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The extremely neutron-deficient isotopes 177,179Au were studied by means of in-beam γ-ray spectroscopy. Specific tagging techniques, α-decay tagging in 177Au and isomer tagging in 179Au, were used for these studies. Feeding of positive-parity, nearly spherical states, which are associated with 2d3/2 and 3s1/2 proton-hole configurations, from the 1i13/2 proton-intruder configuration was observed in 177Au. Such a decay path has no precedent in odd-Au isotopes and it is explained by the effect of mixing of wave functions of the initial state.

The magnetic dipole moments (μ) of 209Tlg (N=128) and 207Tlm (N=126) have been measured for the first time using the in-source laser resonance-ionization spectroscopy technique with the Laser Ion Source and Trap (LIST) at ISOLDE (CERN). The application of the LIST suppresses the usually overwhelming background of the isobaric francium isotopes and allows access to heavy thallium isotopes with A⩾207. The self-consistent theory of finite Fermi systems based on the energy density functional by Fayans et al. well describes the N dependence of μ for 1/2+ thallium ground states, as well as μ for the 11/2− isomeric states in europium, gold and thallium isotopes. The inclusion of particle-vibration coupling leads to a better agreement between the theory and experiment for μ(Tlg, Iπ=1/2+). It is shown that beyond mean-field contributions to μ cannot be neglected at least for thallium isotopes with Iπ=1/2+.

A recently developed portable, on-line capability for γ-ray and conversion-electron spectroscopy, HIGH-TATRA is demonstrated with its application to the study of 183Hg 183Au at ISOLDE. Key details of the low-energy level scheme of the neutron-deficient nuclide 183Au populated in this decay are presented. A broad energy germanium detector is employed to achieve this (the first-ever use of such a device in decay-scheme spectroscopy), by way of a combination of high-gain γ-ray singles spectroscopy and γ–γ coincidence spectroscopy. Further, by combining the γ-ray detectors with a liquid-nitrogen-cooled Si(Li) detector operated under high vacuum, conversion-electron singles and e–γ coincidences are obtained. These data lead to the determination of transition multipolarities and the location of a highly converted (E0 + M1 + E2) transition in the 183Au decay scheme, suggesting a possible new shape coexisting structure in this nucleus. Identification of new intruder and normal states fixes their relative energies in 183Au for the first time. New systematic features in the odd-Au isotopes are presented. [ABSTRACT FROM AUTHOR]

The new chiral ligands I-III based on derivatives of imidazolidin-4-one were synthesised and characterised. The catalytic activity and enantioselectivity of their corresponding copper(II) complexes were studied in asymmetric Henry reactions. It was found that the enantioselectivity of these catalysts is overall very high and depends on the relative configuration of the ligand used; cis- configuration of ligand affords the nitroaldols with major enantiomer S- (up to 97% ee), whereas the application of ligands with trans -configuration led to nitroaldols with major R -enantiomer (up to 96% ee). The "proline-type" ligand IV was also tested in asymmetric aldol reactions. Under the optimised reaction conditions, aldol products with enantioselectivities of up to 91% ee were obtained., (Copyright © 2024, Bartáček et al.)

This study presents an improved synthetic route to ligand ( S )-4-( tert -butyl)-2-(5-(trifluoromethyl)pyridin-2-yl)-4,5-dihydrooxazole and its application as a highly active and enantioselective catalyst in the addition of arylboronic acids to cyclic N -sulfonylketimines. Immobilization of such a ligand was achieved using a commercially available starting material and a PS-PEG TentaGel S NH 2 support, resulting in a stable heterogeneous catalyst. Although the anchored catalyst exhibited a slight reduction in enantioselectivity and a 4-fold decrease in reaction rate, it displayed remarkable stability, enabling 10 consecutive reaction cycles. Furthermore, the successful transition to a continuous flow system demonstrated even higher turnover numbers compared to batch arrangements. These findings provide valuable insights into the development of efficient flow reactors for continuous synthesis of benzosultams, further advancing the field of asymmetric catalysis.

Background: Traumatic brain injury (TBI) is one of the most common trauma-related diagnoses among the elderly population treated in emergency departments (ED). Identification of patients with increased or decreased risk of intracranial bleeding is of clinical importance. The objective of this study was to evaluate the implication of cutaneous impact location (CIL) on the prevalence of intracranial injury after suspected or confirmed TBI irrespective of its severity., Methods: This was a retrospective, single-center, descriptive observational study of geriatric patients aged 65 years and older treated for suspected or confirmed TBI in a trauma surgery ED. The primary outcome of the study was the assessment of a CIL of the injury and its association with the prevalence of intracranial lesions found on a head computed tomography scan., Results: Among 381 patients included in the analysis, the CIL of interest (temporo-parietal and occipital impacts) was present among 178 (46.7%) cases. Thirty-six (9.5%) patients were diagnosed with intracranial bleeding. The prevalence of intracranial bleeding was higher in the CIL of interest group compared with other locations outside (12.9% vs 6.4%; p = 0.030). CIL of interest was a predictor of intracranial bleeding (p = 0.033; OR: 2.17; 95% CI: 1.06 to 4.42)., Conclusion: The CIL of head injury is a predictor of intracranial lesions among geriatric patients with traumatic brain injury. Physicians should be aware of this association when assessing elderly patients with head injuries. More studies are needed to develop a clinical management tool incorporating CIL to guide the diagnosis of TBI in this population., Competing Interests: The authors declare no conflicts of interest in this work., (© 2023 Sedlák et al.)

Background: BRASH syndrome (bradycardia, renal failure, atrioventricular nodal blockade, shock, and hyperkalemia) is a rare clinical condition with potentially severe outcomes. Patients with BRASH syndrome can present with diverse signs and symptoms and are usually in critical condition, but if recognized early, the syndrome is treatable and may have a favorable prognosis., Case Presentation: This case study presents a 74-year-old patient with a history of multiple chronic conditions who was brought to the emergency department with a suspected cerebrovascular accident, altered mental status, and bradycardia. A head computed tomography scan was unremarkable but laboratory results showed hyperkalemia, acidosis, and renal failure with concomitant progressive hypoglycemia. The patient was diagnosed with a BRASH syndrome characterized by a vicious cycle of atrioventricular nodal blockade induced by the potentiated effect of beta-blockers or calcium channel blockers, in combination with progressive hypoglycemia due to the suspected accumulation of anti-diabetic medications, which influenced the presentation and initial triage in the emergency department. She was admitted to the intensive care unit for further management, where she continued to improve and was ultimately discharged in a relatively stable condition., Conclusion: This case study highlights the importance of considering rare and atypical presentations of medical conditions, particularly in elderly patients who may have multiple comorbidities. Early recognition and prompt management of such cases are crucial for improving patient outcomes., (© 2023. The Author(s).)

Palladacycles are key intermediates in catalytic C-H bond functionalization reactions and important precatalysts for cross-couplings. It is commonly believed that palladacycle formation occurs through the reaction of a substrate bearing a C-H bond ortho to a suitable metal-directing group for interaction with, typically, mononuclear "Pd(OAc) 2 " species, with cyclopalladation liberating acetic acid as the side product. In this study, we show that N , N -dimethyl-fluoro-benzyl amines, which can be cyclopalladated either ortho or para to fluorine affording two regioisomeric products, can occur by a direct reaction of Pd 3 (OAc) 6 , proceeding via higher-order cyclopalladated intermediates. Regioselectivity is altered subtly depending on the ratio of substrate:Pd 3 (OAc) 6 and the solvent used. Our findings are important when considering mechanisms of Pd-mediated reactions involving the intermediacy of palladacycles, of particular relevance in catalytic C-H bond functionalization chemistry., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Introduction: The aim of this study was to determine factors that affect post-operative subsidence in split-depression lateral plateau tibial fracture (OTA/AO 41B3.1) which was treated with raft construct through a locking plate., Patients and Methods: The retrospective study evaluated all split-depression lateral plateau tibial fracture cases treated with raft construct through a locking plate between 01/2015 and 04/2020 with a minimum of 12-month follow-up. Data on the patients' age, sex, time from injury to surgery, type of plate, and use of subchondral bone defect filler were retrieved from the hospital database. The measurements of total plateau area (TPA), depressed lateral plateau area (DPA), and maximal plateau depression (MPD) were performed on the patients' pre-operative CT scans. The percentage of DPA to TPA (%DPA) was calculated. Post-operative radiographs were used for the evaluation of plateau subsidence. A subsidence greater than 2 mm was considered a failure., Results: There were 41 consecutive cases of split-depression lateral plateau tibial fracture in the reviewed period. Five cases were excluded, three of them were lost to follow up, 1 patient had no pre-operative CT scan and 1 had a history of cancer. A failure was identified in 11 (31%) cases. Patients in the failure group were older (61.0 vs 50.7 years, p = 0.01), and had a higher incidence of fractures extending into intercondylar eminence (100% vs 56%, p = 0.02). Multiple logistic regression identified DPA (OR = 3.6; 95%CI 1.4-9.5, p < 0.01) and age (OR = 1.2; 95% CI 1.0-1.4, p = 0.02) as predictive factors for plateau subsidence. DPA cut-off value for predicting subsidence greater than 2 mm was 5.8 cm 2 [Area Under the ROC Curve 0.89 (95% CI 0.74-0.97), sensitivity 91%, specificity 80%, p < 0.01)]., Conclusion: Age and depressed lateral plateau area (DPA) in split-depression lateral plateau tibial fracture treated with raft construct through a locking plate are risk factors for post-operative subsidence greater than 2 mm., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany.)

Solvophobicity-driven mesoscale structures that lack any stabilizers are perhaps the most common spontaneously formed stable colloidal objects (particles, droplets). In spite of this, they have been significantly overlooked for a long time and the knowledge on solvophobicity-driven mesoscale structures (SDMSs) is rather limited. Here, we follow up on our previous work on mesoscale solubility [Rak, D.; Sedlák, M. On the Mesoscale Solubility in Liquid Solutions and Mixtures. J. Phys. Chem. B 2019, 123, 1365-1374. 10.1021/acs.jpcb.8b10638] and aim at providing a fully consistent picture of the nature, formation, and stability of SDMSs. We investigate both aqueous and nonaqueous mixtures, showing that this phenomenon is universal and not limited to aqueous systems. An experimental regime diagram is constructed as a function of the concentration of the solvophobic component and the solvophobicity strength given by mixtures of various organic solvents. Aqueous mixtures are investigated using well-defined ternary systems comprising water, ethanol (or other organic solvents), and a series of linear alkanes serving as hydrophobes. This investigation covers unique long-time monitoring of SDMS stability (up to three years). Another parameter studied in detail is the temperature of the mixture. SDMSs are characterized in terms of their shape and size distributions obtained using orthogonal techniques. Last but not least, we bring some insights into the SDMS surface zeta potential─the key quantity behind the stability of SDMSs. We investigate zeta potential as a function of the mixture composition, pH, and temperature.

Many university-taught courses moved to online form since the outbreak of the global pandemic of coronavirus disease (COVID-19). Distance learning has become broadly used as a result of the widely applied lockdowns, however, many students lack personal contact in the learning process. A classical web-based distance learning does not provide means for natural interpersonal interaction. The technology of immersive virtual reality (iVR) may mitigate this problem. Current research has been aimed mainly at specific instances of collaborative immersive virtual environment (CIVE) applications for learning. The fields utilizing iVR for knowledge construction and skills training with the use of spatial visualizations show promising results. The objective of this study was to assess the effectiveness of collaborative and individual use of iVR for learning geography, specifically training in hypsography. Furthermore, the study's goals were to determine whether collaborative learning would be more effective and to investigate the key elements in which collaborative and individual learning were expected to differ-motivation and use of cognitive resources. The CIVE application developed at Masaryk University was utilized to train 80 participants in inferring conclusions from cartographic visualizations. The collaborative and individual experimental group underwent a research procedure consisting of a pretest, training in iVR, posttest, and questionnaires. A statistical comparison between the geography pretest and posttest for the individual learning showed a significant increase in the score (p = 0.024, ES = 0.128) and speed (p = 0.027, ES = 0.123), while for the collaborative learning, there was a significant increase in the score (p<0.001, ES = 0.333) but not in speed (p = 1.000, ES = 0.000). Thus, iVR as a medium proved to be an effective tool for learning geography. However, comparing the collaborative and individual learning showed no significant difference in the learning gain (p = 0.303, ES = 0.115), speed gain (p = 0.098, ES = 0.185), or performance motivation (p = 0.368, ES = 0.101). Nevertheless, the collaborative learning group had significantly higher use of cognitive resources (p = 0.046, ES = 0.223) than the individual learning group. The results were discussed in relation to the cognitive load theories, and future research directions for iVR learning were proposed., Competing Interests: The authors have declared that no competing interests exist.

The human drugs - the antibiotic linezolid ( 1 ) and the anticoagulant rivaroxaban ( 2 ) - belong among modern pharmaceutics, which contain an oxazolidine-2-one moiety bearing a stereogenic center. The chirality of these drugs is a fundamental attribute for their biological activity. Herein, one of the efficient asymmetric syntheses of these drugs was studied in detail. Highly enantioselective catalysts were tested in the key step of the synthetic procedure, i.e., the asymmetric Henry reaction, under different reaction conditions, using several starting aldehydes. The corresponding nitroaldols as chiral intermediates in the syntheses of these drugs were obtained in high yields and enantiomeric excesses of up to 91% ee., (Copyright © 2022, Vrbický et al.)

Diphyllin is a natural arylnaphtalide lignan extracted from tropical plants of particular importance in traditional Chinese medicine. This compound has been described as a potent inhibitor of vacuolar (H + )ATPases and hence of the endosomal acidification process that is required by numerous enveloped viruses to trigger their respective viral infection cascades after entering host cells by receptor-mediated endocytosis. Accordingly, we report here a revised, updated, and improved synthesis of diphyllin, and demonstrate its antiviral activities against a panel of enveloped viruses from Flaviviridae, Phenuiviridae, Rhabdoviridae, and Herpesviridae families. Diphyllin is not cytotoxic for Vero and BHK-21 cells up to 100 µM and exerts a sub-micromolar or low-micromolar antiviral activity against tick-borne encephalitis virus, West Nile virus, Zika virus, Rift Valley fever virus, rabies virus, and herpes-simplex virus type 1. Our study shows that diphyllin is a broad-spectrum host cell-targeting antiviral agent that blocks the replication of multiple phylogenetically unrelated enveloped RNA and DNA viruses. In support of this, we also demonstrate that diphyllin is more than just a vacuolar (H + )ATPase inhibitor but may employ other antiviral mechanisms of action to inhibit the replication cycles of those viruses that do not enter host cells by endocytosis followed by low pH-dependent membrane fusion.

A family of oxazaborines, diazaborinones, triazaborines, and triazaborinones was prepared by reaction of polarized ethylenes, such as β-enaminoamides, with 4-methylbenzenediazonium tetraphenylborates. The reaction conditions (stirring in CH 2 Cl 2 at room temperature (Method A) or stirring with CH 3 COONa in CH 2 Cl 2 at room temperature (Method B) or refluxing in the CH 2 Cl 2 /toluene mixture (Method C)) controlled the formation and relative content of these compounds in the reaction mixtures from one to three products. Substituted oxazaborines gradually rearranged into diazaborinones at 250 °C. The prepared compounds were characterized by 1 H NMR, 13 C NMR, IR, and UV-Vis spectroscopy, HRMS, or microanalysis. The structure of individual compounds was confirmed by 11 B NMR, 15 N NMR, 1D NOESY, and X-ray analysis. The mechanism of reaction of enaminoamides with 4-methylbenzenediazonium tetraphenylborate was proposed.

The transition metal (palladium)-catalysed asymmetric 1,4-addition of arylboronic acids to conjugated enones belong to the most important and emerging strategies for the construction of C-C bonds in an asymmetric fashion. This review covers known catalytic systems used for this transformation. For clarity, we are using the type of ligand as a sorting criterion. Finally, we attempted to create a flowchart facilitating the selection of a suitable ligand for a given combination of enone and arylboronic acid., (Copyright © 2021, Bartáček et al.)

In a recent article, Jadhav and Barigou ( Langmuir 2020, 36 (7), 1699-1708) investigated the question of the existence of stable bulk nanobubbles in water generated by hydrodynamic cavitation, ultrasound cavitation, and the addition of an organic compound (namely, ethanol) to water. They firmly conclude that these procedures result in stable bulk nanobubbles. However, a number of previous works documented that the nanoentities observed in water upon such procedures are not nanobubbles. Here, we analyze work of Jadhav and Barigou and show that conclusions regarding the nanobubble nature of the nanoentities are incorrect and are due to the choice of experimental techniques with weak sensitivity, methodical issues in the use of otherwise proper experimental techniques, and ambiguous outcomes of the rest of experiments.

One of the major obstacles that limits the use of magnetic nanoparticles in biomedical applications is their potential toxicity. In the present study, we evaluated the cytotoxic effects of thiol-functionalized silica-coated iron oxide (Fe 3 O 4 @SiO 2 -SH) nanoparticles using human lung epithelial cells A549. We investigated the effect of Fe 3 O 4 @SiO 2 -SH nanoparticles on the cell viability, proliferation, cell cycle distribution, adhesion, apoptosis, and the orientation of the cytoskeletal networks, as well as on expression of proteins involved in cell death, cell survival, and cell adhesion. We demonstrated that exposure of A549 cells to Fe 3 O 4 @SiO 2 -SH nanoparticles resulted in severe disruption of the actin microfilaments and microtubule cytoskeleton and reduced the size of focal adhesions. Furthermore, cell adhesion was significantly affected as well as the phosphorylation of focal adhesion kinase (FAK), extracellular-signal-regulated kinase (ERK), and p38. Our findings highlight the need for in-depth cytotoxic evaluation of nanoparticles supporting their safer use, especially in biomedical applications., Competing Interests: The authors declare that there are no conflicts of interest.

Polymeric drug carriers exhibit excellent properties that advance drug delivery systems. In particular, carriers based on poly(ethylene oxide)-block-poly(ε-caprolactone) are very useful in pharmacokinetics. In addition to their proven biocompatibility, there are several requirements for the efficacy of the polymeric drug carriers after internalization, e.g., nanoparticle behavior, cellular uptake, the rate of degradation, and cellular localization. The introduction of γ-butyrolactone units into the hydrophobic block enables the tuning of the abovementioned properties over a wide range. In this study, a relatively high content of γ-butyrolactone units with a reasonable yield of ≈60% is achieved by anionic ring-opening copolymerization using 1,5,7-triazabicyclo[4.4.0]dec-5-ene as a very efficient catalyst in the nonpolar environment of toluene with an incorporated γ-butyrolactone content of ≈30%. The content of γ-butyrolactone units can be easily modulated according to the feed ratio of the monomers. This method enables control over the rate of degradation so that when the content of γ-butyrolactone increases, the rate of degradation increases. These findings broaden the application possibilities of polyester-polyether-based nanoparticles for biomedical applications, such as drug delivery systems., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Finding optimal reaction conditions is usually complex, requires many experiments, and is therefore demanding in terms of human, financial, and environmental resources. This work provides a simple workflow for easier design of popular palladium-catalyzed C-H functionalization reactions, where the active palladium catalysts contain carboxylate ligands. The key factor for optimizing reaction conditions is to find a balance between two opposing effects of the carboxylic acid in the reaction mixture: generation of more reactive palladium catalyst versus deactivation of a substrate by its protonation.

A drawback of studies on bulk nanobubbles is the absence of direct proof that the nano-objects reported are really nanobubbles. The aim of our work was to provide such a proof or disproof. We focused on two effects (processes) commonly considered in research on nanobubbles: ultrasonic cavitation and addition of organic compounds to water, which could create in principle a barrier at the gas/water interface contributing to the stability of nanobubbles. We found that both of these processes lead to the generation of nano-objects, which are, however, not bulk nanobubbles. Ultrasonication leads to the formation of fine metal nanoparticles originating from the disintegration of the surface of the metal ultrasonic probe. Addition of organic solutes to water leads to the formation of a population of nanoparticles/nanodroplets originating from the so-called mesoscale solubilization of hydrophobic compounds present in the added solute as molecularly dissolved impurities. Subsequent ultrasonication of such mixtures adds metal nanoparticles and only slightly modifies the size distribution of mesoscale particles. While our results do not dismiss existence of nanobubbles in general, described effects must be seriously taken into account, especially in the case of biomedical applications where they can result in serious side effects.

Iron oxide nanoparticles (IONPs) have a great potential with regard to cell labelling, cell tracking, cell separation, magnetic resonance imaging, magnetic hyperthermia, targeted drug and gene delivery. However, a growing body of research has raised concerns about the possible unwanted adverse cytotoxic effects of IONPs. In the present study, the in vitro cellular uptake, antiproliferative activity, cytotoxicity, genotoxicity, prooxidant, microtubule-disrupting and apoptosis-inducing effect of Fe 3 O 4 @SiO 2 and passivated Fe 3 O 4 @SiO 2 -NH 2 nanoparticles on human renal proximal tubule epithelial cells (HK-2) have been studied. Both investigated silica coated IONPs were found to have cell growth-inhibitory activity in a time- and dose-dependent manner. Determination of cell cycle phase distribution by flow cytometry demonstrated a G1 and G2/M phase accumulation of HK-2 cells. A tetrazolium salt cytotoxicity assay at 24 h following treatment demonstrated that cell viability was reduced in a dose-dependent manner. Microscopy observations showed that both Fe 3 O 4 @SiO 2 and Fe 3 O 4 @SiO 2 -NH 2 nanoparticles accumulated in cells and appeared to have microtubule-disrupting activity. Our study also revealed that short term 1 h exposure to 25 and 100 μg/mL of silica coated IONPs causes genotoxicity. Compared with vehicle control cells, a significantly higher amount of γH2AX foci correlating with an increase in DNA double-strand breaks was observed in Fe 3 O 4 @SiO 2 and Fe 3 O 4 @SiO 2 -NH 2 -treated and immunestained HK-2 cells. The investigated nanoparticles did not trigger significant ROS generation and apoptosis-mediated cell death. In conclusion, these findings provide new insights into the cytotoxicity of silica coated IONPs that may support their further safer use., (Copyright © 2019 Elsevier B.V. All rights reserved.)

We address the question of quantum memory storage for quantum dynamics. In particular, we design an optimal protocol for N→1 probabilistic storage and retrieval of unitary channels on d-dimensional quantum systems. If we access the unknown unitary gate only N times, the optimal success probability of perfect single-use retrieval is N/(N-1+d^{2}). The derived size of the memory system exponentially improves the known upper bound on the size of the program register needed for probabilistic programmable quantum processors. Our results are closely related to probabilistic perfect alignment of reference frames and probabilistic port-based teleportation.

Mycobacterium tuberculosis, the etiologic agent of tuberculosis, is an intracellular pathogen of alveolar macrophages. These cells avidly take up nanoparticles, even without the use of specific targeting ligands, making the use of nanotherapeutics ideal for the treatment of such infections. Methoxy poly(ethylene oxide)- block-poly(ε-caprolactone) nanoparticles of several different polymer blocks' molecular weights and sizes (20-110 nm) were developed and critically compared as carriers for rifampicin, a cornerstone in tuberculosis therapy. The polymeric nanoparticles' uptake, consequent organelle targeting and intracellular degradation were shown to be highly dependent on the nanoparticles' physicochemical properties (the cell uptake half-lives 2.4-21 min, the degradation half-lives 51.6 min-ca. 20 h after the internalization). We show that the nanoparticles are efficiently taken up by macrophages and are able to effectively neutralize the persisting bacilli. Finally, we demonstrate, using a zebrafish model of tuberculosis, that the nanoparticles are well tolerated, have a curative effect, and are significantly more efficient compared to a free form of rifampicin. Hence, these findings demonstrate that this system shows great promise, both in vitro and in vivo, for the treatment of tuberculosis.

We report on a mesoscale solubility reflecting the fact that solubility is achieved not only by the well-known "like likes like" or "like dissolves like" based on molecular solvation but also on mesoscale solubilization of dislike compounds characterized in that the solubility (homogeneous distribution over the whole volume of the system) is achieved on a mesoscale level ranging from tens to hundreds of nanometers. It is shown that mesoscale solubility is a spontaneously occurring, literally everywhere present phenomenon, which was hidden and overlooked for a long time. This paper reveals the physical mechanism of mesoscale solubilization comprising nucleation and aggregation accompanied by the development of significant surface zeta potentials on nanoprecipitates, giving them a long-term stability. We show that mesoscale solubilization is common for aqueous as well as nonaqueous systems. Experiments with organic solvents not capable of self-ionization (self-dissociation) instead of water also shed light on the mechanism of the generation of surface zeta potentials at hydrophobic interfaces. We identified the key parameters enabling the mesoscale solubilization and mapped its occurrence as their function. Mesoscale structures including their formation kinetics, long-term stability, and different types of solubilization procedures were characterized by scattering and ultramicroscopic visualization comprising sizing and counting.

Based on current treatment of Alzheimer's disease, where the carbamate inhibitor Rivastigmine is used, two series of carbamate derivatives were prepared: (i) N-phenylcarbamates with additional carbamate group (1-12) and (ii) N-phenylcarbamates with monosaccharide moiety (13-24). All compounds were tested for the inhibitory effect on both of the cholinesterases, electric eel acetylcholinesterase (eeAChE) and butyrylcholinesterase from equine serum (eqBChE) and the inhibitory activity (expressed as IC 50 values) was compared with that of the established drugs Galanthamine and Rivastigmine. The compounds with two carbamate groups 1-12 revealed higher inhibitory efficiency on both cholinesterases in compared with monosaccharide derived carbamates 13-24 and with Rivastigmine. The significant decrease of inhibitory efficiency on eqBChE (also for eeAChE but in less manner) was observed after deacetalization of monosaccharide. Moreover, the type of inhibitory mechanism of five chosen compounds was studied. It was found, that compounds with two carbamate groups act presumably via a mixed inhibitory mechanism and the compounds with monosaccharide moiety act as non-competitive inhibitors. The lipophilicity of tested compounds was determined using partition coefficient. Specific positions of the inhibitors in the binding sites of cholinesterases were determined using molecular modeling and the results indicate the importance of phenylcarbamate orientation in the catalytic gorges of both enzymes., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The role of polynuclear species in C-H activations assisted by palladium carboxylates has not been clear so far. The summary of the key findings covering this issue shows its important role under certain conditions. However, much more effort is necessary for a deeper understanding of the whole issue.

Reactions catalyzed by palladium(ii) acetate and trifluoroacetic acid (TFA) have a clear preactivation phase. However, the structure of real catalytic species remains unclear. We show that the key species are cyclic trinuclear complexes of composition [Pd 3 (OAc) 6-x (OTFA) x ] (x = 1-6) formed by a sequential ligand exchange from [Pd 3 (OAc) 6 ]. Furthermore, we prove that the trinuclear palladium backbone of the precatalyst remains preserved during the first phase of the C-H activation reaction of acetanilides. In other words, the reaction pathway including the trinuclear species should be taken into account in discussion about mechanisms of the reactions catalyzed by palladium acetates.

This present mini-review covers recently published results on Cu(I) and Cu(II) complexes immobilized on polystyrene carriers, which are used as heterogeneous, eco-friendly reusable catalysts applied for carbon-carbon and carbon-nitrogen forming reactions. Recent advances and trends in this area are demonstrated in the examples of oxidative homocoupling of terminal alkynes, the synthesis of propargylamines, nitroaldolization reactions, azide alkyne cycloaddition, N -arylation of nitrogen containing compounds, aza-Michael additions, asymmetric Friedel-Crafts reactions, asymmetric Mukaiyama aldol reactions, and asymmetric 1,3-dipolar cycloaddition of azomethine ylides. The type of polystyrene matrix used for the immobilization of complexes is discussed in this paper, and particularly, the efficiency of the catalysts from the point of view of the overall reaction yield, and possible enantioselectivity and potential reusing, is reviewed., Competing Interests: The authors declare no conflict of interest.

This review addresses the recent research progress in introducing and elaborating a novel approach to controlled polymer self-assembly into stable nanoparticles using pH-responsive thermosensitive homopolymer polyelectrolytes. Interesting aspect of this approach is that stable polymeric nanoparticles are formed from homopolymers of one type only and without any assembly-triggering additives. The process of their formation can be monitored online e.g. by light scattering and particle size can be finely custom tuned. Obtained nanoparticles have interesting properties and are very stable over long periods of time and over a broad range of salt concentrations including physiological conditions. Much effort was devoted not only to finding optimum experimental protocols and to characterizing resulting nanoparticles in detail, but also to understanding physical processes behind these successful protocols., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A serie of O-substituted N-2-phenylcyclopropylcarbamates was prepared and characterized. These carbamates were tested as inhibitors of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). It was found, that these compounds exhibit moderate inhibition activity with values of IC 50 in the range of 54.8-94.4 μM (for AChE) and up to 5.8 μM (for BChE). The AChE/BChE selectivity for each carbamate was calculated. These values varied from 0.50 to 9.46, two carbamate derivatives inhibited only AChE selectively. The most promising derivative was prepared in all optically pure forms (four isomers). It was found that individual stereoisomers differed only slightly in the inhibition ability. The cytotoxicity of all carbamates was evaluated using the standard in vitro test with Jurkat cells. With regard to their inhibition activity and cytotoxicity as well as easy preparation, O-substituted N-2-phenylcyclopropylcarbamates can be considered as promising compounds for potential medicinal applications.

We have performed a detailed experimental study on aqueous solutions of tertiary butyl alcohol which were a subject of long-standing controversies regarding the puzzling presence of virtually infinitely stable large-scale structures in such solutions occurring at length scales exceeding appreciably dimensions of individual molecules, referred to also as mesoscale structures. A combination of static and dynamic light scattering yielding information on solution structure and dynamics and gas chromatography coupled with mass spectrometry yielding information on chemical composition was used. We show that tertiary butyl alcohol clearly exhibiting such structures upon mixing with water does not contain any propylene oxide, which was previously considered as a source of these structures (an impurity expected to be present in all commercial samples of TBA). More importantly, we show that no mesoscale structures are generated upon addition of propylene oxide to aqueous solutions of TBA. The ternary system TBA/water/propylene oxide exhibits homogeneous mixing of the components on mesoscales. We show that the source of the mesoscale structures is a mesophase separation of appreciably more hydrophobic compounds than propylene oxide. These substances are explicitly analytically identified as well as their disappearance upon filtering out the mesoscale structures by nanopore filtration. We clearly show which substances are disappearing upon filtration and which are not. This enables us to estimate with rather high probability the chemical composition of the mesoscale structures. Visualization of large-scale structures via nanoparticle tracking analysis is also presented. Video capturing the mesoscale particles as well as their Brownian motion can be found in the Supporting Information .

We propose an efficiently measurable lower bound on quantum process fidelity of N-qubit controlled-Z gates. This bound is determined by average output state fidelities for N partially conjugate product bases. A distinct advantage of our approach is that only fidelities with product states need to be measured while keeping the total number of measurements much smaller than what is necessary for full quantum process tomography. As an application, we use this method to experimentally estimate quantum process fidelity F of a three-qubit linear optical quantum Toffoli gate and we find that F≥0.83. We also demonstrate the entangling capability of the gate by preparing Greenberger-Horne-Zeilinger-type three-qubit entangled states from input product states.

The Letter describes the preparation and characterization of a conjugate of isoniazid (INH) with magnetic nanoparticles Fe3O4@SiO2 115±60 nm in size. The INH molecules were attached to the surface of nanoparticles by a covalent pH-sensitive amidine bond. The conjugate was characterized by X-ray diffraction, SEM, dynamic light scattering, IR spectroscopy and microanalysis. The conjugate released isoniazid under in vitro conditions (pH=4; 37 °C; t1/2≈115 s). In addition, the cytotoxicity of the Fe3O4@SiO2-INH conjugate was evaluated in SK-BR-3 cells using the xCELLigence system., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

A detailed experimental and DFT study of the S to N alkyl migration of substituted S-(1(3H)-isobenzofuranon-3-yl)isothiuronium bromide to N,N'-dimethyl-N-(3-oxo-1,3-dihydro-2-benzofuran-1-yl)thiourea provided evidence for the existence of an unusual double displacement mechanism involving two consecutive back-side S(N)2 reactions where a carboxylate anion has a crucial role both as a leaving group as well as an internal nucleophile. The thiazetidine zwitterionic species that is involved in this mechanism as an intermediate was characterized by infrared multiphoton dissociation spectroscopy and was trapped with methyl iodide. It was found that the intermediate has a structure of a free ion pair. The double-displacement mechanism can be considered as a new type of inverse lactone neighboring group participation.

In textbooks, undersaturated solutions of low molar mass compounds and mixtures of freely miscible liquids are considered as homogeneous at larger length scales exceeding appreciably dimensions of individual molecules. However, growing experimental evidence reveals that it is not the case. Large-scale structures with sizes on the order of 100 nm are present in solutions and mixtures used in everyday life and research practice, especially in aqueous systems. These mesoscale inhomogeneities are long-lived, and (relatively slow) kinetics of their formation can be monitored upon mixing the components. Nevertheless, the nature of these structures and mechanisms behind their formation are not clear yet. Since it was previously suggested that these can be nanobubbles stabilized by adsorbed solute at the gas/solvent interface, we devote the current study to addressing this question. Static and dynamic light scattering was used to investigate solutions and mixtures prepared at ordinary conditions (equilibrated with air at 1 atm), prepared with degassed solvent, and solutions and mixtures degassed after formation of large structures. The behavior of large structures in strong gravitational centrifugal fields was also investigated. Systems from various categories were chosen for this study: aqueous solutions of an inorganic ionic compound (MgSO4), organic ionic compound (citric acid), uncharged organic compound (urea), and a mixture of water with organic solvent freely miscible with water (tert-butyl alcohol). Obtained results show that these structures are not nanobubbles in all cases. Visualization of large-scale structures via nanoparticle tracking analysis is presented. NTA results confirm conclusions from our previous light scattering work.