ELECTROCHEMICAL GENERATION OF A CATALYST FOR MICHAEL ADDITION OF DICARBONYL COMPOUNDS AND CYANIDE ANION TO ACRYLOYLFERROCENE

Michael addition of diethyl malonate, ethyl acetoacetate, acetylacetone, and cyanide anion to acryloylferrocene promoted by a catalyst in situ generated from a sacrificial zirconium anode is described. Most of the obtained compounds were identified by comparison of their spectral and physical data with those published elsewhere, whereas the only newly synthesized compound - diethyl 2,2-bis(3-ferrocenyl-3-oxopropyl)malonate - was completely characterized by spectral (IR, 1H- and 13C-NMR), physical and crystallographic (single-crystal X-ray)  data. ELEKTROHEMIJSKO GENERISANJE KATALIZATORA ZA MAJKLOVU ADICIJU DIKARBONILNIH JEDINJENJA I CIJANIDA NA AKRILOILFEROCENOpisana je Majklova adicija dietil-malonata, etil-acetoacetata, acetilacetona i cijanidnog anjona na akriloilferocen pomoću katalizatora generisanog in situ sa rastvorne anode od cirkonijuma. Većina dobijenih jedinjenja je identifikovana poređenjem njihovih fizičkih i spektroskopskih podataka sa literaturnim, a jedino novo jedinjenje je potpuno opisano spektroskopskim (IR, 1H- i 13C-NMR) i fizičkim podacima, kao i podacima iz kristalografske analize X-zracima. HIGHLIGHTSMichael addition of diethyl malonate, ethyl acetoacetate, acetylacetone, and cyanide anion to acryloylferrocene is described.Reaction was promoted by a catalyst in situ generated from a sacrificial zirconium anode.Diethyl 2,2-bis(3-ferrocenyl-3-oxopropyl)malonate, a new compound, was completely characterized by spectral, physical and crystallographic data.Other obtained compounds were identified by comparison of their spectral and physical data with those published elsewhere. 

ART in Europe, 2017: results generated from European registries by ESHRE

© The Author(s) 2021. Published by Oxford University Press on behalf of European Society of Human Reproduction and Embryology. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse, distribution, and reproduction in any medium, provided the original work is properly cited.Study question: What are the data on ART and IUI cycles, and fertility preservation (FP) interventions reported in 2017 as compared to previous years, as well as the main trends over the years? Summary answer: The 21st ESHRE report on ART and IUI shows the continual increase in reported treatment cycle numbers in Europe, with a decrease in the proportion of transfers with more than one embryo causing an additional slight reduction of multiple delivery rates (DR) as well as higher pregnancy rates (PR) and DR after frozen embryo replacement (FER) compared to fresh IVF and ICSI cycles, while the number of IUI cycles increased and their outcomes remained stable. What is known already: Since 1997, ART aggregated data generated by national registries, clinics or professional societies have been gathered and analyzed by the European IVF-monitoring Consortium (EIM) and communicated in a total of 20 manuscripts published in Human Reproduction and Human Reproduction Open. Study design size duration: Data on European medically assisted reproduction (MAR) are collected by EIM for ESHRE on a yearly basis. The data on treatments performed between 1 January and 31 December 2017 in 39 European countries were provided by either National Registries or registries based on personal initiatives of medical associations and scientific organizations. Participants/materials setting methods: Overall, 1382 clinics offering ART services in 39 countries reported a total of 940 503 treatment cycles, including 165 379 with IVF, 391 379 with ICSI, 271 476 with FER, 37 303 with preimplantation genetic testing (PGT), 69 378 with egg donation (ED), 378 with IVM of oocytes, and 5210 cycles with frozen oocyte replacement (FOR). A total of 1273 institutions reported data on 207 196 IUI cycles using either husband/partner's semen (IUI-H; n = 155 794) or donor semen (IUI-D; n = 51 402) in 30 countries and 25 countries, respectively. Thirteen countries reported 18 888 interventions for FP, including oocyte, ovarian tissue, semen and testicular tissue banking in pre- and postpubertal patients. Main results and the role of chance: In 21 countries (20 in 2016) in which all ART clinics reported to the registry, 473 733 treatment cycles were registered for a total population of approximately 330 million inhabitants, allowing a best-estimate of a mean of 1435 cycles performed per million inhabitants (range: 723-3286).Amongst the 39 reporting countries, the clinical PR per aspiration and per transfer in 2017 were similar to those observed in 2016 (26.8% and 34.6% vs 28.0% and 34.8%, respectively). After ICSI the corresponding rates were also similar to those achieved in 2016 (24% and 33.5% vs 25% and 33.2% in 2016). When freeze all cycles were removed, the clinical PRs per aspiration were 30.8% and 27.5% for IVF and ICSI, respectively.After FER with embryos originating from own eggs the PR per thawing was 30.2%, which is comparable to 30.9% in 2016, and with embryos originating from donated eggs it was 41.1% (41% in 2016). After ED the PR per fresh embryo transfer was 49.2% (49.4% in 2016) and per FOR 43.3% (43.6% in 2016).In IVF and ICSI together, the trend towards the transfer of fewer embryos continues with the transfer of 1, 2, 3 and ≥4 embryos in 46.0%, 49.2%, 4.5% and in 0.3% of all treatments, respectively (corresponding to 41.5%, 51.9%. 6.2% and 0.4% in 2016). This resulted in a reduced proportion of twin DRs of 14.2% (14.9% in 2016) and stable triplet DR of 0.3%. Treatments with FER in 2017 resulted in a twin and triplet DR of 11.2% and 0.2%, respectively (vs 11.9% and 0.2% in 2016).After IUI, the DRs remained similar at 8.7% after IUI-H (8.9% in 2016) and at 12.4% after IUI-D (12.4.0% in 2016). Twin and triplet DRs after IUI-H were 8.1% and 0.3%, respectively (in 2016: 8.8% and 0.3%) and 6.9% and 0.2% after IUI-D (in 2016: 7.7% and 0.4%). Amongst 18 888 FP interventions in 13 countries, cryopreservation of ejaculated sperm (n = 11 112 vs 7877 from 11 countries in 2016) and of oocytes (n = 6588 vs 4907 from eight countries in 2016) were the most frequently reported. Limitations reasons for caution: As the methods of data collection and levels of reporting vary amongst European countries, interpretation of results should remain cautious. Some countries were unable to deliver data about the number of initiated cycles and deliveries. Wider implications of the findings: The 21st ESHRE report on ART, IUI and FP interventions shows a continuous increase of reported treatment numbers and MAR-derived livebirths in Europe. Being already the largest data collection on MAR in Europe, efforts should continue to optimize data collection and reporting with the perspective of improved quality control, transparency and vigilance in the field of reproductive medicine. Study funding/competing interests: The study has received no external funding and all costs are covered by ESHRE. There are no competing interests.info:eu-repo/semantics/publishedVersio

Oocyte and ovarian tissue cryopreservation in European countries : statutory background, practice, storage and use

STUDY QUESTION: What is known in Europe about the practice of oocyte cryopreservation (OoC), in terms of current statutory background, funding conditions, indications (medical and ‘non-medical’) and specific number of cycles? SUMMARY ANSWER: Laws and conditions for OoC vary in Europe, with just over half the responding countries providing this for medical reasons with state funding, and none providing funding for ‘non-medical’ OoC. WHAT IS ALREADY KNOWN: The practice of OoC is a well-established and increasing practice in some European countries, but data gathering on storage is not homogeneous, and still sparse for use. Ovarian tissue cryopreservation (OtC) is only practiced and registered in a few countries. STUDY DESIGN, SIZE, AND DURATION: A transversal collaborative survey on OoC and OtC, was designed, based on a country questionnaire containing information on statutory or professional background and practice, as well as available data on ovarian cell and tissue collection, storage and use. It was performed between January and September 2015. PARTICIPANTS/MATERIALS, SETTING AND METHODS: All ESHRE European IVF Monitoring (EIM) consortium national coordinators were contacted, as well as members of the ESHRE committee of national representatives, and sent a questionnaire. The form included national policy and practice details, whether through current existing law or code of practice, criteria for freezing (age, health status), availability of funding and the presence of a specific register. The questionnaire also included data on both the number of OoC cycles and cryopreserved oocytes per year between 2010 and 2014, specifically for egg donation, fertility preservation for medical disease, ‘other medical’ reasons as part of an ART cycle, as well as for ‘non-medical reasons’ or age-related fertility decline. Another question concerning data on freezing and use of ovarian tissue over 5 years was added and sent after receiving the initial questionnaire. MAIN RESULTS AND THE ROLE OF CHANCE: Out of 34 EIM members, we received answers regarding OoC regulations and funding conditions from 27, whilst 17 countries had recorded data for OoC, and 12 for OtC. The specific statutory framework for OoC and OtC varies from absent to a strict frame. A total of 34 705 OoC cycles were reported during the 5-year-period, with a continuous increase. However, the accurate description of numbers was concentrated on the year 2013 because it was the most complete. In 2013, a total of 9126 aspirations involving OoC were reported from 16 countries. Among the 8885 oocyte aspirations with fully available data, the majority or 5323 cycles (59.9%) was performed for egg donation, resulting in the highest yield per cycle, with an average of 10.4 oocytes frozen per cycle. OoC indication was ‘serious disease’ such as cancer in 10.9% of cycles, other medical indications as ‘part of an ART cycle’ in 16.1%, and a non-medical reason in 13.1%. With regard to the use of OoC, the number of specifically recorded frozen oocyte replacement (FOR) cycles performed in 2013 for all medical reasons was 14 times higher than the FOR for non-medical reasons, using, respectively, 8.0 and 8.4 oocytes per cycle. Finally, 12 countries recorded storage following OtC and only 7 recorded the number of grafted frozen/thawed tissues. LIMITATIONS, REASONS FOR CAUTION: Not all countries have data regarding OoC collection, and some data came from voluntary collaborating centres, rather than a national authority or register. Furthermore, the data related to use of OoC were not included for two major players in the field, Italy and Spain, where numbers were conflated for medical and non-medical reasons. Finally, the number of cycles started with no retrieval is not available. Data are even sparser for OtC. WIDER IMPLICATIONS OF THE FINDINGS: There is a need for ART authorities and professional bodies to record precise data for practice and use of OoC (and OtC), according to indications and usage, in order to reliably inform all stakeholders including women about the efficiency of both methods. Furthermore, professional societies should establish professional standards for access to and use of OoC and OtC, and give appropriate guidance to all involved. STUDY FUNDING/COMPETING INTEREST(S): The study was supported by ESHRE. There are no conflicts of interest.peer-reviewe

ART in Europe, 2019 : results generated from European registries by ESHRE

Study question: What are the data and trends on ART and IUI cycle numbers and their outcomes, and on fertility preservation (FP) interventions, reported in 2019 as compared to previous years? Summary answer: The 23rd ESHRE report highlights the rising ART treatment cycles and children born, alongside a decline in twin deliveries owing to decreasing multiple embryo transfers; fresh IVF or ICSI cycles exhibited higher delivery rates, whereas frozen embryo transfers (FET) showed higher pregnancy rates (PRs), and reported IUI cycles decreased while maintaining stable outcomes. What is known already: ART aggregated data generated by national registries, clinics, or professional societies have been gathered and analyzed by the European IVF-Monitoring (EIM) Consortium since 1997 and reported in a total of 22 manuscripts published in Human Reproduction and Human Reproduction Open. Study design, size, duration: Data on medically assisted reproduction (MAR) from European countries are collected by EIM for ESHRE each year. The data on treatment cycles performed between 1 January and 31 December 2019 were provided by either national registries or registries based on initiatives of medical associations and scientific organizations or committed persons in one of the 44 countries that are members of the EIM Consortium. Participants/materials, setting, methods: Overall, 1487 clinics offering ART services in 40 countries reported, for the second time, a total of more than 1 million (1 077 813) treatment cycles, including 160 782 with IVF, 427 980 with ICSI, 335 744 with FET, 64 089 with preimplantation genetic testing (PGT), 82 373 with egg donation (ED), 546 with IVM of oocytes, and 6299 cycles with frozen oocyte replacement (FOR). A total of 1169 institutions reported data on IUI cycles using either husband/partner's semen (IUI-H; n = 147 711) or donor semen (IUI-D; n = 51 651) in 33 and 24 countries, respectively. Eighteen countries reported 24 139 interventions in pre- and post-pubertal patients for FP, including oocyte, ovarian tissue, semen, and testicular tissue banking. Main results and the role of chance: In 21 countries (21 in 2018) in which all ART clinics reported to the registry 476 760 treatment cycles were registered for a total population of approximately 300 million inhabitants, allowing the best estimate of a mean of 1581 cycles performed per million inhabitants (range: 437-3621). Among the reporting countries, for IVF the clinical PRs per aspiration slightly decreased while they remained similar per transfer compared to 2018 (21.8% and 34.6% versus 25.5% and 34.1%, respectively). In ICSI, the corresponding PRs showed similar trends compared to 2018 (20.2% and 33.5%, versus 22.5% and 32.1%) When freeze-all cycles were not considered for the calculations, the clinical PRs per aspiration were 28.5% (28.8% in 2018) and 26.2% (27.3% in 2018) for IVF and ICSI, respectively. After FET with embryos originating from own eggs, the PR per thawing was at 35.1% (versus 33.4% in 2018), and with embryos originating from donated eggs at 43.0% (41.8% in 2018). After ED, the PR per fresh embryo transfer was 50.5% (49.6% in 2018) and per FOR 44.8% (44.9% in 2018). In IVF and ICSI together, the trend toward the transfer of fewer embryos continues with the transfer of 1, 2, 3, and ≥4 embryos in 55.4%, 39.9%, 2.6%, and 0.2% of all treatments, respectively (corresponding to 50.7%, 45.1%, 3.9%, and 0.3% in 2018). This resulted in a reduced proportion of twin delivery rates (DRs) of 11.9% (12.4% in 2018) and a similar triplet DR of 0.3%. Treatments with FET in 2019 resulted in twin and triplet DR of 8.9% and 0.1%, respectively (versus 9.4% and 0.1% in 2018). After IUI, the DRs remained similar at 8.7% after IUI-H (8.8% in 2018) and at 12.1% after IUI-D (12.6% in 2018). Twin and triplet DRs after IUI-H were 8.7% and 0.4% (in 2018: 8.4% and 0.3%) and 6.2% and 0.2% after IUI-D (in 2018: 6.4% and 0.2%), respectively. Eighteen countries (16 in 2018) provided data on FP in a total number of 24 139 interventions (20 994 in 2018). Cryopreservation of ejaculated sperm (n = 11 592 versus n = 10 503 in 2018) and cryopreservation of oocytes (n = 10 784 versus n = 9123 in 2018) were most frequently reported. Limitations, reasons for caution: Caution with the interpretation of results should remain as data collection systems and completeness of reporting vary among European countries. Some countries were unable to deliver data about the number of initiated cycles and/or deliveries. Wider implications of the findings: The 23rd ESHRE data collection on ART, IUI, and FP interventions shows a continuous increase of reported treatment numbers and MAR-derived livebirths in Europe. Although it is the largest data collection on MAR in Europe, further efforts toward optimization of both the collection and the reporting, from the perspective of improving surveillance and vigilance in the field of reproductive medicine, are awaited. Study funding/competing interest(s): The study has received no external funding and all costs are covered by ESHRE. There are no competing interests. Keywords: ICSI; IUI; IVF; data collection; egg donation; fertility preservation; frozen embryo transfer; registry; surveillance; vigilance.peer-reviewe

Attitudes and knowledge of nurses on organ legacy and transplantation

Introduction Nurses represent an important link in mediating between the potential donors and their relatives'consent to organ and tissue transplantation.The message of the Health Department to potential donors about the importance of organ donation was supported by the Serbian Orthodox Church, the army and other institutions through media campaigns. Nurses could contribute to this action by their personal example. Objective The aim of this study was identification and bivariate analysis of nurse attitude about organ donation, their knowledge about the importance of transplantation as treatment methods, as well as the connection between work experience and education level with the formation of attitudes and new skills. Methods In this cross-sectional study, 291 nurses from the Clinical Center of Serbia, Belgrade, filled in the questionnaire on the effect of correlation between the length of the service and level of education on knowledge and attitudes toward organ transplantation and organ donation. Results Out of 291 respondents, 67.4% have completed the nursing school and 32.6% have higher education. The majority (63.9%) of respondents knew that the EEG was the most valid method for determining brain death. The question regarding the possibility of buying organs was answered correctly by 68.7% of respondents. A large majority (91%) would accept organ transplant, if needed, but only 32.0% would be organ donors, and only 0.3% owned a donor card. In contrast, one third of nurses were already blood donors. Conclusion In case of necessary transplantation, nurses would accept someone else's organ, though they do not possess donor cards, but just few would donate their organs. It is possible that prejudice arises from ignorance and distrust in the health policy of the Republic of Serbia. However, besides negative attitude, nurses have expressed interest in learning and professional development in the area of transplantation

New ferrocene containing 3-(arylthio)propan-1-ones: Synthesis, spectral characterization and crystal structure of 3-[(4-chlorophenyl)thio]-1-ferrocenylpropan-1-one, 3-[(4-chlorophenyl)thio]-1-ferrocenyl-3-phenylpropan-1-one and 3-[(4-chlorophenyl)thio]-3-ferrocenyl-1-phenylpropan-1-one

Three series of ferrocene containing 3-(arylthio)propan-1-ones (each of eight examples) have been synthesized by thia-Michael addition of the corresponding thiophenols to acryloylferrocene, 1-ferroceny1-3-phenylprop-2-en-1-one and 3-ferrocenyl-1-phenylprop-2-en-1-one promoted by the catalyst generated from a sacrificial zirconium anode. All the newly synthesized compounds (16 in total) were characterized by spectral data, whereas single crystal X-ray structure analysis was performed for 3-[(4-chlorophenyl)thio]-1-ferrocenylpropan-1-one (1h), 3-[(4-chlorophenyl)thio]-1-ferrocenyl-3-phenylpropan-1 one (2h) and 3-[(4-chlorophenyl)thio]-3-ferrocenyl-1-phenylpropan-1-one (3h). Molecular geometry and structural characteristics of three thiaketones (1h, 2h and 3h) were analysed and compared in detail. It was found that all three molecules do not form classical H-bonds and pi center dot center dot center dot pi interactions (regardless of the presence of 3 or 4 aromatic rings per a molecule). However, all three crystal structures abound in intermolecular C-H center dot center dot center dot pi interactions while 2h and 3h in addition form intramolecular C-H center dot center dot center dot pi as only evident interaction within the molecules. (C) 2013 Elsevier Ltd. All rights reserved

Anodic generation of a zirconium catalyst for Ferrier rearrangement and hetero Michael addition

An efficient catalyst for Ferrier rearrangement and hetero-Michael addition was successfully generated from a sacrificial zirconium anode into media containing reactants for these reactions. Thus, the catalyst generated, successfully promoted the allylic rearrangement of peracetylated D-glucal in the presence of a suitable S-nucleophile, giving the corresponding 2,3-unsaturated D-glucopyranose (pseudoglycal) in good to high yields. This catalyst was also shown to be capable of promoting hetero-Michael conjugate addition of S- and N-nucleophiles to the carbon-carbon double bond of methyl vinyl ketone, resulting in new carbon-sulfur and carbon-nitrogen bond formation. (C) 2012 Elsevier Ltd. All rights reserved

3-(3-Acetylanilino)-1-ferrocenylpropan-1-one

The title ferrocene-containing Mannich base, [Fe(C5H 5)(C16H16NO2)], crystallizes with two independent molecules (A and B) in the asymmetric unit. Molecules A and B have similar conformations. The dihedral angles between the best planes of the benzene and substituted cyclopentadienyl rings are 88.59 (9) and 84.39 (10)° in A and B, respectively. In the crystal, the independent molecules form centrosymmetric dimers via corresponding N - H⋯O hydrogen bonds. The dimers further arrange via C - H⋯π and C - H⋯O interactions. There are no significant interactions between the A and B molecules. © 2012 International Union of Crystallography

Antimicrobial ferrocene containing quinolinones: Synthesis, spectral, electrochemical and structural characterization of 2-ferrocenyl-2, 3-dihydroquinolin-4(1H)-one and its 6-chloro and 6-bromo derivatives

Syntheses of three new ferrocene containing heterocycles - 2-ferroceny1-2,3-dihydroquinolin-4(1H)-one and its 6-chloro and 6-bromo derivatives - starting from 2-aminoacetophenones and ferrocenecarboxaldehyde was achieved in two steps. The aldol condensation of these substrates gave the corresponding 2-aminochalcones in the first stage, whereas a further intramolecular cyclization gives the final products. This cyclization was performed by either a solvent-free microwave irradiation (500 W/5 min) of a mixture of chalcones and mortmorillonite K-10 or by using an acidic catalyst (the mixture of acetic and orthophosphoric acid). The latter method, which can be performed by simple stirring at room temperature or by irradiation in an ultrasonic bath, gave much better results. The obtained compounds were spectrally and electrochemically (cyclic voltammetry) fully characterized, as well as by single-crystal X-ray analysis. A microdilution assay revealed that the three dihydroquinolinones can be regarded as potential lead compounds in the discovery of new antimicrobial drugs due to their very strong and unselective activity towards pathogenic bacteria and one yeast with MIC values (0.01-10.0 mu/mL) lower than that of tetracycline. (C) 2011 Elsevier Ltd. All rights reserved

Synthesis of ferrocene-containing six-membered cyclic ureas via alpha-ferrocenyl carbocations

A series of ferrocene-containing six-membered cyclic ureas (1-aryl-4-ferrocenyl-3-phenyltetrahydropyrimidin-2(1H)-ones) was synthesized (in high-to-excellent yields) by reacting the corresponding amino-propanols with phenyl isocyanate and the subsequent intramolecular cyclization of the thus obtained beta-hydroxy ureas (prompted by acetic acid), via an alpha-ferrocenyl carbocation