profiles between progeny, we analyzed five ice water hash rosin extracts created from five different phenotypes of the same crossing using comprehensive 2-dimensional gas chromatography coupled to time-of-flight mass spectrometry, flame ionization detection, and sulfur chemiluminescence detection. These results were then correlated to results from a human sensory panel, which revealed specific low-concentration compounds that strongly influence sensory perception. We found aroma differences between certain phenotypes that are driven by key minor, nonterpenoid compounds, including the newly reported 3-mercaptohexyl hexanoate. We further report the identification of octanoic and decanoic acids, which are implicated in the production of cheese-like aromas in cannabis. These results establish that even genetically similar phenotypes can possess diverse and distinct aromas arising not from the dominant terpenes, but rather from key minor volatile compounds. Moreover, our study underscores the value of detailed chemical analyses in enhancing cannabis selective breeding practices, offering insights into the chemical basis of aroma and sensory differences.

Calculation of the geometry, absorption spectrum, and first hyperpolarizability of 4,5-dicyanoimidazole derivatives in solution. A multiscale ASEC-FEG study.

We investigate the effects of solvents on the geometry, absorption spectrum, and first hyperpolarizability of six push-pull molecules, each containing a 4,5-dicyanoimidazole group as an electron acceptor and a N,N-dimethylamino group as an electron donor, with systematically extended π-conjugated systems. Geometry optimizations in dichloromethane, methanol, water, and formamide under normal thermodynamic conditions were performed using the average solvent electrostatic configuration-free energy gradient method, which employs a discrete solvent model. The conformational structure of molecules is moderately affected by the environment, with the π-conjugated system becoming more planar in protic solvents. Solvent effects on the first hyperpolarizability result in marked increases that are in line with the red shifts of the absorption spectrum. The hyperpolarizability of smaller molecules within the set may be significantly influenced by the effects of geometry relaxation in highly polar protic solvents. The results illustrate the role of hydrogen bonds in the structure and electronic properties of push-pull molecules in protic environments. For smaller molecules, hydrogen bonds significantly contribute to enhancing the hyperpolarizability, but the effect of these specific interactions becomes less significant with the length of the π-conjugated system.

Listener effort quantifies clinically meaningful progression of dysarthria in people living with amyotrophic lateral sclerosis.

Amyotrophic lateral sclerosis (ALS) is a neurodegenerative motor neuron disease that causes progressive muscle weakness. Progressive bulbar dysfunction causes dysarthria and thus social isolation, reducing quality of life. The Everything ALS Speech Study obtained longitudinal clinical information and speech recordings from 292 participants. In a subset of 120 participants, we measured speaking rate (SR) and listener effort (LE), a measure of dysarthria severity rated by speech pathologists from recordings. LE intra- and inter-rater reliability was very high (ICC 0.88 to 0.92). LE correlated with other measures of dysarthria at baseline. LE changed over time in participants with ALS (slope 0.77 pts/month; p<0.001) but not controls (slope 0.005 pts/month; p=0.807). The slope of LE progression was similar in all participants with ALS who had bulbar dysfunction at baseline, regardless of ALS site of onset. LE could be a remotely collected clinically meaningful clinical outcome assessment for ALS clinical trials.

The dynamic strength index is a reliable and feasible tool to assess neuromuscular performance in male and female handball players.

The aim of this study was to explore the reliability and feasibility of the isometric mid-thigh pull (IMTP) and dynamic strength index (DSI) in semi-professional handball players (seventeen male and eighteen female). A cross-sectional design was used to determine the test-retest reliability of several kinetic metrics registered with a force plates. The peak force, peak relative force, rate of force development (RFD 0-250 ms), and impulse 0-250 ms were selected from the IMTP test, whereas the peak propulsive force was chosen from the countermovement jump test to obtain the DSI. The intraclass correlation coefficient (ICC), coefficient of variation (CV), standard error of the measurement (SEM) and smallest detectable difference (SDD) were calculated. A paired sample t-test was also performed. No significant differences were found between the testing sessions for all variables, except for peak propulsive force for all players (p = 0.036) and DSI for female players (p = 0.037). Reliability for all kinetic metrics was good to excellent (ICC = 0.78-0.97), with low variability (CV ≤ 8.64%), being the SEM scores lower than SDD. In conclusion, the IMTP test and DSI are highly reliable and feasible tools for assessing neuromuscular performance in semi-professional handball players.

A Solar to Chemical Strategy: Green Hydrogen as a Means, Not an End.

Green hydrogen is the key to the chemical industry achieving net zero emissions. The chemical industry is responsible for almost 2% of all CO2 emissions, with half of it coming from the production of simple commodity chemicals, such as NH3, H2O2, methanol, and aniline. Despite electrolysis driven by renewable power sources emerging as the most promising way to supply all the green hydrogen required in the production chain of these chemicals, in this review, it is worth noting that the photocatalytic route may be underestimated and can hold a bright future for this topic. In fact, the production of H2 by photocatalysis still faces important challenges in terms of activity, engineering, and economic feasibility. However, photocatalytic systems can be tailored to directly convert sunlight and water (or other renewable proton sources) directly into chemicals, enabling a solar-to-chemical strategy. Here, a series of recent examples are presented, demonstrating that photocatalysis can be successfully employed to produce the most important commodity chemicals, especially on NH3, H2O2, and chemicals produced by reduction reactions. The replacement of fossil-derived H2 in the synthesis of these chemicals can be disruptive, essentially safeguarding the transition of the chemical industry to a low-carbon economy.

A Review of Immunotherapy in Non-Small-Cell Lung Cancer.

Cancer immunotherapy in the form of immune checkpoint inhibitors has led to a dramatic increase in the survival of patients with lung cancer across all stages. Over the past decade, the field has experienced rapid maturation; however, several challenges continue to complicate patient management. This review aims to highlight the data that led to this dramatic shift in practice as well as to focus on key challenges. These include determining the optimal therapy duration, managing frail patients or those with brain metastases, addressing the challenges posed by immune-related adverse events, and defining the various patterns of clinical and radiological responses to immunotherapy.

Molecular identification and prevalence of plerocercoid larvae (Cestoda: Diphyllobothriidae) in some commercial fish species from Peru.

Diphyllobothriosis, a fish-borne zoonosis in South America, is mainly caused by the Pacific broad tapeworm Adenocephalus pacificus Nybelin, 1931, a parasite of considerable concern in fishery resources due to its impact on public health. A new diphyllobothrid, Diphyllobothrium sprakeri Hernández-Orts et al. Parasites Vectors 14:219, 2021, was recently described from sea lions from the Pacific Coast, but marine fish acting as intermediate hosts are unknown. The objective of this study was to confirm the presence of plerocercoid larvae of Diphyllobothriidae Lühe, 1910 (Cestoda: Diphyllobothriidea) in nine fish species of commercial importance in Peru. Of a total of 6999 fish (5861 Engraulis ringens, 853 Sciaena deliciosa, 6 Sciaena callaensis, 171 Scomber japonicus, 40 Trachurus murphyi, 40 Ariopsis seemanni, 18 Merluccius peruanus, 5 Sarda chiliensis, and 5 Coryphaena hippurus), 183 were infected with plerocercoid larvae, representing a total prevalence of 2.61% and a mean intensity of 3.2. Based on mtDNA cox1 sequences of 43 plerocercoids, a phylogenetic analysis revealed that 41 belong to A. pacificus and two to D. sprakeri. These findings are first molecular data for D. sprakeri larvae, and the infections of E. ringens and T. murphyi by plerocercoid larvae represent the first records of intermediate/paratenic hosts for this species. Hence, the findings of the current study enhance our understanding of the presence of diphyllobothriid species in commercial fish from the Southeastern Pacific Ocean and their potential impact on seafood safety for local human populations.

Recent advancements in bio-based dielectric and piezoelectric polymers and their biomedical applications.

The advent of polymer-based dielectrics marked a significant breakthrough in dielectric materials. However, despite their many advantages, they pose serious environmental threats. Therefore, in recent years, there has been growing interest in bio-based polymers as a sustainable alternative to traditional petroleum-based polymers. Their renewable nature and reduced environmental impact can fulfil the rising demand for eco-friendly substitutes. Beyond their ecological benefits, bio-based polymers also possess distinctive electrical properties that make them extremely attractive in a variety of applications. Considering these, herein, we present recent advancements in bio-based dielectric polymers and nanocomposites. First, the fundamental concepts of dielectric and polymer-based dielectric materials are covered. Then, we will delve into the discussion of recent advancements in the dielectric properties and thermal stability of bio-based polymers, including polylactic acid, polyhydroxyalkanoates, polybutylene succinate, starch, cellulose, chitosan, chitins, and alginates, and their nanocomposites. Other novel bio-based dielectric polymers and their distinct dielectric characteristics have also been pointed out. In an additional section, the piezoelectric properties of these polymers and their recent biomedical applications have been highlighted and discussed thoroughly. In conclusion, this paper thoroughly discusses the recent advances in bio-based dielectric polymers and their potential to revolutionize the biomedical industry while cultivating a more sustainable and greener future.

Novel Dihydropteridinone Derivatives As Potent Inhibitors of the Understudied Human Kinases Vaccinia-Related Kinase 1 and Casein Kinase 1δ/ε.

Vaccinia-related kinase 1 (VRK1) and the δ and ε isoforms of casein kinase 1 (CK1) are linked to various disease-relevant pathways. However, the lack of tool compounds for these kinases has significantly hampered our understanding of their cellular functions and therapeutic potential. Here, we describe the structure-based development of potent inhibitors of VRK1, a kinase highly expressed in various tumor types and crucial for cell proliferation and genome integrity. Kinome-wide profiling revealed that our compounds also inhibit CK1δ and CK1ε. We demonstrate that dihydropteridinones 35 and 36 mimic the cellular outcomes of VRK1 depletion. Complementary studies with existing CK1δ and CK1ε inhibitors suggest that these kinases may play overlapping roles in cell proliferation and genome instability. Together, our findings highlight the potential of VRK1 inhibition in treating p53-deficient tumors and possibly enhancing the efficacy of existing cancer therapies that target DNA stability or cell division.

Theoretical Study of Cyanidin-Resveratrol Copigmentation by the Functional Density Theory.

Anthocyanins are colored water-soluble plant pigments. Upon consumption, anthocyanins are quickly absorbed and can penetrate the blood-brain barrier (BBB). Research based on population studies suggests that including anthocyanin-rich sources in the diet lowers the risk of neurodegenerative diseases. The copigmentation caused by copigments is considered an effective way to stabilize anthocyanins against adverse environmental conditions. This is attributed to the covalent and noncovalent interactions between colored forms of anthocyanins (flavylium ions and quinoidal bases) and colorless or pale-yellow organic molecules (copigments). The present work carried out a theoretical study of the copigmentation process between cyanidin and resveratrol (CINRES). We used three levels of density functional theory: M06-2x/6-31g+(d,p) (d3bj); ωB97X-D/6-31+(d,p); APFD/6-31+(d,p), implemented in the Gaussian16W package. In a vacuum, the CINRES was found at a copigmentation distance of 3.54 Å between cyanidin and resveratrol. In water, a binding free energy ∆G was calculated, rendering -3.31, -1.68, and -6.91 kcal/mol, at M06-2x/6-31g+(d,p) (d3bj), ωB97X-D/6-31+(d,p), and APFD/6-31+(d,p) levels of theory, respectively. A time-dependent density functional theory (TD-DFT) was used to calculate the UV spectra of the complexes and then compared to its parent molecules, resulting in a lower energy gap at forming complexes. Excited states' properties were analyzed with the ωB97X-D functional. Finally, Shannon aromaticity indices were calculated and isosurfaces of non-covalent interactions were evaluated.

Two new records and description of a new Perinereis (Annelida, Nereididae) species for the Saudi Arabian Red Sea region.

Annelid biodiversity studies in the Red Sea are limited and integrative taxonomy is needed to accurately improve reference libraries in the region. As part of the bioblitz effort in Saudi Arabia to assess the invertebrate biodiversity in the northern Red Sea and Gulf of Aqaba, Perinereis specimens from intertidal marine and lagoon-like rocky environments were selected for an independent assessment, given the known taxonomic ambiguities in this genus. This study used an integrative approach, combining molecular with morphological and geographic data. Our results demonstrate that specimens found mainly in the Gulf of Aqaba are not only morphologically different from other five similar Perinereis Group I species reported in the region, but phylogenetic analysis using available COI sequences from GenBank revealed different molecular operational taxonomic units, suggesting an undescribed species, P.kaustianasp. nov. The new species is genetically close and shares a similar paragnath pattern to the Indo-Pacific distributed P.helleri, in particular in Area III and Areas VII-VIII. Therefore, we suggest it may belong to the same species complex. However, P.kaustianasp. nov. differs from the latter mainly in the shorter length of the postero-dorsal tentacular cirri, median parapodia with much longer dorsal Tentacular cirri, posteriormost parapodia with much wider and greatly expanded dorsal ligules. Additionally, two new records are reported for the Saudi Neom area belonging to P.damietta and P.suezensis, previously described only for the Egyptian coast (Suez Canal) and are distributed sympatrically with the new species, but apparently not sympatric with each other.

The role of intermolecular interactions in [Fe(X-salEen)2]ClO4 spin crossover complexes.

Two new spin crossover (SCO) Fe(III) compounds were prepared, their structures were analysed and their magnetic properties were investigated. An exhaustive analysis of the effects of halogen substitution and aromatic ring functionalisation on the magnetic properties of non-solvated Fe(III) perchlorate complexes has been performed. Through comparative analysis, different magnetic profiles were found for the compounds studied, namely F (1), Cl (2), H (3), Br (4a, 4b), and I (5). Using tools like Hirshfeld analysis, the study revealed patterns in octahedral distortions and deviations from the ideal octahedral geometry. The SCO phenomenon as the conducting wire in this study, emphasises the influence of intermolecular interactions on the low spin (LS) to high spin (HS) transitions in these halogen-substituted complexes. The prevalence of H⋯H contributions has been demonstrated, albeit being the weakest and an inverse strength relationship in H⋯X interactions ranging from F to I. The findings not only interpret the intricate balance between halogen substitution, functionalisation, and intermolecular interactions in modulating magnetic properties but also direct future works in designing similar molecular systems.

Linking Patient Encounters across Primary and Ancillary Electronic Health Record Systems: A Comparison of Two Approaches.

Background: To achieve scientific goals, researchers often require integration of data from a primary electronic health record (EHR) system and one or more ancillary EHR systems used during the same patient care encounter. Although studies have demonstrated approaches for linking patient identity records across different EHR systems, little is known about linking patient encounter records across primary and ancillary EHR systems. Objectives: We compared a patients-first approach versus an encounters-first approach for linking patient encounter records across multiple EHR systems. Methods: We conducted a retrospective observational study of 348,904 patients with 533,283 encounters from 2010 to 2020 across our institution's primary EHR system and an ancillary EHR system used in perioperative settings. For the patients-first approach and the encounters-first approach, we measured the number of patient and encounter links created as well as runtime. Results: While the patients-first approach linked 43% of patients and 49% of encounters, the encounters-first approach linked 98% of patients and 100% of encounters. The encounters-first approach was 20 times faster than the patients-first approach for linking patients and 33% slower for linking encounters. Conclusion: Findings suggest that common patient and encounter identifiers shared among EHR systems via automated interfaces may be clinically useful but not "research-ready" and thus require an encounters-first linkage approach to enable secondary use for scientific purposes. Based on our search, this study is among the first to demonstrate approaches for linking patient encounters across multiple EHR systems. Enterprise data warehouse for research efforts elsewhere may benefit from an encounters-first approach.

"You Are Not Wrong About Getting Strong:" An Insight Into the Impact of Age Group and Level of Competition on Strength in Spanish Football Players.

OBJECTIVE: This study aimed to compare the maximum and rapid force production of Spanish football players and explore the differences between age group and level of competition. METHODS: A cross-sectional study was developed to evaluate the peak force (PF), relative PF, and rate of force development over 250 ms (RFD0-250) during the isometric midthigh pull between groups of football players based on age group (senior vs junior) and level of competition (national vs regional). Using a portable isometric rig, 111 football players performed 2 isometric midthigh-pull trials on a force plate. Two-way analysis of variance with Bonferroni post hoc correction was applied, and statistical significance was set at P ≤ .05. The PF, relative PF, and RFD0-250 0, 25, 50, 75, and 100 percentiles were also calculated and descriptively reported, separated by age group and level of competition. RESULTS: The analysis of variance revealed a significant main effect of the level of competition for the PF (P < .001), relative PF (P = .003), and RFD0-250 (P < .001). There was a significant main effect of age group for the PF (P < .001). There was a significant interaction effect of the age group × level of competition for relative PF (P = .014). National players were stronger than regional players on the PF and RFD0-250 (P < .001). Senior players were stronger than junior players for the PF (P < .001). CONCLUSIONS: Maximum and rapid force production are crucial for Spanish football players as they progress in both level of competition and age group. Practitioners should encourage young football players to prioritize strength development to improve their athletic performance.

Differential accumulation of human ß-amyloid and tau from enriched extracts in neuronal and endothelial cells.

While Aß and Tau cellular distribution has been largely studied, the comparative internalization and subcellular accumulation of Tau and Aß isolated from human brain extracts in endothelial and neuronal cells has not yet been unveiled. We have previously demonstrated that controlled enrichment of Aß from human brain extracts constitutes a valuable tool to monitor cellular internalization in vitro and in vivo. Herein, we establish an alternative method to strongly enrich Aß and Tau aggregates from human AD brains, which has allowed us to study and compare the cellular internalization, distribution and toxicity of both proteins within brain barrier endothelial (bEnd.3) and neuronal (Neuro2A) cells. Our findings demonstrate the suitability of human enriched brain extracts to monitor the intracellular distribution of human Aß and Tau, which, once internalized, show dissimilar sorting to different organelles within the cell and differential toxicity, exhibiting higher toxic effects on neuronal cells than on endothelial cells. While tau is strongly concentrated preferentially in mitochondria, Aß is distributed predominantly within the endolysosomal system in endothelial cells, whereas the endoplasmic reticulum was its preferential location in neurons. Altogether, our findings display a picture of the interactions that human Aß and Tau might establish in these cells.