Perfluoroalkylfullerenes

New chemical derivatives that possess the greatest variety of addition patterns than any other class of fullerene derivatives represent an important addition to the existing classes of perfluorocarbons, that is, compounds that are composed only of the two types of atoms, carbon and fluorine. These include aromatic and aliphatic perfluorocarbons such as perfluorodecalin, perfluorononane, hexafluorobenzene, etc., which are important as fluorous solvents used in medicine. The propensity of perfluoroalkylfullerenes (PFAFs) to readily crystallize from organic solutions upon slow evaporation in open air provided a straightforward access to their molecular structures via X-ray crystallography. Another crucial aspect that ensures future success in the characterization of numerous PFAFs of higher fullerenes and endohedral metallofullerenes is the possibility to apply HPLC methodologies to the separation of product mixtures. PFAFs, especially those of C60 and C70, are unique fullerene derivatives in terms of the number of structurally characterized derivatives with different number of RF groups and different addition patterns

Onomatopoeia in representing the semantics of love, affection, and gender relations

The paper describes the sound symbolic nature of linguistic units with the semantics of love, affection, gender relations in German and Russian. It is known that onomatopoeic words with the semantics of blow, the physiological sound of the body and the sounds of speech in German and Russian languages regularly form associated with love, affection, and gender relations. In most cases, this type of semantics is expressed by combination of plosives and sonorants sounds, and also vibrants. Inter-relation between sound and meaning, as well as the soundiconic functions of phonotypes is clarified: voiceless fricative sounds – reflection of pejorativeness, less often – femininity (dearness and softness); explosive and vibrant sounds – reflection of strong feelings, pressure, perseverance, aggressiveness in a relationship

Circulating antiplatelet antibodies in pregnant women with immune thrombocytopenic purpura as predictors of thrombocytopenia in the newborns

Newborns from mothers with immune thrombocytopenic purpura (ITP) have a risk of thrombocytopenia due to passage of maternal antiplatelet antibodies into fetal/neonatal circulation. We looked for predictors of neonatal thrombocytopenia (nTP) in pregnant women with ITP. One hundred pregnant women with platelet count <100 × 109/l, no non-immune causes of thrombocytopenia and increased platelet associated IgG (PA-IgG) were included in the study. Thirty seven and 63 of them gave birth to babies with and without nTP, respectively (nTP+ and nTP− groups). Platelet count, mean platelet volume, PA-IgG, antiplatelet circulating antibodies (cAB), time of ITP onset (before or during pregnancy), and frequency of corticosteroid treatment were compared in these groups. There were no differences in all test parameters between nTP+ and nTP− groups except cAB. These antibodies were detected in 33 out of 37 in nTP+ group and in 2 out of 63 mothers in nTP− group (p < 0.001). The sensitivity of this test was 89% and its specificity was 97%. A strong reverse correlation (r = −0.749, p < 0.001) was established between maternal cAB titer and neonatal platelet count. Antibodies against glycoproteins IIb–IIIa and/or Ib were identified in antigen specific MAIPA (Monoclonal Antibody Immobilization of Platelet Antigen) assay only in 10 out of 19 (53%) test sera with cAB. Antiplatelet cAB in pregnant women with ITP could serve as reliable predictors of nTP in their babies

Targeted Delivery of HSP70 to Tumor Cells via Supramolecular Complex Based on HER2-Specific DARPin9_29 and the Barnase:Barstar Pair

(1) Background: We have previously shown that the use of an artificial supramolecular two-component system based on chimeric recombinant proteins 4D5scFv-barnase and barstar-heat shock protein 70 KDa (HSP70) allows targeted delivery of HSP70 to the surface of tumor cells bearing HER2/neu antigen. In this work, we studied the possibility to using DARPin9_29-barnase as the first targeting module recognizing HER2/neu-antigen in the HSP70 delivery system. (2) Methods: The effect of the developed systems for HSP70 delivery to human carcinomas SK-BR-3 and BT474 cells hyperexpressing HER2/neu on the activation of cytotoxic effectors of the immune cells was studied in vitro. (3) Results: The results obtained by confocal microscopy and cytofluorimetric analysis confirmed the binding of HSP70 or its fragment HSP70-16 on the surface of the treated cells. In response to the delivery of HSP70 to tumor cells, we observed an increase in the cytolytic activity of different cytotoxic effector immune cells from human peripheral blood. (4) Conclusions: Targeted modification of the tumor cell surface with molecular structures recognized by cytotoxic effectors of the immune system is among new promising approaches to antitumor immunotherapy

Radical Trifluoromethylation of Sc\u3csub\u3e3\u3c/sub\u3eN@C\u3csub\u3e80\u3c/sub\u3e

The addition of CF3 radicals to both the I (h) and D (5h) cage-isomers Of SC3N@C-80 by high-temperature reaction of the metallic nitride fullerenes with gaseous CF3I has resulted in the isolation Of SC3N@(C-80-I (h))(CF3)2 and SC3N@(C-80-D (5h))(CF3)(2), which have idealized C-2 and C-s symmetry, respectively. Both new compounds were characterized by F-19 NMR and electronic absorption spectroscopy, mass spectrometry, and quantum-chemical calculations at the DFT level of theory, and the I h cage derivative was also characterized by cyclic voltammetry. The results indicate that both compounds have a p -C-6(CF3)(2) hexagon with endohedral Sc atoms bonded to the sp(2) cage C atoms para to the sp(3) cage C-6(CF3) atoms

Increased Susceptibility of the CD57⁻ NK Cells Expressing KIR2DL2/3 and NKG2C to iCasp9 Gene Retroviral Transduction and the Relationships with Proliferative Potential, Activation Degree, and Death Induction Response

Nowadays, the use of genetically modified NK cells is a promising strategy for cancer immunotherapy. The additional insertion of genes capable of inducing cell suicide allows for the timely elimination of the modified NK cells. Different subsets of the heterogenic NK cell population may differ in proliferative potential, in susceptibility to genetic viral transduction, and to the subsequent induction of cell death. The CD57−NKG2C+ NK cells are of special interest as potential candidates for therapeutic usage due to their high proliferative potential and certain features of adaptive NK cells. In this study, CD57− NK cell subsets differing in KIR2DL2/3 and NKG2C expression were transduced with the iCasp9 suicide gene. The highest transduction efficacy was observed in the KIR2DL2/3+NKG2C+ NK cell subset, which demonstrated an increased proliferative potential with prolonged cultivation. The increased transduction efficiency of the cell cultures was associated with the higher expression level of the HLA-DR activation marker. Among the iCasp9-transduced subsets, KIR2DL2/3+ cells had the weakest response to the apoptosis induction by the chemical inductor of dimerization (CID). Thus, KIR2DL2/3+NKG2C+ NK cells showed an increased susceptibility to the iCasp9 retroviral transduction, which was associated with higher proliferative potential and activation status. However, the complete elimination of these cells with CID is impeded

Sc\u3csub\u3e3\u3c/sub\u3eN@(C\u3csub\u3e80\u3c/sub\u3e-\u3cem\u3eI\u3c/em\u3e\u3csub\u3eh\u3c/sub\u3e(7))(CF\u3csub\u3e3\u3c/sub\u3e)\u3csub\u3e14\u3c/sub\u3e and Sc\u3csub\u3e3\u3c/sub\u3eN@(C\u3csub\u3e80\u3c/sub\u3e-\u3cem\u3eI\u3c/em\u3e\u3csub\u3eh\u3c/sub\u3e(7))(CF\u3csub\u3e3\u3c/sub\u3e)\u3csub\u3e16\u3c/sub\u3e. Endohedral Metallofullerene Derivatives with Exohedral Addends on Four and Eight Triple-Hexagon Junctions. Does the Sc\u3csub\u3e3\u3c/sub\u3eN Cluster Control the Addition Pattern or Vice Versa?

The compounds Sc3N@(C80-Ih(7))(CF3)14 (1) and Sc3N@(C80-Ih(7))(CF3)16 (2) were prepared by heating Sc3N@C80-Ih(7) and Ag(CF3CO2) to 350 °C in a sealed tube. The structures of 1 and 2 were determined by single-crystal X-ray diffraction. They are the first X-ray structures of any endohedral metallofullerene with more than four cage C(sp3) atoms. The structures exhibit several unprecedented features for metallic nitride fullerenes, including multiple cage sp3 triple-hexagon junctions (four on 1 and eight on 2), no cage disorder and little (2) or no (1) endohedral atom disorder, high-precision (C−C esd’s are 0.005 Å for 1 and 0.002 Å for 2), an isolated aromatic C(sp2)6 hexagon on 2, and two negatively charged isolated aromatic C(sp2)5− pentagons on 2 that are bonded to one of the Sc atoms. DFT calculations are in excellent agreement with the two Sc3N conformations observed for 2 (ΔE(calc) = 0.36 kJ mol−1; ΔE(exp) = 0.26(2) kJ mol−1)

Redox-Tuning Endohedral Fullerene Spin States: From the Dication to the Trianion Radical of Sc\u3csub\u3e3\u3c/sub\u3eN@C\u3csub\u3e80\u3c/sub\u3e(CF\u3csub\u3e3\u3c/sub\u3e)\u3csub\u3e2\u3c/sub\u3e in Five Reversible Single-Electron Steps

The first endohedral trianion captured: Sc3N@C80(CF3)2 (see figure) exhibits three reversible reductions and two reversible oxidations and affords the facile generation of the monocation, monoanion, and trianion in solution, which can be characterized by ESR and absorption spectroscopies. This is the first time that such a broad range of charged states of any endohedral fullerene has been spectroscopically characterized