Activation of SBIZrMe2 or SBIZrMeCl and a sheet model for an active component of hydrolytic MAO, (MeAlO)16(Me3Al)6, (16,6) has been studied by DFT. Contact ion-pair formation occurs through the intermediacy of SBIZrMe(Cl) or SBIZrMe2 reacting with sheet 16,6 to furnish SBIZrMe-μ-X(MeAlO)16(Me3Al)6 (2, X=Me, Cl). Contact ion-pairs 2 would be in equilibrium with heterodinuclear catalyst precursors [SBIZrMe2AlMe2][(MeAlO)16(Me3Al)6X] (3 (X=Me, Cl) through reversible binding of Me3Al at higher Al : Zr ratios. Calculations show that formation of ion-pairs 3 from contact ion-pairs 2 is more favourable for the SBIZr compared with the parent Cp2Zr complexes. TD-DFT calculations were conducted on relevant SBIZr complexes to relate the results to earlier spectroscopic studies of catalyst activation using UV-Vis spectroscopy. Finally, propene insertion into ion-pairs 2, SBIZrMe-μ-MeB(C6F5)3 (6) and [SBIZrMe][B(C6F5)4] (7) was studied at M06-2X/TZVP level of theory. These studies suggest that contact ion-pairs 2 are significantly less reactive towards insertion than 6 or 7, in disagreement with experiment.

BACKGROUND: Functional precision medicine (FPM) represents a personalized and efficacious modality for treating malignant neoplasms. However, acquiring sufficient live tissue to perform FPM analyses is complicated by both difficult identification on imaging and radiation necrosis, particularly in cases of recurrence. The authors describe a case of planning biopsy trajectories for an FPM assay in a patient with recurrent high-grade glioma.
METHODS: A 25-year-old male with a history of recurrent high-grade glioma was scheduled for laser ablation and biopsy with ChemoID assaying after regions of potential recurrence were identified on follow-up imaging. Preoperative magnetic resonance (MR) spectroscopy of the regions showed areas of high choline/creatine ratios within lesions of radiation necrosis, which helped in planning the biopsy trajectories to selectively target malignancies for FPM analysis. ChemoID results showed high tumor susceptibility to lomustine, which was implemented as adjuvant therapy.
CONCLUSIONS: FPM therapy in the setting of recurrence is complicated by radiation necrosis, which can present as malignancy on imaging and interfere with tissue acquisition during biopsy or resection. Thus, operative approaches should be carefully planned with the assistance of imaging modalities such as MR spectroscopy to better ensure effective tissue acquisition for accurate FPM analysis and to promote more definitive treatment of recurrence.

The prediction of algal blooms using traditional water quality indicators is expensive, labor-intensive, and time-consuming, making it challenging to meet the critical requirement of timely monitoring for prompt management. Using optical measures for forecasting algal blooms is a feasible and useful method to overcome these problems. This study explores the potential application of optical measures to enhance algal bloom prediction in terms of prediction accuracy and workload reduction, aided by machine learning (ML) models. Compared to absorption-derived parameters, commonly used fluorescence indices such as the fluorescence index (FI), humification index (HIX), biological index (BIX), and protein-like component improved the prediction accuracy. However, the prediction accuracy was decreased when all optical indices were considered for computation due to increased noise and uncertainty in the models. With the exception of chemical oxygen demand (COD), this study successfully replaced biochemical oxygen demand (BOD), dissolved organic carbon (DOC), and nutrients with selected fluorescence indices, demonstrating relatively analogous performance in either training or testing data, with consistent and good coefficient of determination (R2) values of approximately 0.85 and 0.74, respectively. Among all models considered, ensemble learning models consistently outperformed conventional regression models and artificial neural networks (ANNs). However, there was a trade-off between accuracy and computation efficiency among the ensemble learning models (i.e., Stacking and XGBoost) for algal bloom prediction. Our study offers a glimpse of the potential application of spectroscopic measures to improve accuracy and efficiency in algal bloom prediction, but further work should be carried out in other water bodies to further validate our proposed hypothesis.

UNASSIGNED: Functional near infrared spectroscopy (fNIRS) can be used to quantify stump oxygen saturation (SaO2) as one of many possible causes of pain following major amputation. Although commonly used for cerebral perfusion monitoring during carotid or cardiac surgery, it can also be used to monitor tissue perfusion in the lower limb and predict healing following below knee amputation (BKA). The aim of this study was to measure the SaO2 trend as there is no validated oxygen threshold to diagnose insufficient flow into the arterial collateral network currently.
UNASSIGNED: NIRS was used to measure SaO2 while performing treadmill exercise. Two BKA patients with chronic stump pain were asked to perform treadmill exercise while using their prosthesis and NIRS optode applied to the posterior stump to monitor SaO2. Cases 1 and 2 showed a decline in SaO2 of 25% and 18%, respectively, while walking on the prosthesis. After superficial femoral artery (SFA) recanalisation and stenting, Case 1 showed improvement by maintaining SaO2 between 54% and 60% throughout treadmill exercise. In Case 2, perfusion could not be further improved, and the patient underwent through knee amputation.
UNASSIGNED: fNIRS detected compressive ischaemia and exercise induced ischaemia as mechanisms of stump pain. Findings provided the multidisciplinary team with objective information, aiding decision making to treat stump pain.

Excimer formation based on pyrene derivatives stacking has been used to probe conformational changes associated with a variety of protein interactions. Herein, in search for the nature of the protein interactions involved in amyloid proteins aggregation we studied the spectroscopic features of the Nα-acetyl-l-tyrosinamide (NAYA) parent compound and of a well-known aggregate amyloid protein, the α-synuclein (Syn). The aggregation of this amyloid disordered protein has been implicated in the development of Parkinson\'s disease, which is an increasingly prevalent and currently incurable neurodegenerative disorder. Also, Syn aggregation has been widely investigated but, information concerning the conformational alterations in the diverse protein aggregated species at the molecular level, is still scarce. Three different molecular configurations of the NAYA parent compound were at least found to exist in its solutions containing 1,4-dioxane. Two of these NAYA molecular configurations were found to produce a more efficient excimer fluorescence. For Syn solutions containing 1,4-dioxane, one molecular configuration involving the intermolecular interaction between the protein tyrosyl group and the protein peptide bond was found to exhibit excimer fluorescence. This study is the first one reporting the formation of a biological excimer exhibiting fluorescence. Although very weak, this can be used as a signature of protein-protein interactions and, ultimately, enabling to access the complex interactions network existing in the amyloid aggregated species.

The role and importance of the identification of natural products are discussed in the perspective of the study of secondary metabolites. The rapid identification of already reported compounds, or structural dereplication, is recognized as a key element in natural product chemistry. The biological taxonomy of metabolite producing organisms, the knowledge of metabolite molecular structures, and the availability of metabolite spectroscopic signatures are considered as the three pillars of structural dereplication. The role and the construction of databases is illustrated by references to the KNApSAcK, UNPD, CSEARCH, and COCONUT databases, and by the importance of calculated taxonomic and spectroscopic data as substitutes for missing or lost original ones. Two NMR-based tools, the PNMRNP database that derives from UNPD, and KnapsackSearch, a database generator that provides taxonomically focused libraries of compounds, are proposed to the community of natural product chemists. The study of the alkaloids from Urceolina peruviana, a plant from the Andes used in traditional medicine for antibacterial and anticancer actions, has given the opportunity to test different approaches to dereplication, favoring the use of publicly available data sources.

Color is an important communication channel for day-flying butterflies. Chemical (pigmentary) coloration is often supplemented by physical color generated by photonic nanostructures. These nanoarchitectures - which are characteristic for a given species - exhibit wavelength ranges in which light propagation is forbidden. The photonic nanoarchitectures are located in the lumen of the wing scales and are developed individually by each scale during metamorphosis. This self-assembly process is governed by the genes in the nucleus of the scale producing cell. It is crucial to establish well-defined measurement methods for the unambiguous characterization and comparison of colors generated in such a complex manner. Owing to the intricate architecture ordered at multiple levels (from centimeters to tens of nanometers), the precise quantitative determination of butterfly wing coloration is not trivial. In this paper, we present an overview of several optical spectroscopy measurement methods and illustrate techniques for processing the obtained data, using the species Polyommatus bellargus as a test case, the males of which exhibit a variation in their blue structural color that is easily recognizable to the naked eye. The benefits and drawbacks of these optical methods are discussed and compared. Furthermore, the origin of the color differences is explained in relation to differences in the wing scale nanomorphology revealed by electron microscopy. This in turn is tentatively associated with the unusually large genetic drift reported for this species in the literature.

Conjugation of protein therapeutics with polymers like polyethylene glycol (PEG) has been shown to increase their therapeutic efficiency. However, manufacturing of PEGylated drugs requires an additional, carefully controlled reaction step after purifying the protein, followed by further purification of over- and under-PEGylated variants. In this work, we have used a combined spectroscopic and statistical approach for monitoring and control of the PEGylation reaction for G-CSF using near infrared spectroscopy (NIRS). An online NIRS probe deployed in the reaction vessel has been used to track conversion of G-CSF into monoPEGylated and multiPEGylated forms using calibrated partial least squares regression models on the NIRS spectra which are collected in real time every 3 s. A pH probe integrated with a peristaltic pump facilitates automated quenching of the reaction at the targeted time. The NIRS spectra have also been used to build a batch evolution model for the reaction from end-to-end, including the addition of the reactants to the reaction vessel, the progress of the reaction for 70 min, and the final quenching with Tris base. Online spectra are compared against the statistical process control charts of the batch evolution model in real time to detect deviations as soon as they occur. The system was demonstrated for four common deviations in the PEGylation process, namely: delayed quenching time, wrong concentration of reducing agent added, wrong PEG to G-CSF ratio, and wrong sequence of addition of reactants. The system was able to identify all four deviations in real time and alert the operator to take control actions. The PAT approach suggested here embraces the quality by design framework and can be generalized for manufacturing scale monitoring and control of different biotechnology reactions with spectroscopic signatures.

The gas-phase formation and spectroscopic characteristics of ethanimine have been re-investigated as a paradigmatic case illustrating the accuracy of state-of-the-art quantum-chemical (QC) methodologies in the field of astrochemistry. According to our computations, the reaction between the amidogen, NH, and ethyl, C2H5, radicals is very fast, close to the gas-kinetics limit. Although the main reaction channel under conditions typical of the interstellar medium leads to methanimine and the methyl radical, the predicted amount of the two E,Z stereoisomers of ethanimine is around 10%. State-of-the-art QC and kinetic models lead to a [E-CH3CHNH]/[Z-CH3CHNH] ratio of ca. 1.4, slightly higher than the previous computations, but still far from the value determined from astronomical observations (ca. 3). An accurate computational characterization of the molecular structure, energetics, and spectroscopic properties of the E and Z isomers of ethanimine combined with millimeter-wave measurements up to 300 GHz, allows for predicting the rotational spectrum of both isomers up to 500 GHz, thus opening the way toward new astronomical observations.

Central nervous system (CNS) tuberculosis is the second most common presentation after tuberculous meningitis. It is a major cause of morbidity and mortality in the developing countries, accounting for 10-30% of intracranial expansive lesions in these countries against 0.2% in some Western countries. This study aims to report an atypical clinical and radiological manifestation (brain MRI and spectroscopy) of cerebral tuberculoma in order to provide an update on this infectious disease. The study involved a 44-year old female patient with no particular previous history, with headaches persisting for 1 year and complicated by partial secondarily generalized seizures and heaviness at the left hemicorpus with episodes of vomiting without visual disorder or fever or deterioration of general condition after 8 months. Clinical examination showed conscious patient with Glasgow Coma Scale (GCS) 15, equal and reactive pupils, walking and/or standing without fault, with 4/5 left-sided hemiparesis without other neurological signs. Brain MRI objectified right parietal subtentorial plurilobulated isointense poorly differentiated lesion on T1 weighted sequence without contrast agents injection and heterogeneous lesion with hyperintense edge and hypointense fundus, suggesting fleshy process with areas of central necrosis and perilesionnal edema extending in finger-like fashion with intense annular enhancement after gadolinium injection on T2 weighted sequence. Spectroscopy showed glial tumor. The patient received anticonvulsant therapy and macroscopic complete resection. Anatomopathologic analysis showed cerebral tuberculoma. She received antituberculosis drugs with seizure stoppage and deficit recovery after 4 weeks. This study highlights the clinical and radiological polymorphism of cerebral tuberculoma. This is suspected based on laboratory tests as well as on a body of clinical and radiological evidences but definitive diagnosis is based on anatomopathologic analysis. Early management is essential because complications can be severe and result in a poor prognosis.