Pentachlorocyclopropane/base complexes: matrix isolation infrared spectroscopic and density functional study of C-H- - -N hydrogen bonds

Hydrogen-bonded complexes of pentachlorocyclopropane with the bases acetonitrile, ammonia, monomethylamine, and dimethylamine have been isolated and characterized for the first time in argon matrices at 16 K. Coordination of the proton of pentachlorocyclopropane (Pccp) to the electron donor (N) of the base was evidenced by red shifts of the CH stretching mode. These shifts, which range from 22 to 170 cm(-1), increase in the order CH3CN, NH3, (CH3)NH2, and (CH3)2NH. Density functional theory (DFT) calculations at the B3LYP level agree well with experiment and support the formation of 1:1 complexes of Pccp/base. Distinct changes were observed in ring modes as well as CCl and CCl2 modes. The hydrogen bond energy of the complexes varies from 2.95 to 4.22 kcal/mol and is stronger than our previously studied bromocyclopropane-ammonia complex (2.35 kcal/mol, MP2).     

A new mechanism for electron spin echo envelope modulation

Electron spin echo envelope modulation (ESEEM) has been observed for the first time from a coupled heterospin pair of electron and nucleus in liquid solution. Previously, modulation effects in spin-echo experiments have only been described in liquid solutions for a coupled pair of homonuclear spins in nuclear magnetic resonance or a pair of resonant electron spins in electron paramagnetic resonance. We observe low-frequency ESEEM (26 and 52 kHz) due to a new mechanism present for any electron spin with S > 12 that is hyperfine coupled to a nuclear spin. In our case these are electron spin (S = 32) and nuclear spin (I = 1) in the endohedral fullerene N@C(60). The modulation is shown to arise from second-order effects in the isotropic hyperfine coupling of an electron and (14)N nucleus.     

Influence of Cd Content and Se Doping on the Formation of CdSe Nanocrystals in Silica Xerogels: A SAXS Study

Small-angle X-ray scattering (SAXS) experiments were carried out to characterize the structure of the composite formed by CdSe nanocrystals embedded in a popous silica matrix (silica xerogels containing Cd with formamide addition and ultrasound treatment). SAXS results from samples before Se diffusion indicate the presence of heterogeneities with a bimodal size distribution which was associated to the existence of mesopores (pores of several hundred Å) immersed in a nanoporous matrix (characteristic pore radii of 20–30 Å). The diffusion of Se induces the nucleation and growth of CdSe nanocrystals. The average size of the nanocrystals increases with Cd content. Higher Se doses promote the formation of larger nanocrystals (radius of gyration of ∼30 to 50 Å). Anomalous scattering results confirm the existence of Se aggregation associated with CdSe nanocrystal formation and suggest that only partial segregation of Cd and Se occurs.     

Folate-mediated cell targeting and cytotoxicity using thermoresponsive microgels

We describe the design of fluorescent, thermoresponsive microgels surface-functionalized with folic acid. Incubation of these particles with KB cells grown in folate-free medium results in efficient endocytosis of the particles via a receptor-mediated pathway. Laser scanning confocal microscopy and flow cytometry show efficient uptake of folate-modified particles over cationic control particles. Staining of the cells with Lysotracker red, followed by confocal imaging, shows anticorrelation between the particle and endosome fluorescence, which is taken as evidence of particle escape from the endosomes to the cytosol. Finally, the strong dependence of particle swelling on temperature was used to induce particle collapse and aggregation following uptake, which causes significant cytotoxicity. Thus, we have developed polymeric nanoparticles that may display antitumor activity, as they effectively target cancer cells and undergo endosomal escape to the cytosol, and they can then be triggered to cause cell death.     

Interfacial nonradiative energy transfer in responsive core-shell hydrogel nanoparticles

Fluorescently labeled core-shell latex particles composed mainly of the thermoresponsive polymer poly-N-isopropylacrylamide (p-NIPAm) have been synthesized such that an energy transfer donor (phenanthrene) and an energy transfer acceptor (anthracene) are covalently localized in the core and shell, respectively. When the thermally induced particle deswelling is interrogated by photon correlation spectroscopy (PCS), a continuous (non-first order) phase transition is observed. Conversely, when the nonradiative energy transfer (NRET) efficiency is used to probe the collapse of these same particles, the phase transition event is observed to occur over a much smaller temperature range and approaches first-order (discontinuous) behavior. Furthermore, core-shell particles with differing shell thicknesses display identical phase transition temperatures when PCS is used to monitor the transition, while NRET measurements show a clear increase in collapse temperature as the shell thickness is increased. These apparently contradictory results are discussed in terms of a radial phase coexistence that exists in the microgel particles, which arises from a similarly radial inhomogeneity in the cross-linker concentration. The prospects for the NRET technique as a molecular-scale probe of nanostructured microgels are also discussed.     

Precursors to water-soluble dinitrogen carriers. Synthesis of water-soluble complexes of iron(II) containing water-soluble chelating phosphine ligands of the type 1,2-bis(bis(hydroxyalkyl)phosphino)ethane

The reactions of the water-soluble chelating phosphines 1,2-bis(bis(hydroxyalkyl)phosphino)ethane (alkyl = n-propyl, DHPrPE; n-butyl, DHBuPE; n-pentyl, DHPePE) with FeCl(2).4H(2)O and FeSO(4).7H(2)O were studied as routes to water-soluble complexes that will bind small molecules, dinitrogen in particular. The products that form and their stereochemistry depend on the solvent, the counteranion, and the alkyl chain length on the phosphine. In alcoholic solvents, the reaction of FeCl(2).4H(2)O with 2 equiv of DHBuPE or DHPePE gave trans-Fe(L(2))(2)Cl(2). The analogous reactions in water with DHBuPE and DHPePE gave only cis products, and the reaction of FeSO(4).7H(2)O with any of the phosphines gave only cis-Fe(L(2))(2)SO(4). These results are interpreted as follows. The trans stereochemistry of the products from the reactions of FeCl(2).4H(2)O in alcohols is suggested to be the consequence of the trans geometry of the Fe(H(2)O)(4)Cl(2) complex, i.e., substitution of the water molecules by the phosphines retains the geometry of the starting material. The formation of cis-Fe(DHPrPE)(2)Cl(2) is an exception to this result because the coordination of two -OH groups forms two six-membered rings, as shown in the X-ray structure of the molecule. DHBuPE and DHPePE reacted with FeSO(4).7H(2)O in water to initially yield cis-Fe(P(2))(2)SO(4) compounds, but subsequent substitution reactions occurred over several hours to give sequentially trans-Fe(DHBuPE)(2)(H(2)O)(SO(4)) and then trans-[Fe(DHBuPE)(2)(H(2)O)(2)]SO(4). The rate constants and activation reactions for these aquation reactions were determined and are consistent with dissociatively activated mechanisms. The cis- and trans-Fe(L(2))(2)X (X = (Cl)(2) or SO(4)) complexes react with N(2), CO, and CH(3)CN to yield trans complexes with bound N(2), CO, or CH(3)CN. The crystal structures of the cis-Fe(DHPrPE)(2)SO(4), trans-Fe(DHPrPE)(2)(CO)SO(4), trans-Fe(DHBuPE)(2)Cl(2), trans-[Fe(DHBuPE)(2)(CO)(Cl)][B(C(6)H(5))(4)], trans-Fe(DMeOPrPE)(2)Cl(2), trans-Fe(DMeOPrPE)(2)Br(2), and trans-[Fe(DHBuPE)(2)Cl(2)]Cl complexes are reported. As expected from using water-soluble phosphines, the complexes reported herein are water soluble (generally greater than 0.5 M at 23 degrees C).     

Local control over phase transitions in microgel assemblies

Poly( N-isopropylacrylamide) microgels were coassembled with Au nanoparticles into disordered glassy phases and irradiated with a tightly focused laser (lambda = 532 nm) to study crystallization dynamics following a localized photothermal annealing process. The degree of crystallization produced by the annealing process is dependent upon heat flux into the sample at the site of irradiation, the length of irradiation time, and the temperature of the surrounding bulk assembly that functions as a quenching bath. Control over these sample conditions provides a method by which to probe the dynamics of crystallization over a set of microgel concentrations. The mobility, and thus the crystallization, of particles is shown to be frustrated as the microgel concentration is increased. This is in contrast with equilibrium experiments that have shown an increase in particle mobility with microgel concentration that is manifest as an increase in the freezing transition of the bulk assembly with increasing packing density.     

Processable cyanate ester resin from Cis resveratrol

Trans resveratrol isomerizes to cis resveratrol (cRes) with ultra‐violet light and undergoes cyanation to the new compound cRes tricyanate ( 2 ). Monomer 2 polymerizes to a polycyanurate that is remarkably stable to heat with a glass transition temperature > 350 °C and char yield of 73% in air up to 600 °C. The monomer 2 melts at <80 °C with a wide processing window before polymerization. The new thermosetting resin made from a natural product is a useful matrix material for polymer matrix composites requiring high‐performance characteristics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 971–980