Amino-Alcohol Organic-Inorganic Hybrid Sol-Gel Materials Based on an Epoxy Bicyclic Silane: Synthesis and Characterization.

Organic-inorganic hybrids (OIHs) are a type of material that can be obtained using the sol-gel process and has the advantages of organic and inorganic moieties in a single material. Polyetheramines have been widely used in the preparation of this type of material, particularly in combination with epoxy-based alkoxysilanes. Nevertheless, epoxyciclohexylethyltrimethoxysilane (ECHETMS) is a promising alkoxysilane with an epoxy terminal group that is quite unexplored. In this work, four novel OIH materials were synthesized using the sol-gel method. The OIHs were based on Jeffamines® of different molecular weights (D-230, D-400, ED-600, and ED-900), together with ECHETMS. The materials were characterized using multinuclear solid state NMR, FTIR, BET, UV/Vis spectroscopy, EIS, and TGA. The influence of the Jeffamine molecular weight and the suitability of these materials to act as a supporting matrix for heteroaromatic probes were assessed and discussed. The materials show interesting properties in order to be applied in a wide range of sensing applications.

The Fischer protocol for assisted reproductive technology treatment: Real-world data experience comparing elective single versus double embryo transfer with or without comprehensive chromosome screening.

High rates of multiple implantation after assisted reproductive technology (ART) treatment represent one of the major problems for both mothers and their fetuses. Given the availability of techniques intended to identify embryos with the highest chance for development to term, such as comprehensive chromosome screening (CCS) and blastocyst transfer, the decision on the number of embryos to transfer deserves careful consideration. This report presents real-life data from two clinics using the Fischer protocol for cycle programming in patients undergoing ART. Our data indicate that ovarian stimulation using the Fischer protocol provides consistent and optimal ART outcomes in centers following strict quality management standards. However, high multiple implantation rates were observed in fresh and frozen transfer cycles after transferring two embryos - even in patients aged over 39 years. The live birth rates after CCS were superior to those using untested embryos. These findings were held for the three age groups irrespective of the CCS culture day (D1 = PN stages, or D5 = blastocysts). Our results support a single embryo transfer policy, particularly in women under 34 years of age with favorable conditions during ART treatment, i.e., a high number of available fertilized oocytes.

Serum miR-181d-5p levels in response to controlled ovarian stimulation: predictive value and biological function.

The response to controlled ovarian stimulation (COS) for in vitro fertilization (IVF) varies dramatically from one patient to another, affecting success rates. A previous large-scale study identified increased serum miR-181d-5p levels in patients with high response to COS prior to stimulation. We aim to evaluate whether the expression of miR-181d-5p differs according to the ovarian response to COS in women undergoing intracytoplasmic sperm injection (ICSI) cycles. Samples collected prior to COS for ICSI were split into three groups depending on the ovarian response to COS: poor response (PR), <4 oocytes retrieved (n=25); normal response (NR), ≥8 and ≤12 oocytes retrieved (n=21); and high response (HR), >25 oocytes retrieved (n=20). miR-181d-5p serum levels were compared among experimental groups. miR-181d-5p levels were increased in the HR group when compared to the PR (p=0.0001) and NR groups (p=0.0079). miR-181d-5p levels correlated with the number of aspirated follicles (p<0.0001), retrieved oocytes (p<0.0001), and mature oocytes (p=0.0002). Increased miR-181d-5p levels independently predict a high response (p=0.006), with Positive and Negative Predictive Values of 66.7% and 69.4%, respectively. miR-181d-5p was also detected in the ovarian tissue in a mouse model. Moreover, computational analysis of miR-181d-5p predicted targets and promoter region suggested that this miRNA might be involved in the regulation of key signaling pathways and biological processes for female reproductive biology. In conclusion, miR-181d-5p is a promising circulating predictor of high stimulation and potential mediator of the hypothalamus-pituitary-gonad axis, providing opportunities for the individualization of COS protocols.

Macrophage Resistance to Ionizing Radiation Exposure Is Accompanied by Decreased Cathepsin D and Increased Transferrin Receptor 1 Expression.

PURPOSE: To identify a molecular signature of macrophages exposed to clinically relevant ionizing radiation (IR) doses, mirroring radiotherapy sessions. METHODS: Human monocyte-derived macrophages were exposed to 2 Gy/ fraction/ day for 5 days, mimicking one week of cancer patient's radiotherapy. Protein expression profile by proteomics was performed. RESULTS: A gene ontology analysis revealed that radiation-induced protein changes are associated with metabolic alterations, which were further supported by a reduction of both cellular ATP levels and glucose uptake. Most of the radiation-induced deregulated targets exhibited a decreased expression, as was the case of cathepsin D, a lysosomal protease associated with cell death, which was validated by Western blot. We also found that irradiated macrophages exhibited an increased expression of the transferrin receptor 1 (TfR1), which is responsible for the uptake of transferrin-bound iron. TfR1 upregulation was also found in tumor-associated mouse macrophages upon tumor irradiation. In vitro irradiated macrophages also presented a trend for increased divalent metal transporter 1 (DMT1), which transports iron from the endosome to the cytosol, and a significant increase in iron release. CONCLUSIONS: Irradiated macrophages present lower ATP levels and glucose uptake, and exhibit decreased cathepsin D expression, while increasing TfR1 expression and altering iron metabolism.

Hybrid Sol-Gel Matrices Doped with Colorimetric/Fluorimetric Imidazole Derivatives.

Organic-inorganic hybrids (OIH) are materials that can be easily synthesized by the sol-gel method and combine the advantages of organic and inorganic moieties within a single polymeric matrix. Imidazole derivatives are versatile organic compounds that can change their optical properties with the variation of pH due to the protonation or deprotonation of the nitrogen atoms. This work reports the preparation of different OIHs doped with different contents of two imidazole compounds (3a,b). The obtained materials were characterized structurally by FTIR, and the dielectric properties were studied by electrochemical impedance spectroscopy. The optical properties were studied by UV-Vis absorption and fluorescence spectroscopies. The FTIR analysis showed that the presence of the imidazole does not change the structural properties of the matrices. The normalized resistance values obtained for the doped matrices ranged between 8.57 and 9.32 Ω cm2, all being higher than the undoped matrix. The σ ranged between 9.49 and 10.28 S cm-1, being all higher than the pure OIH samples. Compound 3a showed a maximum absorption peak at 390 nm, which is present in the OIH spectra, proving the presence of the compound. In the case of compound 3b, a maximum absorption wavelength at 412 nm was found, and the compound peak was not clear, which may indicate that an interaction between the compound and the matrix occurred. A synergetic effect between the intrinsic emission of the matrix and the fluorescence of 3a is found on the OIH-doped matrices.

Organic-inorganic hybrid sol-gel materials doped with a fluorescent triarylimidazole derivative.

The development of sensors for pH monitoring is of extreme importance in the monitoring of concrete and reinforced concrete structures. Imidazole derivatives are promising probes for pH sensing due to the amphoteric nature of their heterocyclic ring, which can be protonated/deprotonated upon pH changes. In this work, a triarylimidazole was synthesised and used as a dopant in an organic-inorganic hybrid (OIH) sol-gel matrix to obtain a pH-sensitive membrane for further application in optical fibre sensors (OFS). The triarylimidazole probe shows fluorimetric response in pH between 9 and 13, which is the desired range for monitoring carbonation of concrete. This degradation process lowers the highly alkaline pH of concrete (12.5-13) to values below 9, which creates favourable conditions for corrosion of concrete reinforcement. The OIH membranes used were based on Jeffamine THF170 and 3-glycidoxypropytrimethoxysilane precursors, which had already been shown to be suitable and resistant in contact with cement-based materials. The OIHs were doped with three different contents of the triarylimidazole and the structural, dielectric, thermal and optical properties of the pure and doped OIH materials were evaluated. The structural analysis showed that the presence of the triarylimidazole did not change the structural properties of the OIH material. Electrochemical impedance spectroscopy showed that in the doped samples the conductivity increased with the imidazole concentration. The ε r obtained for the doped samples ranged approximately from 11 to 19 and for the pure matrices was 8. Thermal analysis showed that these materials are stable up to 350 °C and that the presence of the probe did not change that feature. The optical properties showed that the prepared OIH materials have promising properties to be used as pH sensitive fluorimetric probes.

SARS-CoV-2 pandemic and repercussions for male infertility patients: A proposal for the individualized provision of andrological services.

The prolonged lockdown of health facilities providing non-urgent gamete cryopreservation-as currently recommended by many reproductive medicine entities and regulatory authorities due to the SARS-CoV-2 pandemic will be detrimental for subgroups of male infertility patients. We believe the existing recommendations should be promptly modified and propose that the same permissive approach for sperm banking granted for men with cancer is expanded to other groups of vulnerable patients. These groups include infertility patients (eg, azoospermic and cryptozoospermic) undergoing medical or surgical treatment to improve sperm quantity and quality, as well as males of reproductive age affected by inflammatory and systemic auto-immune diseases who are about to start treatment with gonadotoxic drugs or who are under remission. In both scenarios, the "fertility window" may be transitory; postponing diagnostic semen analysis and sperm banking in these men could compromise the prospects of biological parenthood. Moreover, we provide recommendations on how to continue the provision of andrological services in a considered manner and a safe environment. Our opinion is timely and relevant given the fact that fertility services are currently rated as of low priority in most countries.

Optical Fiber Sensors for Biocide Monitoring: Examples, Transduction Materials, and Prospects.

Antifouling biocides are toxic to the marine environment impacting negatively on the aquatic ecosystems. These biocides, namely, tributyltin (TBT) and Cu(I) compounds, are used to avoid biofouling; however, their toxicity turns TBT and Cu(I) monitoring an important health issue. Current monitoring methods are expensive and time-consuming. This review provides an overview of the actual state of the art of antifouling paints' biocides, including their impact and toxicity, as well as the reported methods for TBT and Cu(I) detection over the past decade. The principles of optical fiber sensors (OFS) applications, with focus on environmental applications, and the use of organic chemosensors in this type of sensors are debated. The multiplexing ability of OFS and their application on aquatic environments are also discussed.

Synthesis, Optical and Electrical Characterization of Amino-alcohol Based Sol-gel Hybrid Materials.

This manuscript describes the synthesis and characterization of five new organic-inorganic hybrid (OIH) sol-gel materials that were obtained from a functionalized siloxane 3-glycidoxypropyltrimethoxysilane (GPTMS) by the reaction with the new Jeffamine®, namely three different diamines, i.e., EDR-148, RFD-270, and THF-170, a secondary diamine, i.e., SD-2001, and a triamine, i.e., T-403. The OIH sol-gel materials were characterized by UV-visible absorption spectrophotometry, steady-state photoluminescence spectroscopy, and electrochemical impedance spectroscopy. The reported OIH sol-gel materials showed that, with the exception of the samples prepared with Jeffamine® SD-2001, the transmittance values ranged between 61% and 79%. Regarding the capacitance data, the values reported changed between 0.008 and 0.013 nF cm-2. Due to their optical and electrical properties these new OIH materials show promising properties for applications as support films in an optical sensor area such as fiber sensor devices. Studies to assess the chemical stability of the OIH materials in contact with cement pastes after 7, 14, and 28 days were also performed. The samples prepared with THF-170 and GPTMS, when compared to the samples prepared with RFD-270 and T-403, exhibited improved behavior in the cement paste (alkaline environment), showing promising properties for application as support film in optical fiber sensors in the civil engineering field.

Hybrid Sol-gel Coatings for Corrosion Mitigation: A Critical Review.

The corrosion process is a major source of metallic material degradation, particularly in aggressive environments, such as marine ones. Corrosion progression affects the service life of a given metallic structure, which may end in structural failure, leakage, product loss and environmental pollution linked to large financial costs. According to NACE, the annual cost of corrosion worldwide was estimated, in 2016, to be around 3%-4% of the world's gross domestic product. Therefore, the use of methodologies for corrosion mitigation are extremely important. The approaches used can be passive or active. A passive approach is preventive and may be achieved by emplacing a barrier layer, such as a coating that hinders the contact of the metallic substrate with the aggressive environment. An active approach is generally employed when the corrosion is set in. That seeks to reduce the corrosion rate when the protective barrier is already damaged and the aggressive species (i.e., corrosive agents) are in contact with the metallic substrate. In this case, this is more a remediation methodology than a preventive action, such as the use of coatings. The sol-gel synthesis process, over the past few decades, gained remarkable importance in diverse areas of application. Sol-gel allows the combination of inorganic and organic materials in a single-phase and has led to the development of organic-inorganic hybrid (OIH) coatings for several applications, including for corrosion mitigation. This manuscript succinctly reviews the fundamentals of sol-gel concepts and the parameters that influence the processing techniques. The state-of-the-art of the OIH sol-gel coatings reported in the last few years for corrosion protection, are also assessed. Lastly, a brief perspective on the limitations, standing challenges and future perspectives of the field are critically discussed.

PDMS Based Hybrid Sol-Gel Materials for Sensing Applications in Alkaline Environments: Synthesis and Characterization.

Nowadays, concrete degradation is a major problem in the civil engineering field. Concrete carbonation, one of the main sources of structures' degradation, causes concrete's pH to decrease; hence, enabling the necessary conditions for corrosion reinforcement. An accurate, non-destructive sensor able to monitor the pH decrease resistant to concrete conditions is envisaged by many researchers. Optical fibre sensors (OFS) are generally used for concrete applications due to their high sensitivity and resistance to external interferences. Organic-inorganic hybrid (OIH) films, for potential functionalization of OFS to be applied in concrete structures, were developed. Polydimethylsiloxane (PDMS) based sol-gel materials were synthesized by the formation of an amino alcohol precursor followed by hydrolysis and condensation. Different ratios between PDMS and (3-aminopropyl)triethoxysilane (3-APTES) were studied. The synthesized OIH films were characterized by Fourier-transformed infrared spectroscopy (FTIR), UV-Vis spectroscopy, electrochemical impedance spectroscopy (EIS) and thermogravimetric analysis (TGA). The OIH films were doped with phenolphthalein (Phph), a pH indicator, and were characterized by UV-Vis and EIS. FTIR characterization showed that the reaction between both precursors, the hydrolysis and the condensation reactions occurred successfully. UV-Vis characterization confirmed the presence of Phph embedded in the OIH matrices. Dielectric and thermal properties of the materials showed promising properties for application in contact with a high alkaline environment.

IMRT national audit in Portugal.

PURPOSE: The IAEA newly developed "end-to-end" audit methodology for on-site verification of IMRT dose delivery has been carried out in Portugal in 2018. The main goal was to evaluate the physical aspects of the head and neck (H&N) cancer IMRT treatments. This paper presents the national results. METHODS: All institutions performing IMRT treatments in Portugal, 20 out of 24, have voluntarily participated in this audit. Following the adopted methodology, a Shoulder, Head and Neck End-to-End phantom (SHANE) - that mimics an H&N region, underwent all steps of an IMRT treatment, according to the local practices. The measurements using an ionization chamber placed inside the SHANE phantom at four reference locations (three in PTVs and one in the spinal cord) and an EBT3 film positioned in a coronal plane were compared with calculated doses. FilmQA Pro software was used for film analysis. RESULTS: For ionization chamber measurements, the percent difference was within the specified tolerances of ±5% for PTVs and ±7% for the spinal cord in all participating institutions. Considering film analysis, gamma passing rates were on average 96.9%±2.9% for a criterion of 3%/3 mm, 20% threshold, all above the acceptance limit of 90%. CONCLUSIONS: The national results of the H&N IMRT audit showed a compliance between the planned and the delivered doses within the specified tolerances, confirming no major reasons for concern. At the same time the audit identified factors that contributed to increased uncertainties in the IMRT dose delivery in some institutions resulting in recommendations for quality improvement.

Serum metabolites as predictive molecular markers of ovarian response to controlled stimulation: a pilot study.

OBJECTIVE: This study aimed to look into the use of serum metabolites as potential biomarkers of response to controlled ovarian stimulation (COS) in patients undergoing intracytoplasmic sperm injection (ICSI) cycles. METHODS: This case-control study analyzed serum samples from 30 patients aged <36 years undergoing COS for ICSI in a university-affiliated assisted reproduction center from January 2017 to August 2017. The samples were split into three groups based on response to COS as follows: poor responders: <4 retrieved oocytes (PR group, n=10); normal responders: ≥ 8 and ≤ 12 retrieved oocytes (NR group, n=10); and hyper-responders: >25 retrieved oocytes (HR, n=10). The metabolic profiles of the serum samples were compared between the groups through Principal Component Analysis (PCA). Receiver Operating Characteristic (ROC) curves were built to assess the power of the model at predicting response to COS. RESULTS: PCA clearly distinguished between PR, NR and HR, and 10 ions were chosen as potential biomarkers of response to COS. These ions were more specific for PR than for NR. The ROC curve considering PR and NR had an area under the curve of 99.6% (95% CI: 88.9 - 100%). CONCLUSION: The preliminary evidence discussed in this study suggests that serum metabolites may be used as predictive molecular markers of ovarian response to controlled stimulation. The integration of clinical and "omics" findings may allow the migration toward an era of personalized treatment in reproductive medicine.

Ovarian response to stimulation and suboptimal endometrial development are associated with adverse perinatal outcomes in intracytoplasmic sperm injection cycles.

OBJECTIVE: To study which factors affect perinatal outcomes in intracytoplasmic sperm injection (ICSI) cycles. METHODS: Data was obtained from 402 live births born to 307 patients undergoing ICSI cycles in a private university-affiliated IVF center between Jan/2014 and Dec/2015. The influences of the cycles' characteristics on the number of gestational weeks to livebirth (GW), baby birth weight (BW), and baby birth length (BL) were evaluated by linear regression models, adjusted for maternal age and body mass index, number of transferred embryos, number of gestational sacs, and number of born infants. In a subsequent analysis, GW, BW and baby sex were utilized for cycle classification into the groups Appropriate for gestational age (AGA n=256) and Small for gestational age (SGA n=146), which were compared by general linear models adjusted for the same confounder variables. RESULTS: The number of follicles (ß=-0.069 p=0.018) and retrieved oocytes (ß=-0.087 p=0.049) were negatively correlated with BL. The endometrial thickness was positively correlated with GW (ß=0.198 p=0.003) and BW (ß=28.351 p=0.044). When each baby was classified into AGA and SGA groups, it was observed that SGA babies were derived from cycles with higher estradiol levels at hCG day (SGA: 3897.01±550.35 vs. AGA: 2324.78±101.86 p=0.006) and higher number of retrieved oocytes (SGA: 16.70±1.78 vs. AGA: 12.92±0.42 p=0.042). The endometrial thickness was significantly lower in the SGA group (SGA: 10.2±0.23 vs. AGA: 11.68±0.17 vs. p=0.029). CONCLUSION: Higher ovarian response to stimulation and suboptimal endometrial development are associated with adverse perinatal outcomes in ICSI cycles.

Preimplantation genetic testing for monogenic diseases: a Brazilian IVF centre experience.

OBJECTIVE: To describe the cases of preimplantation genetic testing for monogenic diseases (PGT-M) in fertile couples who had undergone intracytoplasmic sperm injection (ICSI) cycles in a Brazilian in vitro fertilisation (IVF) centre and determine whether these cases were different from those reported from the European Society of Human Reproduction and Embryology (ESHRE). METHODS: This retrospective collection included data obtained from ICSI-PGT-M cycles between 2011 and 2016. The disease indication, number of biopsied embryos, biopsy stage, diagnosed and affected embryos, and cycles with embryo to transfer as well as implantation, pregnancy and miscarriage rates were analysed and compared to cycles without genetic diagnosis (PGT) and with ESHRE PGD Consortium collection XIV-XV. RESULTS: From 5,070 cycles performed, 72 had indications for PGT-M. The most common time for biopsy was cleavage-stage; 93% of the embryos had a diagnostic result, 59.4% of which were genetically transferable, resulting in 68% of the cycles with transferred embryos, a 22.1% implantation rate, and a 28.6% pregnancy rate. No differences in clinical outcomes of cycles with PGT-M or without PGT were observed. The day of biopsy and diagnostic success as well as implantation, pregnancy and miscarriage rates were similar to ESHRE collection. CONCLUSIONS: Although the proportion of cases with PGT-M was low, its efficacy was similar to what was reported in the European collection and represents a viable alternative for families at risk of transmitting a genetic disorder to their offspring. The main difference between our and ESHRE collection were the disease indications, which reflected the admixed, multi-ethnic Brazilian population.

Lipidomic profile as a noninvasive tool to predict endometrial receptivity.

For the present study we asked whether the endometrial fluid lipidomic may be a useful approach to predict endometrial receptivity in freeze-all cycles. For this case-control study, endometrial fluid samples were collected from 41 patients undergoing freeze-all cycles. Samples were split depending on the pregnancy outcome: positive group (n = 24) and negative group (n = 17). Data were acquired by the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were applied. A list of potential biomarker ion ratios was obtained and the values were used to build a receiver operating characteristic (ROC) curve to predict pregnancy success. The lipid categories were attributed by LIPID MAPS database. Ion ratios were established according to their correlations and used for the analysis. The PCA showed a tendency of separation between the studied groups, whereas the PLS-DA was able to clearly distinguish them. Fifteen ratios (13 hyper-represented in the negative and two hyper-represented in the positive group) were selected according to their importance for model prediction. These ratios were used to build the ROC curve, which presented an area under curve of 84.0% (95%CI: 69.2-97.4%; p = 0.009). These findings suggest that lipidomic profiling of endometrial fluid may be a valuable tool for identifying the time interval comprising the window of implantation.

Association between parental anthropometric measures and the outcomes of intracytoplasmic sperm injection cycles.

PURPOSE: To study the association between body mass index (BMI), waist circumference (WC), waist-to-hip ratio (WHR), and waist-to-height ratio (WHtR), and response to controlled ovarian stimulation, semen quality, and intracytoplasmic sperm injection (ICSI) outcomes. METHODS: This prospective observational study included data from 402 couples undergoing ICSI between January/2010-September/2016. Participants had their weight, height, waist, and hip measured before ICSI treatment. RESULTS: Gonadotropin dose was positively associated with maternal WHR. Maternal WC and WHR negatively influenced the estradiol level, number of follicles, oocytes, and mature oocytes. Maternal BMI negatively influenced oocyte yield. Semen volume was negatively influenced by male BMI. Sperm concentration was negatively associated with WHR and WHtR. Progressive sperm motility was negatively influenced by all anthropometric measures (AMs). The TMSC was negatively affected by all AM but WC. Significant differences were observed in all ICSI outcomes except pregnancy and miscarriage rates, favoring women with AM below the cut off values compared to women above the cut off. It was observed that men with AM below the cut off values showed significantly higher rates of fertilization, embryo and blastocyst development, implantation, and pregnancy than men above the cut off. When combined maternal and paternal AM were analyzed, significant differences were observed in fertilization, embryo and blastocyst development and implantation rates, favoring couples with normal BMI, WC, and WHR. CONCLUSIONS: Lower AMs have a protective effect on fertility. Awareness and counseling on how to minimize its impact in both partners could improve ICSI outcomes.

Role of religion, spirituality, and faith in assisted reproduction.

Purpose: The purpose of this study is to evaluate the impact of the patient's faith, religion, and spirituality on the outcomes of intracytoplasmic sperm injection (ICSI) cycles. Materials and methods: Eight hundred and seventy-seven patients received a questionnaire containing information on faith, religiosity, and spirituality and the results of the questionnaires were correlated with ICSI outcomes. Patients stated to be Catholic (n = 476), spiritists (n = 93), Evangelical (n = 118), and other religion (n = 32), and 78 did not identify with any religious group. Results: A significant increase in fertilization, high-quality embryos, and pregnancy rate was found among Spiritists and Evangelicals. Patients who included the infertility diagnosis and treatment in their prayers showed an increased pregnancy rate, and those who reported their faith to be affected by the infertility diagnosis presented a decreased high-quality embryos rate. The high-quality embryos rate was increased among patients who answered that their faith contributed to their decision to undergo infertility treatment. The cycle's cancelation was negatively correlated with the frequency of religious meetings, and the frequency of prayers was positively correlated with the response to ovarian stimulation. Finally, belief in treatment success positively influenced the embryo quality. Conclusion: The findings suggest that spirituality plays a role in adjusting the psychological aspects of an infertile patient.