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Excited state dynamics of three iron(II) carbene complexes that serve as prototype Earth-abundant photosensitizers were investigated by ultrafast optical spectroscopy. Significant differences in the dynamics between the investigated complexes down to femtosecond time scales are used to characterize fundamental differences in the depopulation of triplet metal-to-ligand charge-transfer ( 3 MLCT) excited states in the presence of energetically accessible triplet metal-centered ( 3 MC) states. Novel insights into the full deactivation cascades of the investigated complexes include evidence of the need to revise the deactivation model for a prominent iron carbene prototype complex, a refined understanding of complex 3 MC dynamics, and a quantitative discrimination between activated and barrierless deactivation steps along the 3 MLCT → 3 MC → 1 GS path. Overall, the study provides an improved understanding of photophysical limitations and opportunities for the use of iron(II)-based photosensitizers in photochemical applications.

The aim of this study is to investigate the influence of polymer chemistry on the properties of oral dosage forms produced using selective laser sintering (SLS). The dosage forms were printed using different grades of polyvinyl alcohol or copovidone in combination with indomethacin as the active pharmaceutical ingredient. The properties of the printed structures were assessed according to European Pharmacopoeia guidelines at different printing temperatures and laser scanning speeds in order to determine the suitable printing parameters. The results of the study indicate that the chemical properties of the polymers, such as dynamic viscosity, degree of hydrolyzation, and molecular weight, have significant impact on drug release and kinetics. Drug release rate and supersaturation can be modulated by selecting the appropriate polymer type. Furthermore, the physical properties of the dosage forms printed under the same settings are influenced by the selected polymer type, which determines the ideal manufacturing settings. This study demonstrates how the chemical properties of the polymer can determine the appropriate choice of manufacturing settings and the final properties of oral dosage forms produced using SLS., Competing Interests: Jonas Lindh reports financial support was provided by Sweden's Innovation Agency. Maria Stromme reports financial support was provided by Swedish Research Council. Jonas Lindh reports financial support was provided by Merck KGaA. Maria Stromme reports financial support was provided by Erling Persson Family Foundation., (© 2023 Published by Elsevier B.V.)

Steady state and ultrafast spectroscopy on [Fe III (phtmeimb) 2 ]PF 6 (phtmeimb = phenyl(tris(3-methylimidazol-2-ylidene))borate) was performed over a broad range of temperatures. The intramolecular deactivation dynamics of the luminescent doublet ligand-to-metal charge-transfer ( 2 LMCT) state was established based on Arrhenius analysis, indicating the direct deactivation of the 2 LMCT state to the doublet ground state as a key limitation to the lifetime. In selected solvent environments photoinduced disproportionation generating short-lived Fe(iv) and Fe(ii) complex pairs that subsequently undergo bimolecular recombination was observed. The forward charge separation process is found to be temperature-independent with a rate of ∼1 ps -1 . Subsequent charge recombination takes place in the inverted Marcus region with an effective barrier of 60 meV (483 cm -1 ). Overall, the photoinduced intermolecular charge separation efficiently outcompetes the intramolecular deactivation over a broad range of temperatures, highlighting the potential of [Fe III (phtmeimb) 2 ]PF 6 to perform photocatalytic bimolecular reactions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A new generation of octahedral iron(ii)-N-heterocyclic carbene (NHC) complexes, employing different tridentate C^N^C ligands, has been designed and synthesized as earth-abundant photosensitizers for dye sensitized solar cells (DSSCs) and related solar energy conversion applications. This work introduces a linearly aligned push-pull design principle that reaches from the ligand having nitrogen-based electron donors, over the Fe(ii) centre, to the ligand having an electron withdrawing carboxylic acid anchor group. A combination of spectroscopy, electrochemistry, and quantum chemical calculations demonstrate the improved molecular excited state properties in terms of a broader absorption spectrum compared to the reference complex, as well as directional charge-transfer displacement of the lowest excited state towards the semiconductor substrate in accordance with the push-pull design. Prototype DSSCs based on one of the new Fe NHC photosensitizers demonstrate a power conversion efficiency exceeding 1% already for a basic DSSC set-up using only the I - /I 3 - redox mediator and standard operating conditions, outcompeting the corresponding DSSC based on the homoleptic reference complex. Transient photovoltage measurements confirmed that adding the co-sensitizer chenodeoxycholic acid helped in improving the efficiency by increasing the electron lifetime in TiO 2 . Time-resolved spectroscopy revealed spectral signatures for successful ultrafast (<100 fs) interfacial electron injection from the heteroleptic dyes to TiO 2 . However, an ultrafast recombination process results in undesirable fast charge recombination from TiO 2 back to the oxidized dye, leaving only 5-10% of the initially excited dyes available to contribute to a current in the DSSC. On slower timescales, time-resolved spectroscopy also found that the recombination dynamics (longer than 40 μs) were significantly slower than the regeneration of the oxidized dye by the redox mediator (6-8 μs). Therefore it is the ultrafast recombination down to fs-timescales, between the oxidized dye and the injected electron, that remains as one of the main bottlenecks to be targeted for achieving further improved solar energy conversion efficiencies in future work., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In humans and dogs, a temporal decline in semen quality and increased incidence of testicular cancer is hypothesised to be associated with exposure to anthropogenic chemicals, particularly during fetal development. Human studies suggest that differential exposures to environmental chemicals may be associated with geographical differences in male reproductive health. Here we investigate testicular chemical profiles and pathologies in dogs residing in the UK [West Midlands (WM), East Midlands (EM), South East (SE)], Denmark (Copenhagen) and Finland (Vantaa). Testes, surplus from routine castrations, contained region specific differences in relative concentrations of diethylhexyl phthalate (DEHP), polybrominated diphenyl ethers (PBDE) and polychlorinated biphenyls (PCB). Relative to UK regions, testes from dogs living in Finland and Denmark had higher concentrations of PBDE and lower concentrations of DEHP and PCBs. Regional differences in the UK in PCB concentrations were also observed. Dog testes from Finland had fewer pathologies, reduced testicular area stained for Sertoli and germ cells and evidence of reduced cellular proliferation. Since the geographical differences in testis pathologies in dogs parallel reports of regional differences in human testicular cancer, we postulate that this may reflect chemical effects within the testis and that this may be related to environmental influences on male reproductive function.

The aim of this study was to compare the clinical outcomes of implant-supported overdentures (ODs) with either bar-clip or ball attachments. The implant, prosthesis failure, and technical complications were the outcomes analyzed in this retrospective clinical study conducted in a specialty clinic. Seventy-five patients with 242 implants supported by 76 ODs (36 maxillary, 40 mandibular) were included in the study and followed up for 88.8 ± 82.9 months (mean ± standard deviation). Bar-clip and ball attachments were used in 78.9% and 21.1% of the cases, respectively. Forty-three implant failures (17.8%) in 17 prostheses (17/76; 22.4%) were observed in this study. The average period of implant failure was 43.3 ± 41.0 months, and most of them were maxillary turned implants. The bar-clip system demonstrated more complications in the attachment parts compared to the ball attachment system. Poor retention of the prosthesis was similar between the two systems. Loss of implants resulted in the failure of 10 ODs in this study. ODs opposed by natural dentition or fixed prostheses presented with more complications. The Cox proportional hazards model did not show a significant effect on prosthesis failure for any of the factors. These findings indicated that patients with ODs need constant maintenance follow-ups to address the technical complications and perform prosthodontic maintenance regardless of the attachment system used.

The feral pig populations of many countries continue to increase. Scientific studies on population size are scarce, while the numbers of reported observations on presence of and damage caused by feral pigs are increasing. Feral pigs can carry and spread several diseases (including zoonotic), but African Swine Fever (ASF) is of most concern. It is a highly transmissible viral disease associated with an extremely high mortality rate. Since 2009 ASF has appeared in several European countries, with cases being identified first among local feral pigs and consequently in domestic pig production units, indicating a clear linkage with the movement of the feral pig population and the spread of the disease across national boundaries. Control of feral pig populations is currently under discussion. Because massive culling raises questions of animal welfare and ethics, fertility control could represent an important and effective means to control feral pig populations. Contraceptive vaccines have been used with some degree of success in many wild species because they are able to provide a long-term effect without any consequent health problems. However, extensive and efficacious use of vaccines to control feral pig populations is not simple. The aim of this article was to review the progress in immunocontraception use in feral pigs, providing an account of the current status and future perspectives., (© The Author(s) 2019. Published by Oxford University Press on behalf of the American Society of Animal Science. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

The aims of the study were to characterize a nanostructured photoactive titanium dioxide (TiO(2)) coating and to compare the cellular response of human osteoblasts before and after ultraviolet (UV) irradiation of the coating. A specific nanostructured TiO(2) powder (Degussa P-25), which consists of approximately 80% anatase and 20% rutile, was spin-coated onto commercially pure titanium discs, and was heat-treated thereafter. After topographical, chemical and photocatalytic property characterizations, human osteoblasts were cultured on the coated discs before and after UV irradiation. Cell morphology was evaluated by scanning electron microscopy (SEM), and cell viability was analysed by 3-(4,5-dimethylthiazol)-2,5-diphenyltetrazolium bromide (MTT) assay. From the contact angle analysis, the wettability significantly improved after UV irradiation. The cultured cells were flattened with numerous elongated lammellipodia; however, no morphological differences were indicated between -UV and +UV surfaces. The MTT assay analysis showed that -UV surface presented significantly higher viability compared to the +UV surface except for one cell population group at 3h where there were no differences. The nanostructured photoactive TiO(2) surface improved its hydrophilicity by UV irradiation, however no enhancing effect in cell response was confirmed at the time tested compared to the non-irradiated surface., (Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Objective: To evaluate the efficacy and safety of an intraoral electrostimulation device, consisting of stimulating electrodes, an electronic circuit, and a power source, in treating xerostomia. The device delivers electrostimulation through the oral mucosa to the lingual nerve in order to enhance the salivary reflex., Methods: The device was tested on a sample of patients with xerostomia due to Sjögren's syndrome and other sicca conditions in a 2-stage prospective, randomized, multicenter trial. Stage I was a double-blind, crossover stage designed to compare the effects of the electrically active device with the sham device, each used for 1 month, and stage II was a 3-month open-label stage designed to assess the long-term effects of the active device. Improvement in xerostomia severity from baseline was the primary outcome measure., Results: A total of 114 patients were randomized. In stage I, the active device performed better than the sham device for patient-reported xerostomia severity (P<0.002), xerostomia frequency (P<0.05), quality of life impairment (P<0.01), and swallowing difficulty (P<0.02). At the end of stage II, statistically significant improvements were verified for patient-reported xerostomia severity (P<0.0001), xerostomia frequency (P<0.0001), oral discomfort (P<0.001), speech difficulty (P<0.02), sleeping difficulty (P<0.001), and resting salivary flow rate (P<0.01)., Conclusion: Our findings indicate that daily use of the device alleviated oral dryness, discomfort, and some complications of xerostomia, such as speech and sleeping difficulties, and increased salivary output. The results show a cumulative positive effect of the device over the period of the study, from baseline to the end of the trial.

Adsorption of small pellicle proteins statherin or proline-rich protein 1 (PRP1), respectively, and subsequent adsorption of human whole saliva (HWS) or salivary mucin MUC5B, respectively, was studied using ellipsometry and total internal reflectance fluorescence. Differences in elution (using sodium dodecyl sulphate (SDS) solutions) between mixed and single protein films were also investigated. On both hydrophilic and hydrophobized surfaces HWS and MUC5B were found to adsorb to pre-adsorbed layers of statherin and PRP1, respectively. Statherin adsorption on both substrate types showed no or minor exchange by HWS or MUC5B and no change in SDS elution between mixed and single protein films. Small amounts of PRP1 were exchanged by HWS on both surface types and the SDS elutable fractions were similar or larger for mixed films compared to single protein films. PRP1 and MUC5B in sequence showed minor exchange of PRP1 on hydrophilic surfaces, while no exchange could be established on hydrophobized substrates. SDS elutable fractions decreased for PRP1 and MUC5B mixed films compared to single protein films. In conclusion, minor amounts of statherin and PRP1 are exchanged during the time course of the experiments, which indicates that these proteins may to a large extent remain incorporated in the pellicle.

The salivary protein statherin is known to adsorb selectively onto hydroxyapatite (HA), which constitutes the main mineral of the tooth enamel. This adsorption is believed to be crucial for its function as an inhibitor of primary (spontaneous) and secondary (crystal growth) precipitation of calcium phosphate salts present in saliva. A fragment corresponding to the first 21 N-terminus amino acids of statherin (StN21) was previously found to reduce the rate of demineralization of HA. Therefore, the interfacial properties of this peptide and statherin onto silica, hydrophobized silica and HA discs was studied by in situ ellipsometry. Their reversibility induced by dilution and elutability induced by buffer and sodium dodecyl sulfate (SDS) was also determined. The results revealed that statherin adsorbed at a greater extent onto the HA as compared to StN21, suggesting that the hydrogen bonding between the uncharged polar residues at the C-terminal region of statherin and HA contributes to its adsorption. However, on both silica surfaces the peptide adsorption appeared to proceed in a similar way. Onto the hydrophobized silica the adsorption of both peptides was suggested to occur either via multilayer formation or adsorption of aggregates from solution, while onto the hydrophilic silica adsorption of peptide aggregates from solution was the suggested mechanism. Further, both peptides were observed to be strongly adsorbed onto HA, even after SDS treatment, in comparison to the layers adsorbed onto hydrophobized silica. Both peptide layers were found to be weakly adsorbed onto the hydrophilic silica surface as they were totally removed by buffer dilution.

In situ ellipsometry was used to study layer-by-layer film formation on hydrophilic and hydrophobized silica surfaces by alternating sequential adsorption of human mucin MUC5B and cationic proteins lysozyme, lactoferrin, lactoperoxidase or histatin 5, respectively. The stability of the multilayers was investigated by addition of sodium dodecyl sulfate solution (SDS). Atomic force microscopy was employed to investigate morphological structures on the surfaces during the layer-by-layer film build-up. It was clearly shown that, on both hydrophilic and hydrophobized silica, only MUC5B and lactoperoxidase showed the ability for multilayer formation, resulting in an approximately linear increase in adsorbed amount and film thickness with each deposition cycle. The net increase in amounts per cycle was larger on the hydrophilic silica. Further, MUC5B needs to be adsorbed first on the hydrophilic substrates to obtain this fast build-up behavior. Generally, addition of SDS solution showed that a large fraction of the adsorbed film could be desorbed. However, films on the hydrophobized silica were more resistant to surfactant elution. In conclusion, MUC5B-cationic protein multilayers can be formed on hydrophilic and hydrophobized silica, depending on the choice of the cationic protein as well as in which order the build-up is started on hydrophilic silica. Additionally, SDS disrupts the layer-by-layer film formed by MUC5B and lactoperoxidase.

Adsorption of the cationic salivary proteins lactoferrin, lactoperoxidase, lysozyme and histatin 5 to pure (hydrophilic) and methylated (hydrophobized) silica surfaces was investigated by in situ ellipsometry. Effects of concentration (/=lactoperoxidase>lysozyme>/=histatin 5. On hydrophilic silica, the adsorption was most likely driven by electrostatic interactions, which resulted in adsorbed amounts of lactoferrin that indicated the formation of a monolayer with both side-on and end-on adsorbed molecules. For lactoperoxidase the adsorbed amounts were somewhat higher than an end-on monolayer, lysozyme adsorption showed amounts corresponding to a side-on monolayer, and histatin 5 displayed adsorbed amounts in the range of a side-on monolayer. On hydrophobized substrata, the adsorption was also mediated by hydrophobic interactions, which resulted in lower adsorbed amounts of lactoferrin and lactoperoxidase; closer to side-on monolayer coverage. For both lysozyme and histatin 5 the adsorbed amounts were the same as on the hydrophilic silica. The investigated proteins exhibited fast adsorption kinetics, and the initial kinetics indicated mass transport controlled behaviour at low concentrations on both types of substrates. Buffer rinsing and SDS elution indicated that the proteins in general were more tightly bound to the hydrophobized surface compared to hydrophilic silica. Overall, the surface activity of the investigated proteins implicates their importance in the salivary film formation.

Bovine submaxillary mucin (BSM) and chitosan were used to build layer-by-layer structures on solid substrates. The build-up was monitored using in situ ellipsometry to obtain time resolved values of the thickness and adsorbed amount. Additionally surface morphology during build-up was studied by atomic force microscopy (AFM). It was found that the adsorbed amount of the film increases approximately linearly with each deposition cycle on hydrophobized silica whereas construction on silica was found not to be possible at the experimental conditions used. We conclude that sufficient amount of the first mucin layer is crucial for the subsequent multilayer formation. The complex build-up kinetics on hydrophobized silica is characterized by adsorption and redissolution processes and the overall growth is the sum of both processes. AFM imaging on hydrophobized silica also confirmed the presence of redissolution processes and chitosan addition led to a reduction both in the number of surface aggregates and in the roughness of the surface. The present work also shows that by adjusting the relative concentrations of the polyelectrolytes it is possible to change the growth rate considerably. The final structures after deposition of 8 bilayers were found to have a high content of water and film stability test revealed that a substantial amount dissolves when increasing electrolyte concentration or pH of the ambient solution. Human mucin from saliva (MUC5B) was also used to create multilayers with chitosan on hydrophobized silica and it was revealed that no redissolution appears to be present in this system.

Tumour Leydig cells and normal mature Leydig cells lost their steroidogenic response (pregnenolone and testosterone secretion) to LH after 24 h of culture. Immature cells showed a 2-fold increase in the basal pregnenolone secretion and no change in the LH-dependent pregnenolone secretion after 24 h of culture, whereas the LH-dependent steroidogenesis decreased after 48 h. None of the 3 cell preparations showed morphological signs of degeneration during a culture period of more than 7 days. Histochemical 3 beta-hydroxysteroid dehydrogenase activity in isolated immature Leydig cells disappeared during the first 2 days of the culture period and re-appeared after 5--7 days. Testosterone production by mature Leydig cells decreased during the first hours after exposure to LH, whereas pregnenolone secretion remained constant. From these results it was concluded that Leydig cells attached to plastic can be used for investigation of acute actions of LH on steroidogenesis. A perifusion technique for cells attached to plastic was developed and was applied to the kinetics of LH action on steroidogenesis in tumour and immature Leydig cells. The first stimulation of pregnenolone secretion occurred within 5 min, but a full stimulation was only obtained after 20--30 min. This was followed by a gradual decrease in the stimulated steroid secretion to approximately 50% after 60 min.