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Peyronie’s disease (PD), also known as induration penis plastica (IPP), is a clinical condition characterized by the formation of fibrotic plaques onto the tunica albuginea of the penis, which may result into abnormal penile curvature and deformity, erectile dysfunction (ED), and loss of penile length. The combination of these events may result in the impossibility of performing penetrative intercourse [1].

Introduction: Andrological emergencies include a wide array of acute genital injuries which require immediate care from the specialist. Missing or delaying treatment often results in permanent loss of function or, in some cases, loss of the affected organ itself.Evidence acquisition: A comprehensive bibliographic search of PubMed database with up-to-date existing reviews and case reports was performed.Objective: This chapter aims to review major andrological emergencies with peculiar attention to clinical presentation and practical management in order to provide the specialist with reliable information to keep in mind when confronting these challenging occurrences.

Background Several trials have reported on the impact of social restrictions due to SARS-CoV-2 (COVID-19) pandemic on sexual function and psycho-physical well-being. However, data showing modifications of these outcomes over time and at the end of lock-down are scant. Aim We investigated the longitudinal changes in sexual function during social restrictions for COVID-19 pandemic in Italy. Methods A web-based survey was administered to Italian citizens of legal age via social networks. The Beck Depression Inventory Primary Care, the General Health Survey, Female Sexual Function Index, International Index of Erectile Function, UCLA Loneliness Scale-version 3 questionnaires were used to test mental, physical and sexual well-being. The questionnaires were administered at the beginning of the lockdown (T0), 15 days from the first assessment (T1) and 1 month after the end of the restrictions in 2020 (T2). Outcomes Descriptive statistics and multiple regression analysis were applied to investigate changes in sexual function over and at the end of social restrictions. Results Data were available for 2543 people (47.2% of men; 43.4% women; 9.4% undefined). Mean age was 48.3 ± 15.1 years for males and 43.9 ± 13.4 for females. Overall, 2.6% reported depressive symptoms according to Beck Depression Inventory Primary Care, 7.4% reported a high level of UCLA loneliness and 19.4% low levels of general mental health. Mild to severe erectile dysfunction was reported by 59.1% of men at T0, while 68.4% of women reported sexual dysfunction. Sexual function levels remain generally unchanged at further follow-up over the social restriction time period (T1), although those who were sexually active at baseline showed a decrease in sexual function scores. At T2, there was an overall improvement in sexual function scores with a rate of severe erectile dysfunction decreasing from 37.1% to 24.1% from T0 to T2 among males and a significant decrease of female sexual dysfunction from 68.4% to 51.2%. Clinical Implications Young individuals and those with good mental and physical health were more likely to improve sexual function at the end of social restrictions. Strengths & Limitations Valid and reliable questionnaires and longitudinal approach design represent strengths; a large but convenient sample and lack of pre-pandemic baseline data represent limits. Conclusion Social restrictions due to COVID-19 pandemic led to an increase in sexual dysfunctions in both genders. However, these conditions appeared temporary since an overall improvement was observed at the end of lockdown and especially in younger individuals with higher psycho-physical well-being.

Peyronie’s disease is a chronic inflammatory disease involving the formation of plaque in the tunica albuginea of the corpora cavernosa, resulting in penis deformity. It is often associated with penile pain, especially in younger patients, but it is not rare for pain to be absent; the disease is also associated with erectile dysfunction and a depressive state in a large percentage of cases. Objective: Aim of our study was to explore the basic knowledge base and diagnostic and therapeutic practice patterns in Peyronie's disease (PD) of a large number of physicians belonging to the Italian Andrology Society (SIA). Methods: Our survey is based on two questionnaires which were e-mailed to the members of the SIA. The first questionnaire explored diagnostic and therapeutic practice patterns of SIA physicians, while the second questionnaire focused on their knowledge of the disease, as well as their training and level of experience in the specific field. We then planned to compare our outcomes with similar PD surveys from other countries. Results: The first questionnaire was answered by 142 SIA physicians. The second questionnaire was answered by 83 SIA physicians. Most respondents (74.6%) chose penile ultrasonography as first-line diagnostic approach and 47.1% prefer to perform a color Doppler ultrasound after pharmaco-induced erection. Concerning the therapeutic practice patterns in active stage of the disease, most respondents (99.29%) prefer conservative medical therapy. Additionally, most respondents (64.78%), when failure of conservative treatment had been established, considered surgical treatment necessary, specifically corporoplasty, which may be associated with other techniques. Conclusions: The results of our survey show that, in comparison to their foreign counterparts, Italian SIA uro-andrologists have a more proactive diagnostic approach right from when patients first present. When PD is still in its active stage, SIA uro-andrologists mostly opt for medical therapy. In advanced disease or if conservative treatment fails, our survey indicates a greater preference for surgical treatment. Answers to the theoretical knowledge questions showed that SIA physicians have a good understanding of the disease’s etiology, epidemiology, and clinical picture, and of the appropriate indications for treatment.

A 50-year-old man who worked as a helicopter rescue pilot transiently lost consciousness while piloting a helicopter rescue. In the diagnostic process, all tests for the main possible differential diagnoses of loss of consciousness (cardiological and neurological) were performed and yielded normal results. Blood chemistry tests revealed recurrent fasting hypoglycemia and Chromogranin A was at the upper limit of normal. Fine needle aspiration guided by endoscopic ultrasonography was used to diagnose insulinoma-type neuroendocrine tumor of the pancreas. According to the Italian policies, the occupational physician aims to maintain professional skills without neglecting flight safety. A careful analysis of the relationship between the characteristics of the state of health of the aviator and his specific work needs was carried out, and he was given the opportunity to continue working as a rescue pilot thanks to medical therapies associated with organizational interventions in the workplace.

The intrinsic Hamiltonian of the Two-Rotors Model as a quantized classical system in which the rotors are abstract rigid bodies has a D 2 point symmetry and then its eigenstates come in quadruplets. Only one member of each of the two lowest quadruplets was investigated so far, the ground state and the scissors mode. I determine the whole quadruplets which turn out to contain states of negative parity. When the rotors are made of particles, the D 2 symmetry is broken. The actual existence of the new states of the multiplets in atomic nuclei depends on the existence of excited states of the neutron and proton fluids separately odd under inversion of the intrinsic coordinates. The energies of the new states are ω + e , ω + 2 e when one or both rotors have negative parity respectively, where ω is the scissors excitation energy and e is the excitation energy of a single rotor with negative parity. Nonvanishing transitions occur only between states whose energies differ by ω.

I determine the intrinsic Hamiltonian of the relative motion of the constituent fermions of bosonic composites in superfluid fermion systems, assuming the effective fermion-fermion potential to be a sum of separable terms. The derivation is based on an expansion that treats composites, quasiparticles, and their interactions on the same footing. The intrinsic Hamiltonian of the composites is expressed in terms of the solution of the gap equation and of the form factors of the potential. It has the Brillouin-Wigner form, namely it is Hermitian and energy-dependent. In such a context, a solid justification is given for discarding negative energies of the composites. As a check, I rederive the dispersion law of the Bogoliubov-Anderson mode and the spectrum of the Bardasis and Schrieffer Hamiltonian. The possible occurrence of gapped modes depending on the form of the fermion-fermion interaction is discussed. The intrinsic wave functions are derived explicitly in the long wave limit, while their full determination requires numerical calculations.

The severity of coronavirus disease 2019 (COVID‐19) is a crucial problem in patient treatment and outcome. The aim of this study is to evaluate circulating level of sphingosine‐1‐phosphate (S1P) along with severity markers, in COVID‐19 patients. One hundred eleven COVID‐19 patients and forty‐seven healthy subjects were included. The severity of COVID‐19 was found significantly associated with anemia, lymphocytopenia, and significant increase of neutrophil‐to‐lymphocyte ratio, ferritin, fibrinogen, aminotransferases, lactate dehydrogenase (LDH), C‐reactive protein (CRP), and D‐dimer. Serum S1P level was inversely associated with COVID‐19 severity, being significantly correlated with CRP, LDH, ferritin, and D‐dimer. The decrease in S1P was strongly associated with the number of erythrocytes, the major source of plasma S1P, and both apolipoprotein M and albumin, the major transporters of blood S1P. Not last, S1P was found to be a relevant predictor of admission to an intensive care unit, and patient’s outcome. Circulating S1P emerged as negative biomarker of severity/mortality of COVID‐19 patients. Restoring abnormal S1P levels to a normal range may have the potential to be a therapeutic target in patients with COVID‐19.

Sequential neurogenesis determines the functional properties of habenular neurons., The developing brain undergoes drastic alterations. Here, we investigated developmental changes in the habenula, a brain region that mediates behavioral flexibility during learning, social interactions, and aversive experiences. We showed that developing habenular circuits exhibit multiple alterations that lead to an increase in the structural and functional diversity of cell types, inputs, and functional modules. As the habenula develops, it sequentially transforms into a multisensory brain region that can process visual, olfactory, mechanosensory, and aversive stimuli. Moreover, we observed that the habenular neurons display spatiotemporally structured spontaneous activity that shows prominent alterations and refinement with age. These alterations in habenular activity are accompanied by sequential neurogenesis and the integration of distinct neural clusters across development. Last, we revealed that habenular neurons with distinct functional properties are born sequentially at distinct developmental time windows. Our results highlight a strong link between the functional properties of habenular neurons and their precise birthdate.

[EN] Dipicolinic acid (DPA), present in large amount in bacterial spores, has been proposed to act as an endogenous photosensitizer in spore photoproduct formation. The proposed mechanism involves a triplet-triplet energy transfer from DPA to thymine. However, up to now, no spectroscopic studies have been performed to determine the interaction between the endogenous compound and the nucleobase, probably due to its photolability in aqueous solutions. Here, triplet excited state properties of DPA are reported together with its bimolecular quenching rate constant by thymidine, kq of ca. 5.3 × 109 M-1 s-1. To run more reliable studies, a stable methyl ester derivative of DPA, which exhibits the same spectroscopic properties as the parent compound, is also described. Finally, DPA photoproducts are characterized. Studies of their triplet excited state properties have demonstrated that, interestingly, one of them is able to photosensitize thymidine triplet excited state formation., This work was supported by the Spanish Government (project PGC2018-096684-B-I00) and the Generalitat Valenciana (Prometeo/2017/075).

Background Odor-driven behaviors such as feeding, mating, and predator avoidance are crucial for animal survival. The neural pathways processing these behaviors have been well characterized in a number of species, and involve the activity of diverse brain regions following stimulation of the olfactory bulb by specific odors. However, while the zebrafish olfactory circuitry is well understood, a comprehensive characterization linking odor-driven behaviors to specific odors is needed to better relate olfactory computations to animal responses. Results Here, we used a medium-throughput setup to measure the swimming trajectories of 10 zebrafish in response to 17 ecologically relevant odors. By selecting appropriate locomotor metrics, we constructed ethograms systematically describing odor-induced changes in the swimming trajectory. We found that adult zebrafish reacted to most odorants using different behavioral programs and that a combination of a few relevant behavioral metrics enabled us to capture most of the variance in these innate odor responses. We observed that individual components of natural food and alarm odors do not elicit the full behavioral response. Finally, we show that zebrafish blood elicits prominent defensive behaviors similar to those evoked by skin extract and activates spatially overlapping olfactory bulb domains. Conclusion Altogether, our results highlight a prominent intra- and inter-individual variability in zebrafish odor-driven behaviors and identify a small set of waterborne odors that elicit robust responses. Our behavioral setup and our results will be useful resources for future studies interested in characterizing innate olfactory behaviors in aquatic animals. © The Author(s). 2020 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data.

[EN] Transient absorption spectroscopy in combination with in silico methods has been employed to study the interactions between human serum albumin (HSA) and the anti-psychotic agent chlorpromazine (CPZ) as well as its two demethylated metabolites (MCPZ and DCPZ). Thus, solutions containing CPZ, MCPZ or DCPZ and HSA (molar ligand:protein ratios between 1:0 and 1:3) were submitted to laser flash photolysis and the Delta A(max) value at lambda = 470 nm, corresponding to the triplet excited state, was monitored. In all cases, the protein-bound ligand exhibited higher Delta Amax values measured after the laser pulse and were also considerably longer-lived than the non-complexed forms. This is in agreement with an enhanced hydrophilicity of the metabolites, due to the replacement of methyl groups with H that led to a lower extent of protein binding. For the three compounds, laser flash photolysis displacement experiments using warfarin or ibuprofen indicated Sudlow site I as the main binding site. Docking and molecular dynamics simulation studies revealed that the binding mode of the two demethylated ligands with HSA would be remarkable different from CPZ, specially for DCPZ, which appears to come from the different ability of their terminal ammonium groups to stablish hydrogen bonding interactions with the negatively charged residues within the protein pocket (Glu153, Glu292) as well as to allocate the methyl groups in an apolar environment. DCPZ would be rotated 180 degrees in relation to CPZ locating the aromatic ring away from the Sudlow site I of HSA. (C) 2019 Elsevier B.V. All rights reserved., Financial support from Ministerio de Economia, Industria y Competitividad (CTQ2016-78875-P, SAF2016-75638-R, BES-2011-043706), Generalitat Valenciana (Prometeo 2017/075), Xunta de Galicia [Centro Singular de Investigacion de Galicia accreditation 2016-2019 (ED431G/09, ED431B 2018/04) and post-doctoral fellowship to E. L.] and European Union (European Regional Development Fund-ERDF) is gratefully acknowledged. I. A. holds a "Miguel Servet" contract (CP1116/00052) funded by the Carlos III Health Institute. We are grateful to the Centro de Supercomputacion de Galicia (CESGA) for computational facilities.

Background: Since December 2019, COVID-19 has widely spread throughout the world, causing thousands of deaths. Clinical characteristics of COVID-19 patients have been widely reported, but significative disease-associated biomarkers are needed. We aimed to evaluate the prognostic power of circulating sphingosine-1-phosphate (S1P) in COVID-19, to propose S1P as a novel prognostic and predictive biomarker. Methods: Clinical and blood parameters were investigated in 111 COVID-19 patients (COV) and 47 healthy subject (HLT), with a particular focus on patients who required intensive care unit (ICU) admission. We measured serum levels of S1P and its main transporter apolipoprotein M (apoM) by ELISA assay. Correlation with clinical and blood parameters were performed by Pearson correlations. Univariable and multivariable regression analysis were performed to assess the interaction between clinically significant factors and ICU admission. Further, Cox regression was used to evaluate the prognostic power of S1P for ICU admission and mortality. Findings: We reported statistically significant alterations of several blood parameters in COV, as an increase of white blood cells, neutrophil-to-lymphocyte ratio, ferritin, D-dimer and fibrinogen, and a decrease in hemoglobin, lymphocyte count and total proteins. Our major finding is the drop of serum S1P level in COV, strongly associated with the decrease of red blood cells, the major source of plasmatic S1P, and both apoM and albumin, the most important transporters of circulating S1P. The multivariable regression analysis revealed that S1P is the most important predictor for ICU admission (OR:39·45, [95%CI:1·51-1031·60]; p=0·027), and Cox proportional-hazards model demonstrated a high power of S1P in predicting patient’s outcome. Interpretation: COVID-19 patients showed a drastic decrease of serum S1P, suggesting that circulating S1P levels may be clinically used as negative biomarkers to predict severity/mortality of COVID-19. Taken together, our results suggest that restoring S1P at physiological level may represent a novel therapeutic strategy. Funding: Italian Ministry of Health. Declaration of Interests: All authors declare no competing interests. Ethics Approval Statement:This prospective, case-control study was approved by the Ethic Committee of Ospedale San Paolo in Milan, Lombardy, Italy (COST Action n.2020/ST/057).

The possible strategies for the remodulation of the andrological activity were discussed and shared within a team of national experts belonging to the Italian Society of Andrology (SIA). Initiatives for andrologists. With the various provisions of the Prime Minister that have followed all the national and local scientific meetings were canceled. In order to compensate for this abrupt lack of opportunities for scientific meetings, a cycle of live reports was activated on YOUTUBE by recognized experts, to cover many different andrological topics. The YOUTUBE channel was chosen as it can be easily followed by each member without having to download any streaming program, with the possibility to consult the contents without any time limitation. Initiatives for patients In this new context, non-urgent outpatient activities (such as Andrology) have been suspended throughout the national territory.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is the coronavirus that causes an infectious disease, called COVID-19, first detected in patients with pneumonia in Wuhan (People's Republic of China) on December 2019. Italy was the first European country to state the outbreak of the infection and its Council of Ministers declared the state of health emergency on 31.01.2020, then the World Health Organization ruled a global pandemic on 11.03.2020. The nasopharyngeal swab is based on the detection of virus RNA and is the only reliable one for declaring COVID-19 infection. The most common symptoms observed in COVID-19 patients before hospitalization may be fever, chills, cough, dyspnea, asthenia, myalgia and/or arthralgia. This symptomatology can be often complicated in a dramatically increasing manner such as to require hospitalization starting from the third-fourth week. COVID-19 outbreak has dramatically affected the quality of life by changing inter-personal relationships, community life and obviously sexual health. The purpose of this work, based on available evidence, is to provide recommendations to help the population to face their sexual life in this critical period.

To investigate the efficacy, tolerability, and patient’s preference of alprostadil cream for topical use administered within the urethral meatus versus the standard administration route, in erectile dysfunction (ED) treatment. Seventy-one patients (mean age 59.7 ± 9.0 years) affected by ED were analyzed in this multicenter, randomized, two-administration routes, cross-over trial. All patients received a single dose of alprostadil cream applying the dispenser to the tip of the penis (without contacting the urethral meatus) (Standard administration route or ST.AR) alternating with a single dose of alprostadil cream applying the dispenser within the urethral meatus (New administration route or NEW.AR) separated by a one-week washout period, according to randomization. The primary objective of the study was to evaluate the change in International Index of Erectile Function (IIEF-5) total score from baseline to the control visit by comparing the ST.AR and NEW.AR. Secondary objectives of the study were to compare the different methods of administration by evaluating the change in the Sexual Encounter Profile (SEP-2 and SEP-3) questionnaire score and the Patient Reported Outcomes (PROs) by scoring the Patient Self- Assessment of Erection (PSAE) questionnaire. The treatment safety profile was assessed by analysis of adverse events (AEs). Based on the study findings it is evident that the NEW.AR is more efficacious than the ST.AR in improving IIEF-5 and SEP scores from baseline to control visit (IIEF-5: +3.8 vs +6.3; p < 0.001; positive response to SEP-2: 10 vs 27; p = 0.002) and in terms of PSAE (a significant improvement from the baseline in 31% of patients; p < 0.001). As regards the safety profile, no difference in terms of local and systemic side effects was found.

Reduction of nitrobenzene by excess organic electron donor, 12, affords diphenylhydrazine in a reaction where azobenzene oxide and azobenzene are likely intermediates. No cleavage of the N-N σ-bond is seen under photoactivation conditions, whereas traces are seen under thermal activation. Hydrazone derivatives were prepared to explore the cleavage of N-N σ-bonds; the results show that a low-lying LUMO assists the transition state for accepting an electron, and the stabilisation that the potential fragments from N-N bond cleavage afford to the fragments is important in determining whether cleavage is observed.

Odor-driven behaviors such as feeding, mating and predator avoidance are crucial for animal survival. While the zebrafish olfactory circuitry is well understood, a comprehensive description of odor-driven behaviors is needed to better relate olfactory computations to animal responses. Here, we used a medium-throughput setup to measure the swimming trajectories of 10 zebrafish in response to 17 ecologically relevant odors. By selecting appropriate locomotor metrics, we constructed ethograms systematically describing odor-induced changes in the swimming trajectory. We found that fish reacted to most odorants, using different behavioral programs and that combination of few relevant behavioral metrics enabled to capture most of the variance in these innate odor responses. We observed that monomolecular odors in similar chemical categories were weakly clustered based on the behavioral responses, likely because natural odors elicited stronger reactions than the monomolecular odors. Finally, we uncovered a previously undescribed intra and inter-individual variability of olfactory behaviors and suggest a small set of odors that elicit robust responses. In conclusion, our setup and results will be useful resources for future studies interested in characterizing olfactory responses in aquatic animals.

Silylation of primary and secondary amines is reported, using triethylsilane as the silylating reagent in the presence of potassium tert-butoxide (KOtBu). The reaction proceeds well in the presence of 0.2 equiv of KOtBu. In competition experiments, aniline is selectively silylated over aliphatic amines. Computational studies support a catalytic mechanism which is initiated by KOtBu interacting with the silane to form KH and silylated amine. The KH then takes over the role of base in the propagation of the cyclic mechanism, and deprotonates the amine. This reacts with R3SiH to afford the product R3SiNR’R” and regenerate KH.

[EN] Cholesterol (Ch) is an integral part of cell membrane, where it is prone to oxidation. In humans, oxidation of Ch is commonly linked to various pathologies like Alzheimer's disease, atherosclerosis, and even cancer, which proceed via mechanisms involving enzymatic and free radical pathways. The latter begin with hydrogen abstraction (HA) from Ch by a reactive free radical. It has been established that the most efficient HA from Ch occurs at C7, although HA from C4 by peroxyl radicals has recently been observed. Conversely, HA from Ch positions other than the thermodynamically preferred C7 or C4 has never been reported. We have designed a Ch derivative where a benzophenone moiety is linked to C7 by a covalent bond. This mirrors a specific orientation of Ch within a confined environment. Product analysis and time-resolved spectroscopic studies reveal an unprecedented HA from C15, which is a thermodynamically unfavorable position. This indicates that a specific topology of reactants is crucial for the reactivity of Ch. The relative orientation of the reactants can also be relevant in biological membranes, where Ch, polyunsaturated fatty acids, and numerous oxidizing species are confined in highly restricted and anisotropic environments., This work was supported by the Carlos III Institute of Health (Grants No. PII6/01877, "Miguel Servet fellowship" CPII16/00052 to I.A.), and by the Generalitat Valenciana (Prometeo 2017/075). We would like to thank Dr Fedora Grande for sending an exchange student (M.B.). D.N. and G.G. thank NAWI Graz for support.

The infrared behaviour of matrix elements between coherent states of definite color is studied in non-abelian gauge theories. The matrix elements are shown to be finite to the lowest non-trivial order, and to all orders if the soft meson formula for real gluons holds to all orders. Factorization occurs in the fixed angle regime.

In a recent paper it has been shown that a number of rare-earth elements have a definite deviation from axial symmetry, with the triaxiality angle $\ensuremath{\gamma}\ensuremath{\ge}8$ degrees and the ratios of the components of the inertia tensor in qualitative agreement with the irrotational model. Such results have been extracted from experimental data within the J-2 subspace, but scissors-mode resonances, which are most sensitive to the nuclear shape, were not included in the analysis. The irrotational and rigid inertia tensors have an opposite dependence on the triaxiality angle $\ensuremath{\gamma}$ and this affects in a striking way the fine structure of scissors-mode resonances.

Cholesterol (Ch) is an important lipidic building block and a target for oxidative degradation, which can be induced via free radicals or singlet oxygen (1O2). Suprofen (SP) is a nonsteroidal anti-inflammatory drug that contains the 2-benzoylthiophene (BZT) chromophore and has a π,π* lowest triplet excited state. In the present work, dyads (S)- and (R)-SP-α-Ch (1 and 2), as well as (S)-SP-β-Ch (3) have been prepared from β- or α-Ch and SP to investigate the possible competition between photogeneration of biradicals and 1O2, the key mechanistic steps in Ch photooxidation. Steady-state irradiation of 1 and 2 was performed in dichloromethane, under nitrogen, through Pyrex, using a 400 W medium pressure mercury lamp. The spectral analysis of the separated fractions revealed formation of two photoproducts 4 and 5, respectively. By contrast, under the same conditions, 3 did not give rise to any isolable Ch-derived product. These results point to an intramolecular hydrogen abstraction in 1 and 2 from the C7 position of Ch and subsequent C C coupling of the generated biradicals. Interestingly, 2 was significantly more photoreactive than 1 indicating a clear stereodifferentiation in the photochemical behavior. Transient absorption spectra obtained for 1 3 were very similar and matched that described for the SP triplet excited state (typical bands with maxima at ca. 350 nm and 600 nm). Direct kinetic analysis of the decay traces at 620 nm led to determination of triplet lifetimes that were ca. 4.1 μs for 1 and 2 and 5.8 μs for 3. From these data, the intramolecular quenching rate constants in 1 and 2 were determined as 0.78 × 105 s−1. The capability of dyads 1 3 to photosensitize the production of singlet oxygen was assessed by time-resolved near infrared emission studies in dichloromethane using perinaphthenone as standard. The quantum yields (ΦΔ) were 0.52 for 1 and 2 and 0.56 for 3. In conclusion, SP-α-Ch dyads are unique in the sense that they can be used to photogenerate both biradicals and singlet oxygen, thus being able to initiate Ch oxidation from their triplet excited states following either of the two competing mechanistic pathways., Financial support from the Generalitat Valenciana (Prometeo Program), the Spanish Government (CTQ2014-54729-C2-2-P and FPU fellowship for F.P.) and the Carlos III Institute of Health (Grant RIRAAF, RETICS program and Miguel Servet Contract CP11/00154 for I. A.) is gratefully acknowledged.

The occurrence of scissors modes in crystals that have deformed ions in their unit cells was predicted some time ago. The theoretical value of their energy is rather uncertain, however, ranging between ten and a few tens of eV, with the corresponding widths of 10−7to 10−6 eV. Their observation by resonance fluorescence experiments therefore requires a photon spectrometer covering a wide energy range with a very high resolving power. Here, a new experiment is proposed and discussed in which such difficulties are overcome by measuring with a superconducting quantum interference device (SQUID) the variation of the magnetic field associated with the excitation of scissors modes.

Long-standing controversial reports of electron transfer from KOtBu to benzophenone have been investigated and resolved. The mismatch in the oxidation potential of KOtBu (+0.10 V vs SCE in DMF) and the first reduction potential of benzophenone (of many values cited in the literature, the least negative value is −1.31 V vs SCE in DMF), preclude direct electron transfer. Experimental and computational results now establish that a complex is formed between the two reagents, with the potassium ion providing the linkage, which markedly shifts the absorption spectrum to provide a tail in the visible light region. Photoactivation at room temperature by irradiation at defined wavelength (365 or 400 nm), or even by winter daylight, leads to the development of the blue color of the potassium salt of benzophenone ketyl, whereas no reaction is observed when the reaction mixture is maintained in darkness. So, no electron transfer occurs in the ground state. However, when photoexcited, electron transfer occurs within a complex formed from benzophenone and KOtBu. TDDFT studies match experimental findings and also define the electronic transition within the complex as n → π*, originating on the butoxide oxygen. Computation and experiment also align in showing that this reaction is selective for KOtBu; no such effect occurs with NaOtBu, providing the first case where such alkali metal ion selectivity is rationalized in detail. Chemical evidence is provided for the photoactivated electron transfer from KOtBu to benzophenone: tert-butoxyl radicals are formed and undergo fragmentation to form (acetone and) methyl radicals, some of which are trapped by benzophenone. Likewise, when KOC(Et)3 is used in place of KOtBu, then ethylation of benzophenone is seen. Further evidence of electron transfer was seen when the reaction was conducted in benzene, in the presence of p-iodotoluene; this triggered BHAS coupling to form 4-methylbiphenyl in 74% yield.

he influence of non-covalent σ–π orbital interactions on triplet–triplet energy transfer (TTET) through tuning of the donor excitation energy remains basically unexplored. In the present work, we have investigated intermolecular TTET using donor moieties covalently linked to a rigid cholesterol (Ch) scaffold. For this purpose, diaryl ketones of π,π* electronic configuration tethered to α- or β-Ch were prepared from tiaprofenic acid (TPA) and suprofen (SUP). The obtained systems TPA-α-Ch, TPA-β-Ch, SUP-α-Ch and SUP-β-Ch were submitted to photophysical studies (laser flash photolysis and phosphorescence), in order to delineate the influence of steric shielding and σ–π orbital interactions on the rate of TTET to a series of energy acceptors. As a matter of fact, fine tuning of the donor triplet energy significantly modifies the rate constants of TTET in the absence of diffusion control. The experimental results are rationalized by means of theoretical calculations using first principles methods based on DFT as well as molecular dynamics., Financial support from the Generalitat Valenciana (Prometeo Program), the Spanish Government (CTQ2010-19909, SEV-2012-0267 and FPU fellowship for F.P.) and the Carlos III Institute of Health (Grant RIRAAF, RETICS program and Miguel Servet Contract CP11/00154 for I. A.) is gratefully acknowledged. We thank ASIC-UPV for computing time. Dedicated to Prof. Diego Cortes on the occasion of his 60th birthday.

Ultrasound penile examination is an indispensable tool in clinical urology, included among the diagnostic tests available to the clinician for the study of problems of erectile dysfunction (ED), both as baseline examination and integrated by a color Doppler imaging study.