The chiral properties of nickel(II) complexes of porphyrin-porphyrin Tröger\'s base and porphyrin-chlorin spiro-Tröger\'s base with phenyl or 3-methoxyphenyl substitutions in their meso-positions were studied. Enantioseparation of racemic mixtures was investigated via high-performance liquid chromatography (HPLC) on an analytical ReproSil Chiral-NR column. The optimal conditions were utilized for a multimilligram scale isolation with a semipreparative column. The purity of the isolated enantiomers was determined by HPLC and UV-Vis spectroscopy. The absolute configurations of the isolated enantiomers were determined by evaluating the Cotton effect in electronic circular dichroism spectra. The determination was supported by TDDFT calculations, in which good agreement was achieved between the experimental and simulated spectra. The maximum molar ellipticity values, [θ]λmax given in deg ∙ cm2 ∙ dmol-1, were [θ]435 = 1.73 ∙ 107 for phenyl spiroTB and [θ]436 = 1.24 ∙ 107 and [θ]436 = 2.15 ∙ 107 for 3-methoxyphenyl TB and spiroTB, respectively.

In this work, the physical mechanisms of three highly efficient circularly polarized luminescent materials are introduced. The UV-vis spectra are plotted; the transition properties of their electrons at the excited states are investigated using a combination of the transition density matrix (TDM) and the charge difference density (CDD); combining the distribution of electron clouds, the essence of charge transfer excitation in three structures is explained. The resonance Raman spectrum of the three structures at the S1 and S2 excited states are calculated. The M, M-4 and M, M-5 structures are found to produce novel chirality by electronic circular dichroism (ECD) spectrum, and the reasons for the chirality of the M, M-4 and M, M-5 structures are discussed by analyzing the density of transition electric/magnetic dipole moments (TEDM/TMDMs) in different orientations. Finally, the Raman optical activity (ROA) of M, M-4, and M, M-5 are calculated, and the spectra are plotted. This study will provide guidance for the application of carbon-based nanomaterials in organic electronic devices, solar cells, and optoelectronics.

Structural elucidation has always been challenging, and misassignment remains a stringent issue in the field of natural products. The growing interest in discovering unknown, complex natural structures accompanies the increasing awareness concerning misassignments in the community. The combination of various spectroscopic methods with molecular modeling has gained popularity in recent years. In this work, we demonstrated, for the first time, its power to fully elucidate the 2-dimensional and 3-dimensional structures of two epimers in an epimeric mixture of 6-hydroxyhippeastidine. DFT calculation of chemical shifts was first performed to assist the assignment of planar structures. Furthermore, relative and absolute configurations were established by three different ways of computer-assisted structure elucidation (CASE) coupled with ORD/ECD/VCD spectroscopies. In addition, the significant added value of OR/ORD computations to relative and absolute configuration determination was also revealed. Remarkably, the differentiation of two enantiomeric scaffolds (crinine and haemanthamine) was accomplished via OR/ORD calculations with cross-validation by ECD and VCD.

Hypothermic Oxygenated Perfusion (HOPE) of the liver can reduce the incidence of early allograft dysfunction (EAD) and failure in extended criteria donors (ECD) grafts, although data from prospective studies are very limited. In this monocentric, open-label study, from December 2018 to January 2021, 110 patients undergoing transplantation of an ECD liver graft were randomized to receive a liver after HOPE or after static cold storage (SCS) alone. The primary endpoint was the incidence of EAD. The secondary endpoints included graft and patient survival, the EASE risk score, and the rate of graft or other graft-related complications. Patients in the HOPE group had a significantly lower rate of EAD (13% vs. 35%, p = .007) and were more frequently allocated to the intermediate or higher risk group according to the EASE score (2% vs. 11%, p = .05). The survival analysis confirmed that patients in the HOPE group were associated with higher graft survival one year after LT (p = .03, log-rank test). In addition, patients in the SCS group had a higher re-admission and overall complication rate at six months, in particular cardio-vascular adverse events (p = .04 and p = .03, respectively). HOPE of ECD grafts compared to the traditional SCS preservation method is associated with lower dysfunction rates and better graft survival.

In recent decades, fungi-derived naturally occurring quinazolines have emerged as potential drug candidates. Nevertheless, most studies are conducted for bioactivity assays, and little is known about their absorption, distribution, metabolism, and elimination (ADME) properties. To perform metabolic studies, the synthesis of the naturally occurring quinazolinone, fiscalin B (1), and its chloro derivative, 4-((1H-indol-3-yl)methyl)-8,10-dichloro-1-isobutyl-1,2-dihydro-6H-pyrazino[2,1-b]quinazoline-3,6(4H)-dione (2), disclosed as an antibacterial agent, was performed in a gram scale using a microwave-assisted polycondensation reaction with 22% and 17% yields, respectively. The structure of the non-natural (+)-fiscalin B was established, for the first time, by X-ray crystallography as (1R,4S)-1, and the absolute configuration of the naturally occurring fiscalin B (-)-1 was confirmed by comparison of its calculated and experimental electronic circular dichroism (ECD) spectra as (1S,4R)-1. in vitro metabolic studies were monitored for this class of natural products for the first time by ultra-high-performance liquid chromatography (UHPLC) coupled with high-resolution mass spectrometry (HRMS). The metabolic characteristics of 1 and 2 in human liver microsomes indicated hydration and hydroxylation mass changes introduced to the parent drugs.

The aim of this study was to [1] characterize distribution of Erdheim-Chester Disease (ECD) by 18F-FDG PET/CT and [2] determine the utility of metabolic (18F-FDG PET/CT) imaging versus anatomic imaging (CT or MRI) in evaluating ECD patients for clinical trial eligibility.
18F-FDG PET/CT and corresponding CT or MRI studies for ECD patients enrolled in a prospective registry study were reviewed. Sites of disease were classified as [1] detectable by 18F-FDG PET only, CT/MRI only, or both and as [2] measurable by modified PERCIST (mPERCIST) only, RECIST only, or both. Descriptive analysis was performed and paired t test for between-group comparisons.
Fifty patients were included (mean age 51.5 years; range 18-70 years). Three hundred thirty-three disease sites were detected among all imaging modalities, 188 (56%) by both 18F-FDG PET and CT/MRI, 67 (20%) by 18F-FDG PET only, 75 (23%) by MRI brain only, and 3 (1%) by CT only. Of 178 disease sites measurable by mPERCIST or RECIST, 40 (22%) were measurable by both criteria, 136 (76%) by mPERCIST only, and 2 (1%) by RECIST only. On the patient level, 17 (34%) had mPERCIST and RECIST measurable disease, 30 (60%) had mPERCIST measurable disease only, and 0 had RECIST measurable disease only (p < 0.0001).
Compared with anatomic imaging, 18F-FDG PET/CT augments evaluation of disease extent in ECD and increases identification of disease sites measurable by formal response criteria and therefore eligibility for clinical trials. Complementary organ-specific anatomic imaging offers the capacity to characterize sites of disease in greater anatomic detail.
ClinicalTrials.gov Identifier: NCT03329274.

This work demonstrates resonance Raman optical activity (RROA) spectra of three truncated vitamin B12 derivatives modified within the nucleotide loop. Since truncated cobalamins possess sufficiently high rotational strength in the range of ROA excitation (532 nm), it was possible to record their spectra in the resonance condition. They showed several distinct spectral features allowing for the distinguishing of studied compounds, in contrast to other methods, i.e., UV-Vis absorption, electronic circular dichroism, and resonance Raman spectroscopy. The improved capacity of the RROA method is based here on the excitation of molecules via more than two electronic states, giving rise to the bisignate RROA spectrum, significantly distinct from a parent Raman spectrum. This observation is an important step in the dissemination of using RROA spectroscopy in studying the complex structure of corrinoids which may prove crucial for a better understanding of their biological role.

Conducted electrical weapons (CEW) are ubiquitous in law enforcement given their unique ability to physically incapacitate violently resisting subjects. Early use of animal models to study CEW incapacitation effectiveness (e.g. porcine model with 4-limb strain gauges) proved to be poorly predictive of human incapacitation effectiveness. In a previously published human study, we developed a methodology for the prospective assessment of the incapacitation effectiveness of CEWs in highly motivated human subjects. Here we use this methodology in Part 1 to compare the incapacitation effectiveness of the newly released Axon® (formerly TASER® International) T(ASER) 7 to the TASER X26E, the \"gold standard\", and the TASER X2, a current model. The T7 has a new \"adaptive cross-connect\" technology that may improve incapacitation effectiveness in the scenario of small spreads between probe pairs, a common cause of weapon \"failure\" in the field. In Part 2, we use our methodology to test the functionality of the T7 cross-connect technology by comparing different bay and probe configurations. This is the first published study in the literature comparing different CEW models using this human model. For Part 1, 29 subjects completed the study and had data available for analysis. For Part 2, 21 subjects completed the study and had data available for analysis. The subjects were motivated to complete the task of reaching a suspended martial arts dummy 3.4 m (11 ft) away while being exposed \"under power\" to the CEW. In Part 1, subjects were assigned to 1 of 6 groups with probe spreads of 10, 20, and 30 cm (4, 8, 12 in). Subjects were exposed to a \"control\" CEW (either the X2 or X26E) and the T7 on alternating sides. Exposures with the X2 and T7 included 2 bay-exposures. In Part 2, 21 subjects were assigned to 1 of 5 groups of different T7 bay and probe configurations all with a theoretical effective spread of 30 cm (12 in). Subjects were rated on their progress towards successfully reaching the dummy and on the extent of limb incapacitation using a quasi-blinded expert-observer scoring panel based on high-speed video review. In Part 1, all CEW models achieved maximal or near-maximal subject control with the 30 cm probe spread. With probe spreads of 10 and 20 cm the pooled data showed the T7 to be superior to the X2 for goal achievement (p < 0.001) and limb incapacitation (p = 0.002) mostly driven by differences seen with the 10 cm spread (2-bay exposures). The T7 was non-inferior to the X26E. In Part 2, there was no statistical significance between the limb capture scores, but there was a statistically significant difference in goal scores. The results overall validate that the T7 CEW cross-connect feature performed as expected. The T7 adaptive cross-connect feature with two simultaneous deployed probe pairs demonstrated a significant improvement in incapacitation effectiveness compared to the current X2 CEW with two simultaneously deployed probe pairs. Small probe spreads are a common reason for limited incapacitation effectiveness in the field and this study suggests the T7 may offer an improvement in this scenario. The T7, with single-bay exposures, was non-inferior to the single-bay X26E.

In 1,1,2,2-tetrachloroethane-d2 , the 129 Xe NMR spectrum of the Xe@cryptophane-223 complex bearing seven acetate groups (Xe@1 complex) shows an unusually broad signal compared with that of its congeners (Chapellet, LL. et al. J. Org. Chem. 2015;80:6143-6151). To interpret this unexpected behaviour, a 1 H NMR analysis and a thorough study of the chiroptical properties of 1 as a function of the nature of the solvent have been performed. The 1 H NMR spectra of 1 reveal that a self-encapsulation phenomenon takes place in DMSO-d6 and 1,1,2,2-tetrachloroethane-d2 solvents. Thanks to the separation of the two enantiomers of 1 by HPLC on chiral stationary phase, the two enantiomers of 1 have been studied in detail by polarimetry, electronic (ECD), and vibrational (VCD) circular dichroism spectroscopies. Except for ECD spectroscopy, these chiroptical techniques reveal spectroscopic changes as a function of the nature of the solvent. For instance, in DMSO and 1,1,2,2-tetrachloroethane, in which the self-encapsulation phenomenon takes place, the sign of the specific optical rotation of [CD(-)254 ]-1 and [CD(+)254 ]-1 is changed. These results have then been compared with those obtained with cryptophane-223 bearing only one acetate group on the propylenedioxy linker (compound 2) and with cryptophane-223 bearing six acetate groups (compound 3). A self-encapsulation phenomenon is also observed with compound 2. Finally, compounds 2 and 3 show different chiroptical properties compared with those obtained with the two enantiomers of compound 1.

To identify changes in endothelial cell density (ECD) and central corneal thickness (CCT) in eyes undergoing femtosecond laser-assisted cataract surgery (FLACS) compared with conventional phacoemulsification surgery (CPS).
This is an intraindividual randomised, controlled clinical trial. One eye was randomised to receive FLACS, while the contralateral eye of the same patient received CPS. The femtosecond laser pretreatment included creating main and side-port corneal incisions, capsulotomy and lens fragmentation. Non-contact endothelial cell microscopy and pachymetry were performed preoperatively and at postoperative day 1, week 1, month 1 and month 3.
A total of 134 paired eyes from 67 patients were included in the analysis. ECD was not significantly different between the two groups at either postoperative month 1 (2370±580 cells/mm2 and 2467±564 cells/mm2 in FLACS and CPS groups, respectively; p=0.18) or at postoperative month 3 (2374±527 cells/mm2 and 2433±526 cells/mm2 in FLACS and CPS groups, respectively; p=0.19). No significant difference was observed in the mean CCT values between the two groups over the follow-up period (p>0.05).
Postoperative corneal ECD and CCT were comparable between FLACS and CPS during the 3 months\' follow-up period.