Tailoring the surface charge of dextran-based polymer coated SPIONs for modulated stem cell uptake and MRI contrast

Tracking stem cells in vivo using non-invasive techniques is critical to evaluate the efficacy and safety of stem cell therapies. Superparamagnetic iron oxide nanoparticles (SPIONs) enable cells to be tracked using magnetic resonance imaging (MRI), but to obtain detectable signal cells need to be labelled with a sufficient amount of iron oxide. For the majority of SPIONs, this can only be obtained with the use of transfection agents, which can adversely affect cell health. Here, we have synthesised a library of dextran-based polymer coated SPIONs with varying surface charge from −1.5 mV to +18.2 mV via a co-precipitation approach and investigated their ability to be directly internalised by stem cells without the need for transfection agents. The SPIONs were colloidally stable in physiological solutions. The crystalline phase of the particles was confirmed with powder X-ray diffraction and their magnetic properties were characterised using SQUID magnetometry and magnetic resonance. Increased surface charge led to six-fold increase in uptake of particles into stem cells and higher MRI contrast, with negligible change in cell viability. Cell tracking velocimetry was shown to be a more accurate method for predicting MRI contrast of stem cells compared to measuring iron oxide uptake through conventional bulk iron quantification

Sterically restricted tin phosphines, stabilized by weak intramolecular donor-acceptor interactions

Funding: Engineering and Physical Sciences Research Council (EPSRC)Four related sterically restricted pen-substituted acenaphthenes have been prepared containing mixed tin phosphorus moieties in the proximal 5,6-positions (Acenap[SnR3][(PPr2)-Pr-i]; Acenap = acenaphthene-5,6-diyl; R-3 = Ph-3 (1), Ph2Cl (2), Me2Cl (3), Bu2Cl (4)). The degree of intramolecular P-Sn bonding within the series was investigated by X-ray crystallography, solution and solid-state NMR spectroscopy, and density functional theory (DFT/B3LYP/SBKJC/PCM) calculations. All members of the series adopt a conformation such that the phosphorus lone pair is located directly opposite the tin center, promoting an intramolecular donor acceptor P -> Sn type interaction. The extent of covalent bonding between Sn and P is found to be much greater in triorganotin chlorides 2-4 in comparison with the triphenyl derivative 1. Coordination of a highly electronegative chlorine atom naturally increases the Lewis acidity of the tin center, enhancing the Ip(P)-sigma*(Sn-Y) donor acceptor 3c-4e type interaction, as indicated by conspicuously short Sn-P peri distances and significant (1)J(P-31,Sn-119) spin spin coupling constants (SSCCs) in the range 740-754 Hz. Evidence supporting the presence of this interaction was also found in solid-state NMR spectra of some of the compounds which exhibit an indirect spin spin coupling on the same order of magnitude as observed in solution. DFT calculations confirm the increased covalent bonding between P and Sn in 2-4, with notable WBIs of ca. 0.35 obtained, in comparison to 0.1 in 1.PostprintPeer reviewe

Rhodium(III) and iridium(III) half-sandwich complexes with tertiary arsine and stibine ligands

This work was financially supported by the EPSRC and the EPSRC National Mass Spectrometry Service Centre (NMSSC) Swansea.The syntheses of rhodium(III) and iridium(III) half sandwich complexes containing tertiary arsine and stibine ligands of the form [Cp*M(L)Cl2] (M = Rh, Ir; L = AsEt3, AsPh3, SbPh3) are reported. These compounds represent infrequent examples of rhodium and iridium metal complexes bearing arsenic or antimony ligands. All new compounds were fully characterised using 1H and 13C NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. DFT calculations show the formation of the complexes from (Cp*MCl2)2 and EPh3 (E = P, As, Sb) to be highly exothermic, although the enthalpic driving force is decreasing in the expected sequence P > As > Sb.PostprintPeer reviewe

Delivering services by building and running virtual organisations

Non peer reviewedPostprin

Reactivity profile of a peri-substitution-stabilized phosphanylidene-phosphorane : synthetic, structural, and computational studies

The authors thank the EaStChem, EPSRC, and the COST actions CM0802 PhoSciNet and CM1302 SIPs for financial support.The reactions of peri-substitution-stabilized phosphanylidene-phosphorane 1 with [AuCl(tht)] or [PtCl2(cod)] afford binuclear complexes [((1)(AuCl)2)2] 2 and [((1)(PtCl2))2] 3, in which four electrons of the ligand are used in bonding to two metal atoms in the bridging arrangement. Reactions of 1 with [Mo(CO)4(nbd)] or (RhCl2Cp*)2 afford mononuclear complexes [(1)2Mo(CO)4] 4 and [(1)RhCl2Cp*] 5, in which two electrons of the ligand are used to form terminal complexes. Formation of these complexes disrupts the negative hyperconjugation at the P–P bond to various extents, which is mirrored by variations in their P–P bond distances (2.179(4)–2.246(4) Å). The P–P bond is ruptured upon formation of Pd diphosphene complex 6, which is likely to proceed through a phosphinidene intermediate. In air, 1 is fully oxidized to phosphonic acid 7. Reactions of 1 with chalcogens under mild conditions generally afford mixtures of products, from which the trithionated 8, dithionated 9, diselenated 10, and monotellurated 11 species were isolated. The bonding in the chalcogeno derivatives is discussed using DFT (B3LYP) and natural bond orbital analysis, which indicate a contribution from dative bonding in 8–10. The buttressing effect of the peri backbone is shown to be an essential factor in the formation of the single push–double-pull bis(borane) 13. This is demonstrated experimentally through a synthesis parallel to that used to make 13, but lacking the backbone, which leads to different products. The P–P bond distances in the reported products, as well as additional species, are correlated with Wiberg bond indices, showing very good agreement for a variety of bonding modes, including the negative hyperconjugation.PostprintPostprintPeer reviewe

Risk of skin cancer after neonatal phototherapy : retrospective cohort study

Peer reviewedPostprin

Characteristics associated with noncompliance of current pitch smart guidelines in high school baseball pitchers throughout the United States

BACKGROUND: Although pitch count and rest guidelines have been promoted for youth and adolescent baseball players for nearly 2 decades, compliance with guidelines remains poorly understood. PURPOSE/HYPOTHESIS: The purpose of this study was to determine the frequency of compliance with Major League Baseball (MLB) Pitch Smart guidelines as well as the association between compliance and range of motion (ROM), strength, velocity, injury, and pitcher utilization. It was hypothesized that pitchers in violation of current recommendations would have increased strength, velocity, and injury. STUDY DESIGN: Case-control study; Level of evidence, 3. METHODS: This was a prospective, multicenter study of 115 high school pitchers throughout the United States. Pitchers were surveyed about their compliance with current off-season, rest-related guidelines, and history of injury. During the preseason, pitchers underwent standardized physical examinations, and pitch velocity was measured. Pitch counts were collected during the baseball season that followed. Dynamometer strength testing of shoulder forward flexion, and external rotation as well as grip strength was recorded. We compared pitchers who were compliant with recommendations with those who were noncompliant using Student RESULTS: Based on preseason data, 84% of pitchers had violated current Pitch Smart guidelines. During the season, 14% had at least 1 violation of the Pitch Smart guidelines. Across both the preseason survey and in-season pitch counts, 89% of players had at least 1 violation of the Pitch Smart guidelines. While there were no significant differences in ROM or strength, the noncompliant group had higher maximum pitch velocity than the compliant group (74 ± 8 vs 69 ± 5 mph [119 ± 13 vs 111 ± 8 kph], respectively; CONCLUSION: Most high school pitchers were not fully compliant with current Pitch Smart guidelines, and they tended to overestimate their peak velocity by 7 mph (11 kph). Pitchers who threw with greater velocity were at higher risk for violating Pitch Smart recommendations