Structural, magnetic and spectral properties of tetrahedral cobalt(ii) silanethiolates: a variety of structures and manifestation of field-induced slow magnetic relaxation.

Blue crystals of five heteroleptic cobalt(ii) silanethiolates 1-5 have been obtained by the reaction of [Co{SSi(tBuO)3}2(NH3)]2 with aminopyridines and aminomethylpyridines at an appropriate molar ratio and their structural, spectral, thermal and magnetic properties have been established and described. All complexes 1-5 contain Co(ii) ions in a tetrahedral CoN2S2 environment formed by (tBuO)3SiS- residues and pyridines and present variable structures. Complexes 1-3 are mononuclear [Co{SSi(tBuO)3}2(L1)2] (L1 = 2-aminopyridine 2AP, 3-aminopyridine 3AP, and 4-aminopyridine 4AP). The application of 3AMP and 4AMP (3-aminomethylpyridine and 4-aminomethylpyridine) allows either dinuclear complex 4 [Co{SSi(tBuO)3}2(µ-3AMP)]2 or 1D coordination polymer 5 with the formula of [Co{SSi(tBuO)3}2(µ-4AMP)]n to be obtained. The molecular structures of 1-5 were determined by single-crystal X-ray and powder diffraction, UV-vis and FTIR spectrocopy for solid samples and their thermal properties were characterized by TG-DSC and TG-FTIR methods. The dc and ac magnetic and EPR studies of polycrystalline samples have been performed. For all complexes, the obtained data show a behavior typical of paramagnetic high-spin Co(ii) ions in a tetrahedral geometry, with a considerable contribution of the ZFS effect in a low temperature range. All complexes were also probed for SIM behavior. The modeling of the magnetic and EPR data was done for samples 1, 3, 4 and 5 to estimate ZFS parameters. The obtained results imply a negative value of the axial parameter D in complex 4 and positive D values for the rest of the compounds. A comparative magneto-structural analysis of complexes 4 and 5 points to the high sensitivity of the single-ion magnetic anisotropy of tetrahedral Co(ii) complexes to subtle changes in the first and second coordination spheres of Co(ii) ions.

Utilization of shale cuttings in production of lightweight aggregates.

The development of technologies for unconventional hydrocarbon exploration requires designing procedures to manage drilling waste that are consistent with the waste management hierarchy. In view of this, the possibility to apply shale drill cuttings as a prospective additive (replacing bentonite) to fly ash used for the production of lightweight aggregates (LWAs) was investigated. Moreover, a facile, waste-free method of LWAs production with using shales was proposed. Cuttings were characterized in terms of their mineralogical and elemental composition (XRD and XRF) as well as thermophysical behavior (TG-DTA and fusibility test). The sintered product, in turn, was assessed taking into account its structure, physicochemical and mechanical properties. It was found that the composition of the shale drill cuttings meets the conditions required for the bloating (as expressed by the SiO2/ΣFlux and Al2O3/SiO2 ratios) and binding processes (Al2O3 content), essential for the aggregates production. In comparison to bentonite, shales provided an additional source of kaolinite, which thermal transformation to mullite is crucial for the formation of mechanically durable structure of the aggregate. Moreover, the bulk density of the sintered product was found to be less than 1200 kg/m3, and the dry particle density below 2000 kg/m3, confirming that the obtained porous material belong to lightweight aggregates with accordance to European standard (UNE-EN-13055-1). The porosity of LWA was found to be higher (even up to 50%), thus the apparent density lower, compared with the reference product containing bentonite. These properties were accompanied by the relatively high crushing resistance which was up to 4.4 N/mm2. Hereby, usefulness of shale drill cuttings for LWAs production was confirmed.

The role of purinergic P2Y12 receptor blockers on the angiogenic properties of endothelial cells: an in vitro study.

Pharmacotherapy with agents that inhibit platelet function has proven to be effective in the treatment of acute coronary syndrome. Proper re-endothelization after angioplasty prevents adverse cardiovascular events. Therefore, in this in vitro study we examined how antiplatelet P2Y12 receptor blockers can affect endothelial cells' angiogenic properties. Endothelial cells were exposed to ticagrelor, prasugrel and clopidogrel in their highest concentrations obtained in serum after the treatment with loading and clinical doses. Further, the viability, apoptosis, and necrosis were tested and the following angiogenic properties such as proliferation, migration, invasiveness, tube formation, wound healing and the production of angiogenic mediators (bFGF, PDGF, MMP-2, Ang-2, TIMP-1). The results of this study showed that P2Y12 receptor blockers in the tested concentrations are safe for endothelial cells. They neither induced necrosis or apoptosis nor changed the endothelial cell viability, migration, invasiveness, tube formation, wound healing, the production of VEGF or its receptors. However, they reduced cell proliferation. It was shown that out of these three drugs, ticagrelor in its loading concentration had the most potent angiogenic property. It reduced cell proliferation and changed the production of angiogenic (bFGF, MMP-2) and angiostatic mediators (Ang-2). In conclusion, P2Y12 receptor blockers in the concentrations obtained in the serum during standard therapy reduced endothelial cell proliferation. Despite this slight antimitogenic effect, they did not change endothelial cell tube formation or wound healing. Out of the three tested drugs, ticagrelor had the most potent angiogenic effect in vitro, but not strong enough to disturb tube formation and wound healing.

Weight loss-dependent and -independent effects of moderate calorie restriction on endothelial cell markers in obesity.

Endothelial cell dysfunction in obesity can be reduced by calorie restriction (CR), however it is unclear whether this benefit requires a concomitant weight loss or is it simply related to the reduced calorie intake per se. In our study serum was drawn from 41 obese women who were undergoing an 8-week dietary intervention with 15 - 30% energy deficit, and from 48 age- and sex-matched controls of normal weight. Serum was analysed for biomarkers of endothelial cell function, oxidative stress and inflammation. Compared with non-obese individuals, the obese patients had lower serum levels of nitric oxide (NO), adiponectin, and decreased serum antioxidant status. They also had significantly higher levels of adhesive molecules, thrombomodulin (TM), von Wilebrand factor (vWF), asymmetric dimethylarginine (ADMA), tumor necrosis factor-α (TNF-α), interleukin-6 (IL-6), and leptin. To further characterize the effect of moderate CR, the patients were ranked into two comparable groups according to the extent of weight loss - below and above the median (-5.8 kg). A moderate dietary intervention did not correct adiponectin, antioxidant status, vWF, TM, and plasminogen activator inhibitor-1 (PAI-1) but ameliorated changes in other parameters. Only changes in NO and - to a lesser degree - in sE-selectin showed a clear relationship with the magnitude of weight reduction. By contrast, a beneficial reduction in TNF-α occurred equally in patients who lost more or less weight after caloric restriction. We concluded that moderate calorie restriction could still improve several parameters of endothelial cell function irrespective of whether it was accompanied by changes in body mass. However, a significant improvement in nitric oxide, a key mediator of endothelial well-being, requires a substantial reduction in body weight.

Predicting the critical micelle concentrations of aqueous solutions of ionic liquids and other ionic surfactants.

Some ionic liquids (ILs) are structurally analogous to surfactants, especially those that consist of a combination of organic and inorganic ions. The critical micelle concentration (CMC) is a basic parameter of surface chemistry and colloid science. A significant amount of research has already been carried out to determine the CMCs of ILs. However, because of the many varied cation/anion combinations, it is a daunting task to measure the CMCs of all possible ILs. Herein we suggest a general rule for predicting the CMCs of ionic surfactants in water based on data from COSMO-RS calculations. In accordance with the Stauff-Klevens rule, the molecular volume (V(m)) is sufficient to describe similar homologous series of cationic surfactants such as imidazolium- and ammonium-based ionic liquids with varying side-chain lengths. However, to also include anionic surfactants like Na[C(n)SO(4)] in a more general correlation, V(m) has to be exchanged by the cubed molecular radius (r3(m)) and the molecular surface has to be used as an additional descriptor. Furthermore, to describe double amphiphilic compounds like [C(4)MIm][C(8)SO(4)], the enthalpies of mixtures calculated by COSMO-RS have to be taken into account. The resulting equation had allowed us to predict the CMCs of all of the 36 tested surfactants with an error similar to or smaller than the usual experimental errors (18 different cations, 10 different anions: root mean squared error (rmse)=0.191 logarithmic units; R(2)=0.994). We discuss the factors governing micelle formation on the basis of our calculations and show that the structure of our equation can be related to Gibbs' theory of crystallization.

1-(N-trifluoroacetylamino)alkylphosphonic acids: synthesis and properties.

The 1-(N-trifluoroacetylamino)alkylphosphonic acids (TFA-AA(P)) - sub-products in the synthesis of O,O-dialkyl 1-(N-trifluoroacetylamino)alkylphosphonates and O,O-diethyl 1-aminoalkylphosphonates, were synthesized in two-stage transformations of 1-aminoalkylphosphonic acids including: trifluoroacetylation of 1-aminoalkylphosphonic acids (AA(P)) using a trifluoroacetic anhydride/trifluoroacetic acid reagent (AA(P) + TFAA/TFA-->2) and subsequent hydrolysis of the intermediary compounds 2 into desired TFA-AA(P) (2-->TFA-AA(P)). These intermediates 2 presented mixtures of the type of mixed anhydrides of TFAA and 1-(N-trifluoroacetylamino)alkylphosphonic, pyrophosphonic and polyphosphonic acids, which underwent rapid and quantitative conversion to corresponding TFA-AA(P) during treatment with an excess of water. The title acids were isolated by direct evaporation of the corresponding post-reaction mixtures, and their physicochemical proprieties, including deacylation abilities, were determined. TFA-AA(P) compounds can be re-converted into the starting amino acids AA(P) under respectively mild conditions (AA(P)-->TFA-AA(P)-->AA(P)).

Education / training in supportive and palliative care in central and eastern Europe. Results of a questionnaire survey.

During the totalitarian era terminal care was excluded from the health care system, and oncology, including education in the field, was rather neglected. The political and economic reforms that started in the 1990s in the countries of eastern and central Europe enhanced the development of palliative care and improvements in cancer treatment standards. This survey was performed to assess the current status of education and training in supportive and palliative care. A questionnaire was prepared and distributed by the authors to national leaders in palliative/supportive care. Data obtained from 16 countries indicate progress in palliative care provision and education, though it is held up by economic difficulties and by the lack of regulations in countries engaged in reforms of their health care systems. Training in supportive care is deficient; the discipline is usually perceived as the management of side-effects of anticancer treatment, so that it is not separated from clinical oncology. Access to professional literature should be improved, and the creation of national literatures should be encouraged. The role of local leaders, NGOs and professional associations must be emphasized. The main goals are: improvement of education, and better quality and availability of palliative and supportive care, not only for patients with cancer but also in other progressive life-threatening diseases.

Effect of bacteriological status on pressure ulcer healing in patients with advanced cancer.

OBJECTIVES: This study aimed to identify the quantitative and qualitative bacteriological status of pressure ulcers in patients with advanced cancer, and the effects on the healing process. METHOD: We recruited 34 patients with advanced cancer who had 38 superficial grade II and III pressure ulcers. Patients were randomly allocated to treatment with Lyofoam/polyurethane foam dressing (Seton) or Aquagel/hydrogel dressing (Wytw.Opatrunków). Efficacy, treatment times and healing rates were noted. Qualitative studies were undertaken on 38 pressure ulcers and quantitative bacteriological studies on 19 ulcers. RESULTS: There was no statistical difference between the two treatment groups in efficacy, healing rates and treatment times. Bacteriological assessment identified 92 species. CONCLUSION: The bacteria did not cause any clinical signs of infection. Variations in the number and types of bacteria in individual wounds did not correlate to the grade of ulcer or the dressing used.

Type I 5'-iodothyronine deiodinase activity and mRNA are remarkably reduced in renal clear cell carcinoma.

The purpose of this study was to compare thyroid hormone metabolism between non-cancerous tumor-surrounding human kidney tissues and renal clear cell carcinomas (RCCC). The material consisted of samples taken from 10 RCCC patients of both sexes and three grades of differentiation, G1 to G3. We showed that, similar to rat tissue, type I 5' monodeiodinase (5'DI) expression is heterogeneous within the human kidney. We also found a poor correlation between 5'DI activity and mRNA level in non-cancerous tumor-surrounding tissue suggesting significant post-transcriptional regulation of 5'DI expression by an unidentified process in the human kidney. In all RCCC tissues both 5'DI activity and mRNA levels were undetectable. This suggests either loss of human 5'DI gene expression during neoplastic transformation or the origination of RCCC from a tubular cell type that does not express 5'DI.

The effects of midazolam and morphine on analgesic and sedative activity of ketamine in rats.

The aim of this study was to investigate possible interactions between the analgesic activity of ketamine (an N-methyl-D-aspartate antagonist), midazolam (a benzodiazepine derivative) and morphine using the tail-flick test in rats. Animals were treated s.c. with ketamine (1.0-10.0 mg/kg), midazolam (0.3 mg/kg), or morphine (0.6 mg/kg) alone. or in combination The strongest analgesic effect of ketamine was observed after 3.0 mg/kg. In higher doses no enhancement of ketamine activity were found. After morphine and ketamine (3.0 mg/kg) or morphine, midazolam and ketamine co-administration. higher antinociceptive effects compared to ketamine activity were found. Rats administered midazolam and ketamine (3.0 mg/kg) showed a decrease of the effect of ketamine analgesia, and the antinociceptive effect of the three-component mixture was lower than after co-injection of morphine and ketamine. The interaction of these two compounds with ketamine (5.0 mg/kg) occurred in a different manner, because midazolam led to a strong enhancement of ketamine analgesia. After morphine and ketamine (5.0 mg/kg) administration, very weak increase of ketamine analgesia was observed. The results of this study allow better understanding of the alteration of the analgesic effects of low doses of ketamine under the influence of morphine and midazolam.

[Research from the Palliative Care Department in Poznan on treatment of neoplasm pain with Durogesic (transdermal fentanyl)]. / Doswiadczenia Kliniki Opieki Paliatywnej w Poznaniu w leczeniu bólu nowotworowego preparatem Durogesic (przezskórny fentanyl).

Transdermal Fentanyl (TF, Durogesic) is a strong opioid analgesic which is used in the treatment of cancer pain. In this article we described basic properties and dosing guidelines for TF and our own experience with use of Durogesic in the treatment of cancer pain. In this open study TF was administered in 16 pts aged of 30-88 (mean 62 +/- 17) years with advanced cancer who suffered from strong cancer pain and who had previously been treated with morphine (11 pts), buprenorphine (1 pt), tramadol (2 pts) and non-opioid analgesics (2 pts). Analgesic efficacy and side-effects of TF were appraised. The time of the treatment was 7-235 (mean 77 +/- 58) days, the dose range 25-600 (mean 129 +/- 117) micrograms/h. The mean initial dose of Durogesic was 94 +/- 99 micrograms/h and the final dose of fentanyl patch was 156 +/- 149 micrograms/h. Good analgesic effect was achieved in 11 pts (69%), partial effect in 2 pts (12%), unsatisfactory analgesia in 3 pts (19%). The treatment was well tolerated and the most frequent adverse reactions were constipation in 10 pts (63%) and drowsiness in 4 pts (25%). During the therapy with TF we didn't encounter serious side-effects which would cause cessation of the treatment. Results of our study confirmed that TF was an effective analgesic most commonly used in pts with stable nociceptive pain especially when opioid analgesics could not be administered orally.

Potential uses of topical opioids in palliative care--report of 6 cases.

Opioids used topically may exercise several useful clinical effects. Opioids may cause immediate local analgesia and also may work indirectly through decreasing the inflammation process. In this article we describe six patients treated with topical opioids because of cutaneous pain due to tumor infiltration. skin ulcers of malignant and non-malignant origin, severe oral mucositis, pain due to knee arthrosis and severe tenesmoid pain. In all but one case, topical morphine provided rapid relief which lasted usually for 7-8 h. The side effects of topical opioids were none or minimal. Possible mechanisms of topical analgesia are discussed.

A single cysteine, Cys-64, is essential for assembly of tenascin-C hexabrachions.

Tenascin-C is a large, multimeric extracellular matrix protein that is found in a variety of tissues and can have profound effects on cell adhesion. It is secreted from cells as a hexamer of six identical chains called a hexabrachion. Disulfide bonding among tenascin subunits mediates intracellular assembly into hexamers. The amino-terminal assembly domain consists of heptad repeats and at least six cysteine residues (Cys-64, -111, -113, -140, -146, -147) that could be involved in multimerization. We have now determined the requirements for these cysteine residues during hexamer assembly. Our results show that only Cys-64 is required to form the hexameric structure. Mutation of Cys-64 to glycine resulted in release of trimer intermediates, which probably form via the heptad repeats, but no hexamers were secreted. In contrast, individual or pairs of mutations of each of the other cysteines had no effect on tenascin hexamer formation, and inclusion of any other cysteine mutations along with C64G did not further disrupt the multimer pattern. However, when all six cysteines were mutated, monomers were the major extracellular form. Together, these results show that trimers are an intermediate of tenascin-C assembly and that Cys-64 is essential for formation of hexabrachions.

[The quality of life in particular phases of disease in women treated for genital neoplasms]. / Jakosc zycia w poszczególnych fazach choroby u kobiet leczonych z powodu nowotworów narzadów plciowych.

The authors have performed psychological analysis in women with diagnosed neoplasma of the genital organs. All of them were treated with radiotherapy. The quality of life depended on the phase of the disease in which they had been.

Palliative/hospice care in Poland.

The first hospice in eastern Europe was the Hospicium in Krakow, which was created 10 years ago. Three years later the leading independent Polish hospice, Hospitium Pallotinum, was founded in Gdansk. This hospice helped to organize more than 20 similar groups, usually Catholic agencies which offer home care programmes. The University Palliative Care Service in the Academy of Medical Sciences in Poznan, which was created in 1988, consists of a home care team caring for 600 patients a year and has a seven-bed inpatient unit. It offers an education programme for physicians, nurses, medical and pharmacy students as well as a research programme. There is currently an academic link between the Poznan Palliative Care service and Sir Michael Sobell House in Oxford, sharing medical and nursing education in palliative care. The educational courses and conferences have been attended by international speakers offering education which will help to change the attitudes of professional health care workers and the public. We hope that the Polish Ministry of Health and Welfare and the government will be interested in establishing policies that will cover the cost of palliative care in the newly developing health care system.