Encapsulation of small gas molecules by cryptophane-111 in organic solution. 1. Size- and shape-selective complexation of simple hydrocarbons.

The reversible trapping of small hydrocarbons and other gases by cryptophane-111 (1) in organic solution was characterized with variable-temperature (1)H NMR spectroscopy. Characteristic spectral changes observed upon guest binding allowed kinetic and thermodynamic data to be readily extracted, permitting quantification and comparison of different host-guest interactions. Previous work (J. Am. Chem. Soc. 2007, 129, 10332) demonstrated that 1, the smallest cryptophane to date, forms a complex with xenon with remarkably high affinity. Presently, it is shown that 1 also exhibits slow exchange dynamics with methane at reduced temperatures (delta(bound) = -5.2 ppm) with an association constant K(a) = 148 M(-1) at 298 K. In contrast, ethane and ethylene are poorly recognized by 1 with K(a) values of only 2 M(-1) and 22 M(-1), respectively; moreover, chloromethane (whose molecular volume is similar to that of xenon, approximately 42 A(3)) is not observed to bind to 1. Separately, molecular hydrogen (H(2)) gas is observed to bind 1, but in contrast to other ligands presently studied, H(2) complexation is spectrally manifested by fast exchange throughout virtually the entire range of available conditions, as well as by a complex dependence of the guest (1)H resonance frequency upon temperature and host concentration. Taken together, these results establish 1 as a selective host for small gases, with implications for the design of size- and geometry-selective sensors targeted for various gas molecules.

pH-Sensitive MR Responses Induced by Dendron-Functionalized SPIONs.

We report a series of investigations of the pH-sensitive magnetic resonance (MR) responses of various surface-functionalized SPIONs (superparamagnetic iron oxide nanoparticles). First, functionalization of ~12 nm highly monocrystalline SPION cores with three different generations of melamine-dendrons was optimized to give agents with high molar relaxivities (e.g. R2m ~300 mM-1·s-1 at 7 T and R1m ~20-30 mM-1·s-1 at 0.5 T) and excellent aqueous stabilities. Molar relaxivities were found to exhibit great sensitivity to pH at physiologically-relevant ionic strengths, with sharp inflections observed at pH values near the pKa of the melamine monomer. The strength of the effect was observed to grow with increasing dendron generation (with concomitant shift in the position of the main pH inflection). Opposing behavior in R2m and R2m * trends may be exploited to provide a ratiometric MR response to pH. Combined with TEM and corresponding MR measurements from solutions of varying ionic strengths, these results are consistent with the pH-sensitive behavior originating from transient, reversible SPION clustering modulated by an interplay between SPION surface charge density and solution ionic strength. Studies of SPION cellular uptake and MR response in HeLa cell cultures are also presented. Finally, comparisons with the MR responses of SPIONs with alternative functionalities-derivatives of nitrilotriacetic acid or poly(1-vinylimidazole)-indicate that these types of pH-sensitive MR responses can be highly dependent upon the chemical composition of the surface species (and thus amenable to modulation through rational design).

Generation of laser-polarized xenon using fiber-coupled laser-diode arrays narrowed with integrated volume holographic gratings.

Volume holographic gratings (VHGs) can be exploited to narrow the spectral output of high-power laser-diode arrays (LDAs) by nearly an order of magnitude, permitting more efficient generation of laser-polarized noble gases for various applications. A approximately 3-fold improvement in (129)Xe nuclear spin polarization, P(Xe), (compared to a conventional LDA) was achieved with the VHG-LDA's center wavelength tuned to a wing of the Rb D(1) line. Additionally, an anomalous dependence of P(Xe) on the xenon density within the OP cell is reported-including high P(Xe) values (>10%) at high xenon partial pressures (approximately 1000 torr).

NMR studies of chloroform@cryptophane-A and chloroform@bis-cryptophane inclusion complexes oriented in thermotropic liquid crystals.

Oriented inclusion complexes of chloroform@cryptophane-A and chloroform@bis-cryptophane were prepared using a nematic thermotropic liquid crystal (ZLI 1132), and the alignment and magnetic resonance properties of these host-guest systems were studied via (13)C NMR of the labeled guests. Large (1)H-(13)C dipolar splittings for (13)CHCl(3) guests indicated significantly enhanced (approximately 2-fold) ordering for the trapped vs. free ligands under all conditions studied, with similar ordering observed for the two complexes-despite significant differences in size and motional freedom between the hosts. For each environment, variable-temperature studies permitted the sign and magnitude of the order parameter for chloroform's C-H bond to be independently determined from the (13)C chemical shift anisotropy (CSA) shifts (via the gradient method) and the restored (1)H-(13)C dipolar couplings. In both systems, the results are consistent with overall alignment of the complexes such that the cage principal axis lies roughly perpendicular to the LC director.