Profound importance of the conventional O-H⋯O hydrogen bond versus a considerable blue shift of the Csp2-H bond in complexes of substituted carbonyls and carboxyls.

Using quantum chemical approaches, we investigated the conventional O-H⋯O and nonconventional Csp2-H⋯O hydrogen bonds between carboxylic acids and aldehydes in 21 stable complexes. The strength of complexes is determined by the conventional O-H⋯O bond together with the nonconventional Csp2-H⋯O hydrogen bond, in which the former one is 4-5 times as strong as the latter one. Proportional linear correlations of the interaction energy with both individual energies of the O-H⋯O and Csp2-H⋯O hydrogen bonds are proposed. Different impacts of electron-donating and electron-withdrawing groups in substituted formaldehyde and formic acid on characteristics of conventional and nonconventional hydrogen bonds, as well as the strength of both hydrogen bond types and complexes, are also evaluated. Following complexation, it is noteworthy that the largest blue shift of the Csp2-H stretching frequency in the Csp2-H⋯O bond up to 105.3 cm-1 in CH3CHO⋯FCOOH is due to a decisive role of the O-H⋯O hydrogen bond, which has been rarely reported in the literature. The obtained results show that the conventional O-H⋯O hydrogen bond plays a pivotal role in the significant blue shift of the Csp2-H stretching frequency in the nonconventional Csp2-H⋯O hydrogen bond. Remarkably, the considerable blue shift of the Csp2-H stretching frequency is found to be one H of C-H in formic acid substituted by the electron-withdrawing group and one H in formaldehyde substituted by the electron-donating group. In addition, the change in the Csp2-H stretching frequency following complexation is proportional to both changes of electron density in σ*(Csp2-H) and σ*(O-H) orbitals, in which a dominant role of σ*(O-H) versus σ*(Csp2-H) is observed.

Barriers for pregnancy and perceptions of gender discrimination of urologists in training in France: Results of a national survey.

INTRODUCTION: Gender discrimination seems more prevalent in surgery than other medical specialties. In addition, female urologists are more likely to have obstetric complications and to be discouraged from starting a family during training. The objective of this study was to determine the prevalence of perceived gender discrimination and barriers for pregnancy during fellowship, among French urology residents and fellows. MATERIAL AND METHODS: The French Association of Urologists in Training performed a national online survey between August and September 2022. Participants were assured that their participation was anonymous. Respondents were questioned on demographics, gender discrimination and on pregnancy barriers during fellowship. RESULTS: In total, 153 members answered the questionnaire out of the 427 members of the association (36%), among which 75 women (49%). Thirty nine percent of the female respondents found that their gender was a barrier in their career advancement, versus 1% of the male (P<0.0001). Forty female respondents (53%) perceived that female urologists earned less respect than their male counterparts versus 22% of the male (P<0.0001). Among the female respondents, 19 (25%) have felt that it would not be possible to become pregnant at the time they would have wanted it and 7 (9%) reported having already been threatened to lose a fellowship position in case of a pregnancy. CONCLUSION: This survey found a high prevalence of gender discrimination among French urologists in training, perceived in majority by women. Female urologists perceived obstacles and received threats when wanting to become pregnant during their training.

Toward an optimization of empirical antibiotic therapy in acute graft pyelonephritis: A retrospective multicenter study.

OBJECTIVE: Acute graft pyelonephritis (AGPN) is the most frequent infectious complication in kidney transplant recipients (KTR). The treatment of acute community-acquired (CA) pyelonephritis is based on third-generation cephalosporins (3GC) and fluoroquinolones. Cefepime or a piperacillin-tazobactam combination are more often used in healthcare-associated (HCA) infections. However, these recommendations do not consider the resistance observed in KTRs. The objective of our study was to define the most appropriate empirical antibiotherapy for AGPN in KTRs according to the CA and HCA settings. To answer this question, we assessed the prevalence of resistance to different antibiotics usually recommended for urinary tract infections (UTIs) in the general population. METHODS: Observational, retrospective, multicenter study covering all episodes of AGPN occurring in hospitalized KTRs in 2019. RESULTS: A total of 210 patients were included in 7 centers and 244 episodes of AGPN were analyzed (158 CA-AGPN and 86 HCA-AGPN). The prevalence of 3GC and fluoroquinolone resistance was 23 % (n = 36) and 30 % (n = 50) in CA infections (n = 158), and 47 % (n = 40) and 31 % (n = 27) in HCA infections (n = 86), respectively. Cefepime resistance rate was 19 % (n = 30) in CA-AGPN and 29 % (n = 25) in HCA-AGPN. Piperacillin-tazobactam combination had resistance rates > 15 % in both CA and HCA infections. The only antimicrobials with resistance rates < 10 % were aminoglycosides and carbapenems. CONCLUSION: None of the antibiotics recommended in empirical treatment in UTIs has shown a resistance rate of less than 10% with regard to AGPN. Therefore, none of them should be used as monotherapy. A combination therapy including amikacin could be an appropriate strategy in this setting.

A stylet use may be beneficial for elective and rescue intubation of prematurely born infants < 30 weeks.

BACKGROUND: Recent studies have reported that using a stylet does not provide any advantages during intubation within a diverse infant population. Our research focuses on the issue, specifically in premature infants who undergo elective or rescue intubation (EI or RI) in the delivery room (DR). METHODS: We conducted a single-center retrospective observational study comparing the number of intubation attempts, the duration of intubation procedure until successful, and the rate of associated desaturations exceeding 20%. We derived outcomes from video recordings and performed statistical analyses. RESULTS: We have analyzed 104 intubation attempts in 70 infants with a mean gestational age and birth weight of 25±1.9 weeks and 736±221 grams, respectively; 39 of these attempts involved stylet use, and 65 did not. 75% of infants requiring intubation were less than 26 weeks of gestational age. The use of a stylet increased the rate of successful initial attempts [OR (95% CI) 4.3 (1.3-14.8), P=0.019], reduced the duration of the intubation procedure [median (IQR) seconds: 43 (30-72) vs 140 (62-296), P<0.001], and decreased the occurrences of desaturation exceeding 20% (13% vs 50%, P=0.003). CONCLUSION: The benefits of using a stylet during rescue and elective intubations of premature infants in the delivery room outweigh the potential harms. Its use may be advantageous in settings where proactive approaches are implemented for periviable infants.

Indicuen, a new hopane from Parmotrema indicum Hale growing in Vietnam.

One new hopane-type triterpene, indicuen (1), along with eight known compounds (2-9) were isolated from the n-hexane extract of the lichen Parmotrema indicum Hale. The chemical structures of isolated compounds were identified by interpretation of their spectroscopic data (1D, 2D NMR and HRESIMS) combined with DFT-NMR chemical shift calculations and subsequent assignment of DP4+ probabilities and by comparison with the literature. Indicuen represents for a rare hopane bearing a 1-carboxyethyl substituent at C-21 in lichens. Compounds 1-3 and 5-8 were evaluated for α-glucosidase inhibition and cytotoxicity against K562 and HepG2 cancer cell lines. Compounds 1, 5 and 7 exhibited moderate α-glucosidase inhibition with IC50 values of 201.1, 156.3 and 187.4 µM, respectively. Compound 1 also showed weak cytotoxicity toward K562 cell line while others showed no activity.

Expanding Active Surveillance Criteria for Low- and Intermediate-risk Prostate Cancer: Can We Accurately Predict the Risk of Misclassification for Patients Diagnosed by Multiparametric Magnetic Resonance Imaging-targeted Biopsy?

Models predicting the risk of adverse pathology (ie, International Society of Urological Pathology [ISUP] grade group ≥3, pT3, and/or pN1) among patients operated by radical prostatectomy (RP) have been proposed to expand active surveillance (AS) inclusion criteria. We aimed to test these models in a set of 1062 low-risk and favorable intermediate-risk prostate cancer (PCa) patients diagnosed by multiparametric magnetic resonance imaging (MRI) and MRI-targeted biopsy. We hypothesized that the inclusion of radiological features into a novel model would improve patient selection. Performance was assessed using discrimination, calibration, and decision curve analysis (DCA). Available models were characterized by poor discrimination (areas under the receiver operating characteristic curve [AUCs] of 59% and 60%), underestimation of predicted risk on calibration plots, and a small amount of net benefit against a probability threshold of 40-50% at the DCA. The development of a novel model slightly improved discrimination (AUC of 63% vs 59%, p = 0.001, and 63% vs 60%, p = 0.07) and net benefit against threshold probabilities of ≥30%. This first multicenter study demonstrated the poor performance of models predicting adverse pathology and that implementation of MRI and MRI-targeted biopsy in this setting was not associated with a clear improvement in patient selection. Patients harboring low-risk or favorable intermediate-risk PCa and candidates for RP cannot be referred accurately to an AS program without a non-negligible risk of misclassification. PATIENT SUMMARY: We tested prediction models that could expand the selection of prostate cancer patients for active surveillance. Models were inaccurate and associated with a high risk of misclassification despite the implementation of multiparametric magnetic resonance imaging and targeted biopsies.

Role of O-H⋯O/S conventional hydrogen bonds in considerable Csp2 -H blue-shift in the binary systems of acetaldehyde and thioacetaldehyde with substituted carboxylic and thiocarboxylic acids.

Stable binary complexes of RCZOH⋯CH3CHZ (R = CH3, H, F; Z = O, S) are due to contributions from the O-H⋯O/S and Csp2 -H⋯O/S hydrogen bonds. The strength of Csp2 /O-H⋯O is 1.5 to 2 times greater than that of the Csp2 /O-H⋯S bond. The substitution of H(Csp2 ) of HCZOH by CH3 causes a decrease in complex stability, while the opposite trend occurs for the F atom. A very large red shift of the O-H stretching frequency in O-H⋯O/S bonds was observed. A surprising Csp2 -H blue shift up to 104.5 cm-1 was observed for the first time. It is found that the presence of O-H⋯O/S hydrogen bonds and a decisive role of intramolecular hyperconjugation interactions in the complex cause a significant blue shift of the Csp2 -H covalent bonds. A striking role of O compared to the S atom in determining the blue shift of Csp2 -H stretching vibration and stability of binary complexes is proposed. The obtained results show that the ratio of deprotonation enthalpy and proton affinity could be considered as an index for the classification of the non-conventional hydrogen bond. SAPT2+ results show that the strength of RCSOH⋯CH3CHS complexes is dominated by electrostatic and induction energies, while a larger contribution to the stability of remaining complexes is detected for the electrostatic component.

Importance of water and intramolecular interaction governs substantial blue shift of Csp2 -H stretching frequency in complexes between chalcogenoaldehydes and water.

Geometrical structure, stability and cooperativity, and contribution of hydrogen bonds to the stability of complexes between chalcogenoaldehydes and water were thoroughly investigated using quantum chemical methods. The stability of the complexes increases significantly when one or more H2O molecules are added to the binary system, whereas it decreases sharply going from O to S, Se, or Te substitution. The O-H⋯O H-bond is twice as stable as Csp2 -H⋯O and O-H⋯S/Se/Te H-bonds. It is found that a considerable blue-shift of Csp2 -H stretching frequency in the Csp2 -H⋯O H-bond is mainly determined by an addition of water into the complexes along with the low polarity of the Csp2 -H covalent bond in formaldehyde and acetaldehyde. The Csp2 -H stretching frequency shift as a function of net second hyperconjugative energy for the σ*(Csp2 -H) antibonding orbital is observed. Remarkably, a considerable Csp2 -H blue shift of 109 cm-1 has been reported for the first time. Upon the addition of H2O into the binary systems, halogenated complexes witness a decreasing magnitude of the Csp2 -H stretching frequency blue-shift in the Csp2 -H⋯O H-bond, whereas CH3-substituted complexes experience the opposite trend.