Search

We optimize the internuclear geometry and electronic structure of a model chiral system to achieve a maximal photoelectron circular dichroism (PECD) in its one-photon ionization by circularly polarized light. The electronic structure calculations are performed by the single center method, while the optimization is done using quantum alchemy employing a Taylor series expansion. Thereby, the effect of bond lengths and uncompensated charge distributions on the chiral response of the model is investigated theoretically in some detail. It is demonstrated that manipulating a chiral asymmetry of the ionic potential may enhance the dichroic parameter (i.e., the PECD) of the randomly oriented model system well beyond β1 = 25%. Furthermore, we demonstrate that quantum alchemy is applicable to PECD despite the unusually strong coupling of spatial and electronic degrees of freedom and discuss the relative impact of the individual degrees of freedom in this model system. We define the necessary conditions for the computational design of PECD for real (non-model) chiral molecules using our approach. [ABSTRACT FROM AUTHOR]

Flavan‐3‐ol monomers are the building blocks of proanthocyanidins (PACs), natural compounds from plants shown to mediate specific biologic activities on dentin. While the stereochemistry of the terminal flavan‐3‐ols, catechin (C) versus epicatechin (EC), impacts the biomechanical properties of the dentin matrix treated with oligomeric PACs, structure–activity relationships driving this bioactivity remain elusive. To gain insights into the modulatory role of the terminal monomers, two highly congruent trimeric PACs from Pinus massoniana only differing in the stereochemistry of the terminal unit (Trimer‐C vs. Trimer‐EC) were prepared to evaluate their chemical characteristics as well as their effects on the viscoelasticity and biostability of biomodified dentin matrices via infrared spectroscopy and multi‐scale dynamic mechanical analyses. The subtle alteration of C versus EC as terminal monomers lead to distinct immediate PAC‐trimer biomodulation of the dentin matrix. Nano‐ and micro‐dynamic mechanical analyses revealed that Trimer‐EC increased the complex moduli (0.51 GPa) of dentin matrix more strongly than Trimer‐C (0.26 GPa) at the nanoscale length (p < 0.001), whereas the reverse was found at the microscale length (p <.001). The damping capacity (tan δ) of dentin matrix decreased by 70% after PAC treatment at the nano‐length scale, while increased values were found at the micro‐length scale (~0.24) compared to the control (0.18 ; p <.001). An increase in amide band intensities and a decrease of complex moduli was observed after storage in simulated body fluid for both Trimer‐C and Trimer‐EC modified dentin. The stereochemical configuration of the terminal monomeric units, C and EC, did not impact the chemo‐mechanical stability of dentin matrix. [ABSTRACT FROM AUTHOR]

This study introduces a new NMR-based methodology for identification (ID) and quantification (purity, strength) assays of widely used amino acids. A detailed analysis of four amino acids and their available salts was performed with both a high-field (600 MHz) and a benchtop (60 MHz) NMR instrument. To assess sensitivity constraints, samples for 1H NMR analysis were initially prepared using only 10 mg of analyte and 1 mg of maleic acid (MA) as an internal calibrant (IC) and secondary chemical shift reference. The characteristic dispersion of the peak patterns indicating the presence or absence of a counterion (mostly chloride) was conserved at both high and low-field strength instruments, showing that the underlying NMR spectroscopic parameters, i.e., chemical shifts and coupling constants, are independent of the magnetic field strength. However, as the verbal descriptions of 1H NMR spectra are challenging in the context of reference materials and pharmaceutical monographs, an alternative method for the identification (ID) of amino acids is proposed that uses 13C NMR patterns from multiplicity-edited HSQC (ed-HSQC), which are both compound-specific and straightforward to document. For ed-HSQC measurements, the sample amount was increased to 30 mg of the analyte and several acquisition parameters were tested, including t 1 increments used in the pulse program, number of scans, and repetition time. Excellent congruence with deviations <0.1 ppm was achieved for the 13C chemical shifts from 1D 13C NMR spectra (150 MHz) vs. those extracted from ed-HSQC (15 MHz traces). Finally, all samples of amino acid candidate reference materials were quantified by 1H qNMR (abs-qHNMR) at both 600 and 60 MHz. At high field, both IC and relative quantitations were performed, however, with the low-field instrument, only the IC method was used. The results showed that the analyzed reference material candidates were generally highly pure compounds. To achieve adequately low levels of uncertainty for such high-purity materials, the sample amounts were increased to 100 mg of analytes and 10 mg of the IC and replicates were analyzed for selected amino acids. [Display omitted] • 1H NMR identifies free amino acids and distinguishes them from their salts. • Indirect 13 C NMR measurement via 2D HSQC can serve as innovative identity assay. • Congruence in IC- and rel-qHNMR is diagnostic for chemical purity and water content. • Sample size and replicates are key for absolute qHNMR or high-purity compounds. • Benchtop NMR is suitable for pharmaceutical identity, quantity, and purity assays. [ABSTRACT FROM AUTHOR]

Introduction: Ultrasound-guided lavage (UGL) is a minimally invasive percutaneous treatment for rotator cuff calcific tendinopathy (RCCT). It involves the use of a syringe containing saline and/or anesthetic solution injected directly into the calcification allowing aspiration of the fragmented calcific material. The aim of this systematic review is to investigate if UGL is effective in improving pain, function, quality of life, range of motion (ROM), and in promoting complete resorption of calcifications in patients with RCCT., Evidence Acquisition: Only randomized controlled trials considering people diagnosed with RCCT, at any stage and at any time of the onset of symptoms treated with UGL, were included. Embase, CENTRAL, CINHAL, PEDro and MEDLINE were explored up until May 2024. Two independent authors selected randomized controlled trials by title and abstract; afterwards, the full text was thoroughly evaluated. The risk of bias (ROB) was assessed using the Cochrane risk of bias 2 (ROB2) tool and the certainty of evidence was evaluated through the GRADE approach., Evidence Synthesis: Seven studies (709 subjects) were included. Overall, three studies were judged as low risk of bias. Pooled results showed non-significant differences between UGL and extracorporeal shock-wave therapy (ESWT) at 12 weeks (SMD=-0.52, 95% CI -1.57, 0.54, P=0.34, I 2 =93%) and at 26 weeks (MD=-1.20, 95% CI -2.66, 0.27, P=0.11, I 2 =82%), while a significant difference favoring UGL (SMD=-0.52, 95% CI -0.85, -0.19, P=0.002, I 2 =38%) resulted at 52 weeks. In regard to function, pooled results showed non-significant difference between UGL and ESWT at 6 weeks (MD=3.34, 95% CI -11.45, 18.12, P=0.66, I 2 =79%) and at 52 weeks (SMD=0.10, 95% CI -0.40, 0.60, P=0.69, I 2 =30%). Considering the rate of resorption of calcifications between UGL combined with subacromial corticosteroid injection (SCI) versus injection alone, pooled results showed significant difference favoring UGL at <52 weeks (RR=1.63 95% CI 1.34, 1.98, P<0.00001, I 2 =0%). Certainty of evidence ranged from low to very low., Conclusions: UGL seems to be a reasonable and safe treatment for RCCT, however compared to other non/mini-invasive approaches, UGL showed doubtful results in controlling pain and increasing function and rate of calcifications resorption. These results should be interpreted with caution because certainty of evidence ranged from low to very low.

Objective: To culturally adapt and validate the Italian version of the Shoulder Instability-Return to Sport after Injury (SI-RSI-I) scale., Methods: The SI-RSI-I was developed by adapting the Anterior Cruciate Ligament-Return to Sport Index-Italian version and replacing the term "knee" with "shoulder." Subsequently, it underwent validation following COSMIN recommendations. The study involved athletic participants who experienced SI. They completed the SI-RSI-I together with other measurement instruments: Western Ontario Shoulder Instability Index, Kerlan-Jobe Orthopedic Clinic Score, EuroQol-5D-5L, and Numeric Pain Rating Scale. The following psychometric properties were investigated: structural validity, internal consistency, test-retest reliability, measurement error, and construct validity., Results: The study included 101 participants (age mean [SD] 28.5 [7.4] y; 83 males, 18 females). The SI-RSI-I showed a single-factor structure, excellent internal consistency (α = .935), and excellent test-retest reliability (ICC = .926; 95% CI, .853-.964). The standard error of measurement was 6.1 points, and the minimal detectable change was 17.0 points. Furthermore, SI-RSI-I demonstrated moderate to strong correlations with all reference scales, confirming 8 out of 9 (88.0%) hypotheses, thus establishing satisfactory construct validity., Conclusion: The SI-RSI-I has demonstrated robust internal consistency, reliability, validity, and feasibility as a valuable scale for assessing psychological readiness to return to sport in Italian athletes with SI.

Background/aim: The objective of this study was to assess the role of iodine ( 125 I) plaque brachytherapy in the management of uveal melanoma., Patients and Methods: This is a retrospective study of 50 patients (median age 67 years; range=33-86 years) with uveal melanoma, treated with 125 I plaque brachytherapy at the University Hospital of Pisa. Uveal melanoma was diagnosed with A-scan and B-scan standardized echography, fluorescein angiography, indocyanine green-angiography, optical coherence tomography, and/or magnetic resonance imaging. The primary outcomes assessed were local control, overall survival, disease progression, globe preservation, and metastases. Secondary outcomes were acute and late radiation adverse effects., Results: Inclusion criteria comprised Eastern Cooperative Oncology Group performance status ≤2, life expectancy >6 months, and tumor thickness ≤10 mm and\or diameter ≤20 mm. All the patients were treated with 125 I plaque brachytherapy, with a prescription dose of 85 Gy to the tumor apex. The 5-year rate of local control, progression-free survival, metastasis-free survival, enucleation-free survival, and overall survival were 83.0%, 81.4%, 90.3%, 83.1%, and 92.1% respectively. Twenty-four patients (48.0%) had one or more acute and late toxicities. The most common acute adverse events (CTCAE vs. 5.0) grade 1-3 were conjunctivitis and eye pain (6.0%). Regarding late events, radiation retinopathy grade 1-3 occurred in 18.0% of cases, while grade 1-3 vitreous hemorrhage in 2.5%., Conclusion: 125 I plaque brachytherapy offers an effective and safe approach for selected cases of uveal melanoma, due to the reported satisfactory results in terms of local control, eye conservation and survival., (Copyright © 2024, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.)

Introduction: The main goal of this scoping review is to highlight the clinical features of subjects with rotator cuff calcific tendinopathy (RCCT), in order to identify and map this condition clinical criteria, and thus to be able to hypothesize such pathology before imaging investigations., Methods: Four databases were consulted up to January 2023. The obtained results were reported following the PRISMA-ScR and the Joanna Briggs Institute reviewer's manual was used as guideline for conducting the review. No time and geographical restrictions were applied., Results: A total of 851 records have been identified, with 50 studies meeting the inclusion criteria. Subjects with RCCT mostly reported nightly, acute and severe pain with spontaneous onset. Symptoms were mostly unilateral. Subjects were mostly women aged between 30 and 60. Deficit in active and passive range of motion was reported, mainly during abduction and forward flexion. Endocrine and metabolic disorders were described as comorbidity, in particular diabetes and thyroid disorders., Conclusion: In this scoping review, the most relevant RCCT clinical features were detected. These clinical criteria, predictive for shoulder RCCT, can be crucial to help all clinicians suspect this musculoskeletal disease early and with certainty, thus allowing for an appropriate and prompt diagnosis path., Level of Evidence: III., Competing Interests: The authors declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article., (© The Author(s) 2024.)

Bupleurum plantagineum Desf. (Apiaceae) is a plant endemic to North Africa, including Algeria. It is used as natural medicine, due to its anti-inflammatory, antioxidant and hepatoprotective properties. In this work, we studied the chemical composition of the essential oil (EO) obtained by hydro-distillation from B. plantagineum leaves collected from the national park of Gouraya (Bejaïa), Algeria. Thirty components were identified in the EO by Gas chromatography-Mass Spectrometry(GC-MS) (relative abundance: 96.7%). Monoterpene hydrocarbons (56.8%) were the predominant, followed by oxygenated monoterpenes (36.7%). The main components were cis -chrysanthenyl acetate (33.5%), α-pinene (18.4%), myrcene (16.5%) and ( E )-anethole (4.9%). This volatile profile differs from those reported for other Bupleurum spp. and for B. plantagineum from Algeria, suggesting the identification of a new chemotype. Overall, our results represent a contribution to the characterisation of natural products from Algeria and the preservation of its natural biodiversity. The same results will also represent a starting point for further studies on B. plantagineum .