Proof of ion-pair structures in ammonium-based protic ionic liquids using combined NMR and DFT/PCM-based chemical shift calculations.

The self-assembly of triethylammonium bis(trifluoromethylsulfonyl)imide, i.e. [(C2H5)3NH][TFSI], in chloroform and aqueous solutions has been investigated using 1H NMR spectroscopy and computational (DFT/PCM prediction) methods. We have examined a number of ion pairs formed between the [(C2H5)3NH]+ cation with different conformations of alkyl substituents as well as various dispositions of the multi-site [TFSI]- anion. Based on the agreement between the calculated (DFT) and observed 1H NMR chemical shifts, [(C2H5)3NH][TFSI] in chloroform formed lipophilic complexes with effective N+-HN or N+-HO hydrogen bonding, whereas hydrophilic complexes with Cα-HO and Cα-HF hydrogen bonding are found in aqueous solutions. This study provides a new insight into the self-aggregation of ammonium PILs incorporating the widely used [TFSI]- anion and demonstrates the importance of solvent effects on chemical shifts. The simulations with explicit and implicit dielectric continuum solvents are found to be the most realistic method, yielding a representative ensemble of structures.

Effect of low water content in protic ionic liquid on ions electrosorption in porous carbon: application to electrochemical capacitors.

The effect of low water content (<20, 150, 1000, 10 000 ppm) in triethylammonium bis[(trifluoromethyl)sulfonyl]imide - [(C2H5)3N+H][TFSI-] - protic ionic liquid (PIL) on the performance of activated carbon (AC) electrodes as well as AC/AC electrochemical capacitors (ECs) is reported. Under negative polarization, hydrogen electrosorption onto carbon is enhanced along with the increase of water content in PIL, whereas the resulting desorption peaks are shifted to lower potential values, evidencing lower sorption energy when hydrogen is stored from moisture containing PIL. Cyclic voltammetry (CV) investigations on PIL-based ECs demonstrated that the evolution of the Stern layer nanostructure at positive and negative potentials is asymmetrical. The results revealed comparable electrochemical performance for PIL containing 150 and 1000 ppm of H2O, due to similar operation of the positive electrode, where [TFSI-] anions are adsorbed in the outer Helmholtz plane, and the negative one, where hydrogen is stored through the reduction of the intermediate hydronium cation. By contrast, a cell with "dry" PIL (<20 ppm of water) displayed a distinctive operation due to hydrogen electrosorption directly through reduction of the protonated cation, and selective adsorption of [TFSI-] anions, which occurs thanks to the high polarizability and image force (IF) created by their induced charge. Galvanostatic cycling with potential limitation (GCPL) showed comparable capacitance values whatever the water content in PILs up to 1000 ppm, yet electrochemical impedance spectroscopy (EIS) revealed higher capacitance as well as better retention at higher frequencies with the PIL containing 150 ppm of water. Hence, 150 ppm is reasoned to be an optimal value for diffusion and adsorption of ions. The nature of current collectors (aluminum or stainless steel) has a determining role in their polarization behavior, and consequently the potential range of electrodes as well as ion diffusion into the activated carbon porosity, influencing the observed capacitance values (CEIS/2.0V: 170 vs. 128 F g-1, for Al and SSt, respectively).

Further delineation of the classical Smith-Lemli-Opitz syndrome phenotype at different patient ages: clinical and biochemical studies.

We present here extensive clinical and biochemical data on thirteen SLOS (type I) patients with proven defect in cholesterol biosynthesis for further delineation of the classical SLOS phenotype at different patient ages.

[Recurrent abdominal pain in children]. / Nawracajace bóle brzucha u dzieci.

In the paper the results are presented of an analysis of the causes of recurrent abdominal pain in 294 children hospitalized at the Gastroenterology Department, Childrens Health Centre, and the accepted diagnostic programme is evaluated. The children were referred to the CHC, as a rule with a suggestion of organic causes of recurrent abdominal pain. On the basis of carried out examinations the following was diagnosed: in 111 children organic causes (37.8% of the studied group), in 94 children recurrent abdominal pain of functional aetiology (32%), in 53 children psychological background (18%), and in 36 children mixed organic and functional background. These proportions between those groups is the result of the selection carried out at earlier stages of the diagnostic process. In the paper, the correctness and validity of the accepted diagnostic programme are also demonstrated.

[Evaluation of microtest in dextran gel for blood group serology]. / Ocena mikrometody z zastosowaniem zelu dekstranowego w serologii grup krwi.

Microtest in gel was compared to the traditional, immunohaematological methods. Blood samples of 1.032 persons were tested. From the results presented in this paper we conclude that Gel-test is specific, clear, easy to perform and more sensitive than the traditional methods. It can be used for red cell phenotyping and antibody detection as well. By this technique it was possible to establish the specificity of antibodies of Rh system not found by any other method. The advantage of this test is that nearly all unspecific reactions could be eliminated. The disadvantage concerned the high sensitivity in the detection of cold, clinically insignificant allo- and autoantibodies. Therefore, some modifications for the elimination of these unfavourable reactions were introduced.

Critical evaluation of the ADCC test.

The activity of monocytes in the ADCC test against human red blood cells sensitized with anti-Rh antibodies is unquestionable, however, a participation of lymphocytes in this reaction is still controversial. The aim of this paper was to test the cytotoxic activity of monocytes and lymphocytes isolated from human peripheral blood against erythrocytes coated with anti-C + D antibodies of Rh system. Due to some individual changes in the activity of mononuclears observed in the ADCC test, it was of interest to test how this activity changes with time, in individual healthy subjects. Both types of mononuclears were observed to damage the sensitized non-treated as well as papain-treated red cells. The cytotoxic activity of these cells, however, showed substantial deviation in the same person.

The comparison of susceptibility of two target cells (HuRBC and L1210) to antibody dependent lymphocyte cytotoxicity.

Antibody-dependent lymphocyte cytotoxicity was compared in two test procedures. Human erythrocytes (group O R1R1 or R2R2) and mouse lymphoma cells (line L1210) were used as target cells. Anti-Rh (anti-C + D) serum obtained from a hyperimmunized blood donor and serum obtained from rabbit immunized with L1210 cells were used as the source of antibody specific for target cells. In both tests, lymphocytes (PBL) or mononuclear cells (MNC) isolated from heparinized or defibrinated blood were used as effectors. In both tests comparable results were obtained.

[Antibody-dependent cytotoxic activity of peripheral blood lymphocytes in healthy subjects]. / Zalezna od przeciwcial aktywnosc cytotoksyczna limfocytów krwi obwodowej u zdrowych osób.

A method of determining the cytotoxic activity of peripheral blood lymphocytes against Rh-positive erythrocytes labelled with 51Cr and sensitized with anti-D antibody is described. A measure of this activity was the cytotoxic index reflecting the intensity of erythrocytolysis, and expressed as per cent of released 51Cr. The method was applied in investigations of lymphocytes of 54 blood donors. The values of the cytotoxic index ranged from 60% to 94%, the arithmetical mean was 76 +/- 10%. The obtained results are an introduction to further investigations on changes of lymphocytes K in blood diseases.

[Detection of light chains of warm-type autoantibodies in autoimmune hemolytic anemia with the aid of an autoanalyzer]. / Wykrywanie lancuchów lekkich autoprzeciwcial typu cieplego w niedokrwistosciach autoimmunohemolitycznych przy uzyciu autoanalizatora.

A method was evolved for detection of light chains of erythrocyte autoantibodies using a Technicon II AutoAnalyser with properly selected dilutions of bromelin and methylcellulose and anti-kappa and anti-lambda sera. It was demonstrated that the method is superior to the direct Coombs test because it made possible detection of one or both light chains in warm autoantibodies coating the erythrocytes of 20 patients with autoimmunohaemolytic anaemias in whom they could not have been detected by the manual method. It was found that in warm-type autoantibodies light chains can be detected always and that in some cases only one light chain is found.

[Rare erythrocyte phenotypes imitating weak variant of antigen A]. / Rzadkie fenotypy krwinek czerwonych imitujace slaba odmiane antygenu A.

Two phenotypes with defect of sialic acid in the cell membrane of erythrocytes due to some unknown factor, imitating the weak variant of antigen A are reported. One of them found in a healthy candidate for blood donation was called Tn. The second one associated with thrombocytopenia and anaemia differed from all as yet classified ones in that it had simultaneously increased expression of antigen H and lack of reaction with Dolichos biflorus lectin. For demonstrating the diagnostic difficulties differentiation against the weak variant of antigen A approaching A3 is described.

[Light chains of warm autoantibodies in patients with autoimmune hemolytic anemia. Long-term observation]. / Wieloletnia obserwacja lancuchów lekkich autoprzeciwcial typu cieplego u chorych z niedokrwistoscia autoimmunohemolityczna.

In 18 patients with autoimmunohaemolytic anaemia presence of light chains of IgG autoantibodies was south for by the method of direct antiglobulin reaction. In 11 patients variability was observed in the detection of light chains. The authors discuss the possible causes of this observation: variable participation of different cell lines in the production of autoantibodies and changes in the conformation of immunoglobulin molecule in the erythrocyte.