Building complexity in O2-binding copper complexes : site-selective metalation and intermolecular O2-binding at dicopper and heterometallic complexes derived from an unsymmetric ligand

A novel unsymmetric dinucleating ligand (LN3N4) combining a tridentate and a tetradentate binding sites linked through a m-xylyl spacer was synthesized as ligand scaffold for preparing homo- and dimetallic complexes, where the two metal ions are bound in two different coordination environments. Site-selective binding of different metal ions is demonstrated. LN3N4 is able to discriminate between CuI and a complementary metal (M′ = CuI, ZnII, FeII, CuII, or GaIII) so that pure heterodimetallic complexes with a general formula [CuIM′(LN3N4)]n+ are synthesized. Reaction of the dicopper(I) complex [CuI 2(LN3N4)]2+ with O2 leads to the formation of two different copper-dioxygen (Cu2O2) intermolecular species (O and TP) between two copper atoms located in the same site from different complex molecules. Taking advantage of this feature, reaction of the heterodimetallic complexes [CuM′(LN3N4)]n+ with O2 at low temperature is used as a tool to determine the final position of the CuI center in the system because only one of the two Cu2O2 species is formed

Selective Ortho-Hydroxylation–Defluorination of 2-Fluorophenolates with a Bis(m-oxo)dicopper(III) Species

The bis(mu-oxo) dicopper(III) species [Cu-III 2(mu-O)(2)(m-XYLMeAN)](2+) (1) promotes the electrophilic ortho-hydroxylation-defluorination of 2-fluorophenolates to give the corresponding catechols, a reaction that is not accomplishable with a (eta(2) : eta(2)-O-2) dicopper(II) complex. Isotopic labeling studies show that the incoming oxygen atom originates from the bis(mu-oxo) unit. Ortho-hydroxylation-defluorination occurs selectively in intramolecular competition with other ortho-substituents such as chlorine or bromine

Pró-fármaco ativado por enzima, uma estratégia promissora na quimioterapia

Strategies that promote selective activation of prodrugs by enzymes can be divided into two major classes: 1) deliver of a monoclonal antibody-enzyme immunoconjugate that can recognize a specific antigen and promote the prodrug to a citotoxic drug, with a high selectivity for the target cells, and 2) selective gene delivery encoding an enzyme that can promote the prodrug to a citotoxic drug for the target cells. In this article are discussed ADEPT (antibody-directed enzyme prodrug therapy), GDEPT (gene-directed enzyme prodrug therapy), VDEPT (virus-directed enzyme prodrug therapy), GPAT (genetic prodrug activation therapy) and PDEPT (polymer-directed enzyme prodrug therapy) approaches, their clinical trials, advantages, disadvantages and perspectives.

Impact of maternity care policy in Catalonia: a retrospective cross-sectional study of service delivery in public and private hospitals

Background: As a result of the growing number of interventions that are now performed in the context of maternity care, health authorities have begun to examine the possible repercussions for service provision and for maternal and neonatal health. In Spain the Strategy Paper on Normal Childbirth was published in 2008, and since then the authorities in Catalonia have sought to implement its recommendations. This paper reviews the current provision of maternity care in Catalonia. Methods: This was a descriptive study. Hospitals were grouped according to their source of funding (public or private) and were stratified (across four strata) on the basis of the annual number of births recorded within their respective maternity service. Data regarding the distribution of obstetric professionals were taken from an official government survey of hospitals published in 2010. The data on obstetric interventions (caesarean, use of forceps, vacuum or non-specified instruments) performed in 2007, 2010 and 2012 were obtained by consulting discharge records of 44 public and 20 private hospitals, which together provide care in 98% of all births in Catalonia. Proportions and confidence intervals were calculated for each intervention performed in all full-term (3742 weeks) singleton births. Results: Analysis of staff profiles according to the stratification of hospitals showed that almost all the hospitals had more obstetricians than midwives among their maternity care staff. Public hospitals performed fewer caesareans [range between 19.20% (CI 18.84-19.55) and 28.14% (CI 27.73-28.54)] than did private hospitals [range between 32.21% (CI 31.78-32.63) and 39.43% (CI 38.98-39.87)]. The use of forceps has decreased in public hospitals. The use of a vacuum extractor has increased and is more common in private hospitals. Conclusions: Caesarean section is the most common obstetric intervention performed during full-term singleton births in Catalonia. The observed trend is stable in the group of public hospitals, but shows signs of a rise among private institutions. The number of caesareans performed in accredited public hospitals covers a limited range with a stable trend. Among public hospitals the highest rate of caesareans is found in non-accredited hospitals with a lower annual number of births.

Impact of maternity care policy in Catalonia: a retrospective cross-sectional study of service delivery in public and private hospitals

Background: As a result of the growing number of interventions that are now performed in the context of maternity care, health authorities have begun to examine the possible repercussions for service provision and for maternal and neonatal health. In Spain the Strategy Paper on Normal Childbirth was published in 2008, and since then the authorities in Catalonia have sought to implement its recommendations. This paper reviews the current provision of maternity care in Catalonia. Methods: This was a descriptive study. Hospitals were grouped according to their source of funding (public or private) and were stratified (across four strata) on the basis of the annual number of births recorded within their respective maternity service. Data regarding the distribution of obstetric professionals were taken from an official government survey of hospitals published in 2010. The data on obstetric interventions (caesarean, use of forceps, vacuum or non-specified instruments) performed in 2007, 2010 and 2012 were obtained by consulting discharge records of 44 public and 20 private hospitals, which together provide care in 98% of all births in Catalonia. Proportions and confidence intervals were calculated for each intervention performed in all full-term (3742 weeks) singleton births. Results: Analysis of staff profiles according to the stratification of hospitals showed that almost all the hospitals had more obstetricians than midwives among their maternity care staff. Public hospitals performed fewer caesareans [range between 19.20% (CI 18.84-19.55) and 28.14% (CI 27.73-28.54)] than did private hospitals [range between 32.21% (CI 31.78-32.63) and 39.43% (CI 38.98-39.87)]. The use of forceps has decreased in public hospitals. The use of a vacuum extractor has increased and is more common in private hospitals. Conclusions: Caesarean section is the most common obstetric intervention performed during full-term singleton births in Catalonia. The observed trend is stable in the group of public hospitals, but shows signs of a rise among private institutions. The number of caesareans performed in accredited public hospitals covers a limited range with a stable trend. Among public hospitals the highest rate of caesareans is found in non-accredited hospitals with a lower annual number of births.

Cross-country data on the quantity of schooling: a selective survey and some quality measures

We survey a number of papers that have focused on the construction of cross-country data sets on average years of schooling. We discuss the construction of the different series, compare their profiles and construct indicators of their information content. The discussion focuses on a sample of OECD countries but we also provide some results for a large non-OECD sample.

Inorganic Nanoparticles and the Immune System: Detection, Selective Activation and Tolerance

The immune system is the responsible for body integrity and prevention of external invasion. On one side, nanoparticles are no triggers that the immune system is prepared to detect, on the other side it is known that foreign bodies, not only bacteria, viruses and parasites, but also inorganic matter, can cause various pathologies such as silicosis, asbestosis or inflammatory reactions. Therefore, nanoparticles entering the body, after interaction with proteins, will be either recognized as self-agents or detected by the immune system, encompassing immunostimulation or immunosuppression responses. The nature of these interactions seems to be dictated not specially by the composition of the material but by modifications of NP coating (composition, surface charge and structure). Herein, we explore the use of gold nanoparticles as substrates to carry multifunctional ligands to manipulate the immune system in a controlled manner, from undetection to immunostimulation. Murine bone marrow macrophages can be activated with artificial nanometric objects consisting of a gold nanoparticle functionalized with peptides. In the presence of some conjugates, macrophage proliferation was stopped and pro-inflammatory cytokines were induced. The biochemical type of response depended on the type of conjugated peptide and was correlated with the degree of ordering in the peptide coating. These findings help to illustrate the basic requirements involved in medical NP conjugate design to either activate the immune system or hide from it, in order to reach their targets before being removed by phagocytes. Additionally, it opens up the possibility to modulate the immune response in order to suppress unwanted responses resulting from autoimmunity, or allergy or to stimulate protective responses against pathogens.

Delivery Reliability: Timely and Quantitative Accuracy in a Forest Industry Company

The primary objective of this thesis was to research delivery reliability of mill business unit of a forest industry company, especially timely and quantitative accuracy of sales orders. Delivery reliability is an important factor of customer satisfaction, which has a great influence for success of a company. The secondary objective was to find out reasons for possible problems of delivery reliability and give propositions for improvable performances. The empirical part of the thesis based on reporting database of the forest industry company’s ERP-software and detailed information of the mill system. The delivery reliability results of the mill business unit were compared to delivery reliability of similar mill business unit inside the forest industry company. The research results expressed problems in the supply chain. The delivery reliability reporting should be also developed further. This would advance delivery reliability monitoring. The improvement propositions of the thesis were logistic operation mode estimation, particular benchmarking of the compared mill business unit and more detailed survey on production delivery reliability.

Human papillomavirus (HPV) in mothers before and after delivery – a three year follow-up study.

Human papillomavirus (HPV) infections in mothers are important to consider since pregnancy may affect the outcome of the infection and the mother may transmit HPV to the child. This thesis is part of the 3-year Finnish Family HPV Study on HPV infection dynamics within 329 families. The presence of maternal HPV antibodies and HPV DNA in placenta, umbilical cord blood and breast milk was examined. In addition, genital and oral HR-HPV carriage was studied among mothers with one or two pregnancies. At enrollment, seropositivity to HPV 6, 11, 16, 18 and 45 was recorded in 53 %, 21 %, 35 %, 21 % and 9 % of the mothers, respectively. Age at sexual debut, number of sexual partners, a history of genital warts and antibodies to LR/HR-HPV predicted HR/LR-HPV-seropositivity. During follow-up 27 %, 14 %, 17 %, 17 % and 7 % of the mothers seroconverted to the tested HPV-types, respectively. Decay of HPV-antibodies was rare. The mother’s new pregnancy was of minor impact in the outcome of oral and cervical HR-HPV infections. HPV-DNA was present in 4.2 % and 3.5 % of the placentas and umbilical cord blood samples, and in 4.5 % and 19.7 % of the breast milk samples collected at day 3 and month 2 postpartum, respectively. HPV-positivity in placenta/cord blood was related to a history of abnormal pap-smears or genital warts, and raised the risk of the neonate being HPV-positive at birth. The mode of delivery did not predict the HPVstatus of neonate, placenta, or cord blood. HPV DNA in breast milk was associated with oral HPV status of the father, but not with HPV status of the neonate. The results indicate that exposure to HPV is common and that part of the exposure might take place already early in life. Contrary to the common claim, pregnancy is not a risk factor for HPV.

Highly selective transport of mercury(II) ion through a bulk liquid membrane

In this work carrier-facilitated transport of mercury(II) against its concentration gradient from aqueous 0.04 M hydrochloric acid solution across a liquid membrane containing isopropyl 2-[(isopropoxycarbothiolyl)disulfanyl]ethane thioate (IIDE) as the mobile carrier in chloroform has been investigated. Sodium thiocyanate solution (1.6 M) was the most efficient receiving phase agent among several aqueous reagents tested. Various parameters such as investigated. Under optimum conditions the transport of Hg(II) across the liquid membrane is more than 97% after 2.5 h. The carrier, IIDE, selectively and efficiently could able to transport Hg (II) ions in the presence of other associated metal ions in binary systems.

Low metal loading catalysts used for the selective hydrogenation of styrene

A series of Group VIII metal catalysts was obtained for the semi-hydrogenation of styrene. Catalysts were characterized by Hydrogen Chemisorption, TPR and XPS. Palladium, rhodium and platinum low metal loading prepared catalysts presented high activity and selectivity (ca. 98%) during the semi-hydrogenation of styrene, being palladium the most active catalyst. The ruthenium catalyst also presented high selectivity (ca. 98%), but the lowest activity. For the palladium catalyst, the influence of the precursor salt and of the reduction temperature on the activity and selectivity were studied. The following activity series was obtained: PdN-423 > PdCl-673 > PdCl-373> PtCl-673 > RhCl-673 >> RuCl-673. As determined by XPS, differences in activity could be attributed, at least in part, to electronic effects.

Selective hydrogenation of furfural on Ir/TiO2 catalysts

Titania-supported Ir catalysts were used in the hydrogenation of furfural. Reactions were carried out in a stirred batch type reactor at 0.62MPa and 363K using a 0.10M solution of furfural in a 1:1 mixture n-heptane -ethanol as solvent. Catalysts containing 2 wt% of Ir were reduced in H2 flow at different temperatures in the range 473-773K. The catalysts were characterized by H2 chemisorption, TEM, TPR, TPD of NH3 and XPS. Conversion of furfural is higher at lower reduction temperatures, but leads to byproducts whereas reduction at higher temperatures shows selectivity to furfuryl alcohol close to 100%.

Influence of ni addition to a low-loaded palladium catalyst on the selective hydrogenation of 1-heptyne

Semi-hydrogenation of alkynes has industrial and academic relevance on a large scale. To increase the activity, selectivity and lifetime of monometallic catalysts, the development of bimetallic catalysts has been investigated. 1-Heptyne hydrogenation over low-loaded Pd and Ni monometallic and PdNi bimetallic catalysts was studied in liquid phase at mild conditions. XPS results suggest that nickel addition to Pd modifies the electronic state of palladium as nickel loading is increased. Low-loaded Pd catalysts showed the highest selectivities (> 95%). The most active prepared catalyst, PdNi(1%), was more selective than the Lindlar catalyst.

Synchronous scanning phosphorimetry for the selective determination of chrysene: a metrological study

Room-temperature phosphorimetry was used to quantify trace levels of chrysene in sugar-cane spirits and in fish bile. A selective phosphorescence enhancer (AgNO3) and synchronous scanning allowed the detection of ng amounts of chrysene. Accuracy (113 ± 17%) and selectivity was evaluated using the CRM-NIST-1647d - Priority Pollutant Polycyclic Aromatic Hydrocarbons in acetonitrile. Analysis of sugar-cane spirit samples enabled recovery of 108 ± 18% which agreed with the one achieved using HPLC. Method's uncertainty was equivalent to 3.4 ng of the analyte, however, the analyte pre-concentration (SPE) improved sensibility and minimized the relative uncertainty. Characterization and homogeneity studies in fish bile were also performed.

Selective and non-extractive spectrophotometric determination of cefdinir in formulations based on donor-acceptor complex formation

Cefdinir has broad spectrum of activity and high prescription rates, hence its counterfeiting seems imminent. We have proposed a simple, fast, selective and non-extractive spectrophotometric method for the content assay of cefdinir in formulations. The method is based on complexation of cefdinir and Fe under reducing condition in a buffered medium (pH 11) to form a magenta colored donor-acceptor complex (λ max = 550 nm; apparent molar absorptivity = 3720 L mol-1 cm-1). No other cephalosporins, penicillins and common excipients interfere under the test conditions. The Beer's law is followed in the concentration range 8-160 µg mL-1.