Heteroleptic Copper(I)-Based Complexes Incorporating BINAP and π-Extended Diimines: Synthesis,Catalysis and Biological Applications

A series of copper-based photocatalysts of the type Cu(NN)(BINAP)BF₄ were synthesized bearing π-extended diimine ligands. Their behavior in several photocatalytic processes were evaluated and revealed acceptable levels of activity in an SET process, but negligible activity in PCET or ET processes. Suitable activity in ET processes could be restored through modification of the ligand. The BINAP-derived complexes were then evaluated for activity against triple-negative breast cancer cell lines. Controls indicated that copper complexes, and not their ligands, were responsible for activity. Encouraging activity was displayed by a homoleptic complex Cu(dppz)₂BF₄.     

Catalytically active mu-Oxodiiron(IV) oxidants from Iron(III) and dioxygen

The reaction between an Fe(III) complex and O(2) to afford a stable catalytically active diiron(IV)-mu-oxo compound is described. Phosphonium salts of orange five-coordinated Fe(III)-TAML complexes with an axial aqua ligand ([PPh(4)]1-H(2)O, tetraamidato macrocyclic Fe(III) species derived from 3,3,6,6,9,9-hexamethyl-3,4,8,9-tetrahydro-1H-1,4,8,11-benzotetraazacyclotridecine-2,5,7,10(6H,11H)-tetraone) react rapidly with O(2) in CH(2)Cl(2) or other weakly coordinating solvents to produce black mu-oxo-bridged diiron(IV) complexes, 2, in high yields. Complexes 2 have been characterized by X-ray crystallography (2 cases), microanalytical data, mass spectrometry, UV/Vis, Mossbauer, and (1)H NMR spectroscopies. Mossbauer data show that the diamagnetic Fe-O-Fe unit contains antiferromagnetically coupled S = 1 Fe(IV) sites; diamagnetic (1)H NMR spectra are observed. The oxidation of PPh(3) to OPPh(3) by 2 was confirmed by UV/Vis and GC-MS. Labeling experiments with (18)O(2) and H(2)(18)O established that the bridging oxygen atom of 2 derives from O(2). Complexes 2 catalyze the selective oxidation of benzylic alcohols into the corresponding aldehydes and bleach rapidly organic dyes, such as Orange II in MeCN-H(2)O mixtures; reactivity evidence suggests that free radical autoxidation is not involved. This work highlights a promising development for the advancement of green oxidation technology, as O(2) is an abundant, clean, and inexpensive oxidizing agent.     

The thermal dissociation of the [Co(NH3)6]Cl3 and [Co(NH3)6]Br3 complexes in vacuo

The thermal dissociation of the complexes, [Co(NH₃)₆]X₃(X^?=Cl, Br), was studied in vacuo using the techniques of thermogravimetry, evolved gas analysis and mass spectrometric analysis. It was found that the reaction stoichiometry was identical to that previously determined in air but that the type of intermediate compounds formed were different. The dissociation occurred by the reactions:

     

An analysis of PTFE surfaces modified by exposure to glow discharges

A detailed analysis is reported of the chemical and physical modifications which occur to PTFE surfaces exposed to glow discharges in ammonia gas and in air. The analytical methods used were infra-red attenuated total reflectance and differential attenuated total reflectance spectroscopy, X-ray photoelectron spectroscopy, contact angle measurements and scanning electron microscopy. The suitability for bonding with adhesives and the stability of the modified surfaces to attack by oxidizing acids are also reported.     

Self-immobilization and/or thermal treatment for preparing silica-poly(methyloctylsiloxane) stationary phases

Batches of poly(methyloctylsiloxane) (PMOS)-loaded silica were prepared by the deposition of PMOS, into the pores of HPLC silica. Portions of PMOS-loaded silica were allowed to remain at ambient temperature, without further treatment for 2, 9, 20, 31, 51, 105 and 184 days after preparation to undergo self-immobilization (irreversible adsorption of a layer of polymer on silica at ambient temperature in the absence of initiators). Other portions were subjected to a thermal treatment (100 degrees C for 4h) after 1, 2, 5, 7, 9, 15, 20, 25, 70, 111 and 184 days. Self-immobilized and thermally treated samples were characterized by % C, 29Si cross-polarization magic angle spinning (CP/MAS) NMR spectroscopy and reversed-phase column performance. The results show that thermal immobilization accelerates the distribution and rearrangement of the polymer on the silica surface. However, from the time that a monolayer has been formed by self-immobilization (approximately 100 days for PMOS on Kromasil silica), the thermal treatment does not alter this configuration and, thus, does not change the resulting chromatographic parameters.     

Point defects in NiAl near the equiatomic composition

Perturbed γ-γ angular correlation spectroscopy was applied to study the structure and properties of point defects near¹¹¹In probes in quenched and annealed NiAl samples with five compositions in the range c_Ni=48–52%. Quadrupole interaction signals are analysed in terms of near-neighbor Ni-vacancy and nextnear-neighbor Ni antisite atom defects. Large mono- and divacancy concentrations were observed in all samples after quenching. For c_Ni<50%, the vacancy defects could not be annealed out (structural defects). For C_Ni>50%, large quenched-in vacancy concentrations annealed out near 500°C. For c_Ni=50%, most vacancies annealed out near 500°C, but about 35% of the¹¹¹In probes retained a trapped monovacancy. This is attributed to a very low value of the formation enthalpy of a vacancy next to the In probe, estimated to be 0.16(2) eV. A lesser annelaing stage detected at 300°C is tentatively attributed to diffusion of Al-vacancies.     

A Near-Quadratic Algorithm for Fence Design

A part feeder is a mechanism that receives a stream of identical parts in arbitrary orientations and outputs them oriented the same way. Various sensorless part feeders have been proposed in the literature. The feeder we consider consists of a sequence of fences that extend partway across a conveyor belt; a polygonal part P carried by the belt is reoriented by each fence it encounters. We present an O(m + n² log³n)-time algorithm to compute a sequence of fences that uniquely orients P, if one exists, where m is the total number of vertices and n is the number of stable edges of P. We reduce the problem to searching for a path in a state graph that has O(n³) edges. By exploiting various geometric properties of this graph, we show that it can be represented implicitly and that a desired path can be computed in O(m + n² log³n) time. We believe that our technique is quite general and could be applicable to other part-manipulation problems as well.     

Characterizing the Evolution of Porosity during Controlled Drug Release

Nuclear magnetic resonance (NMR) techniques have been successfully used to characterize the evolving pore structure of partially soluble pharmaceutical pellets as they absorb water and release soluble components. The restricted diffusivity of water trapped within pellets, which have been immersed in water for differing times, has been measured by pulsed field gradient NMR. These measurements have been used to calculate the surface-to-volume ratio and tortuosity of the pore structure. A one-shot Carr–Purcell–Meiboom–Gill sequence has been used to measure the spin–spin (T ₂) relaxation time of water trapped within the pellets. These data have been regularized and then analyzed by the Brownstein–Tarr model to provide a pore size distribution for the pellets as a function of increasing immersion time. It has been found that pore structure changes significantly as water enters the pellet matrix. Two pellet formulations (herein referred to as placebo and drug-loaded) were studied and showed the same trends of a decreasing surface-to-volume ratio and tortuosity with increasing immersion time. At an immersion time of 10 min, both of these parameters decreased to approximately 70% of their values compared to an immersion time of 2 min. The placebo material tested consistently had both a higher tortuosity and surface-to-volume ratio than the drug-loaded material. At an immersion time of 2 min, the tortuosity for the placebo and drug-loaded materials were about 18 and about 10, respectively, and surface-to-volume ratios of about 6 μm⁻¹ and about 5 μm⁻¹, respectively. The materials tested also show changes in their pore size distribution with immersion time. In both formulations the mean and modal pore sizes increase with immersion time. The placebo material maintains an approximately similar mean and modal pore size, about 2 μm over the timescales studied, suggesting a more symmetric pore size distribution. In the drug-loaded pellets the mean pore size is much higher than the modal pore size, their values being 6.5 and 2.1 μm after 10 min immersion time, respectively. Authors' address: Michael D. Mantle, Department of Chemical Engineering, University of Cambridge, Pembroke Street, Cambridge CB2 3RA, UK