Free Space Optical Link Utilizing a Modulated Retro-Reflector Intended for Planetary Duplex Communication Links Between an Orbiter and Surface Unit

Presented are simulation and experimental results that provide duplex optical-free space communication links with minimal power and pointing requirements by using a modulated retro-reflector (MRR) for planetary communications. The design is the MRR resides on the surface of a planet or moon, where energy is scarce, while the source of the communication laser resides on an orbiter to achieve satellite-to-ground communications. Also, a simulated scenario using the Mars Reconnaissance Orbiter (MRO) is provided for real world potential results. The information sent through this communication path can range from raw scientific data to multimedia files such as videos and pictures. Bidirectional communications is established with the MRR by using a nested pulse position modulation (PPM) structure. This modulation scheme is then evaluated for its validity in a proof-of-concept experiment. Initial results indicate a promising return-link performance of at least 300 kbps in the nested arrangement

Preparation of heteronuclear bridging methylene complexes

The reactions of the titanacyclobutane complexes (η^5-C_5H_5)_2TiCH_2CRR'CH_2 (la, R = R' = Me; lb, R = Me, R' = Pr) with M-X compounds (M =Ti, Zr, Rh, Ir, Pd, Pt; X = Cl, OMe) have been investigated. The titanacyclobutanes have been found to react as sources of (η^5-C_5H_5)_2TiCH_2, giving (η^5-C_5H_5)_2Ti(μ –CH_2)(μ-X)ML_n (L_n = ancillary ligands) products. Several such complexes have been isolated as crystalline solids; however, only (η^5-C_5H_5_2Ti(μ-CH_2)(μ-X)Rh(η^4-l,5-cyclooctadiene) is stable in solution at 25°C. The complex η^5-C_5H_5)_2iTi(μ-CH_2)(μ-Cl)Ti(η^5-C_5Me_5)Cl was found to react with CO to form the bridging ketene complex (η^5-C_5H_5)_2Ti-μ, η^2(C,O)-(OCCH_2)Ti(η^5-C_5Me_5)Cl_2

On the motion of hairy black holes in Einstein-Maxwell-dilaton theories

Starting from the static, spherically symmetric black hole solutions in massless Einstein-Maxwell-dilaton (EMD) theories, we build a "skeleton" action, that is, we phenomenologically replace black holes by an appropriate effective point particle action, which is well suited to the formal treatment of the many-body problem in EMD theories. We find that, depending crucially on the value of their scalar cosmological environment, black holes can undergo steep "scalarization" transitions, inducing large deviations to the general relativistic two-body dynamics, as shown, for example, when computing the first post-Keplerian Lagrangian of EMD theories

Ru-based Z-selective metathesis catalysts with modified cyclometalated carbene ligands

A series of cyclometalated Z-selective ruthenium olefin metathesis catalysts with alterations to the N-heterocyclic carbene (NHC) ligand were prepared. X-Ray crystal structures of several new catalysts were obtained, elucidating the structural features of this class of cyclometalated complexes. The metathesis activity of each stable complex was evaluated, and one catalyst, bearing geminal dimethyl backbone substitution, was found to be comparable to our best Z-selective metathesis catalyst to date

Tuning the formal potential of ferrocyanide over a 2.1 V range

We report the synthesis and characterization of homoleptic borane adducts of hexacyanoferrate(II). Borane coordination blueshifts d–d transitions and CN IR and Raman frequencies. Control over redox properties is established with respect to borane Lewis acidity, reflected in peak anodic potential shifts per borane of +250 mV for BPh_3 and +350 mV for B(C_6F_5)_3. Electron transfer from [Fe(CN-B(C_6F_5)_3)_6]^(4−) to photogenerated [Ru(2,2′-bipyridine)_3]^(3+) is very rapid, consistent with voltammetry data. Coordination by Lewis acids provides an avenue for selective modification of the electronic structures and electrochemical properties of cyanometalates

Preparation of heteronuclear bridging methylene complexes

The reactions of the titanacyclobutane complexes (η^5-C_5H_5)_2TiCH_2CRR'CH_2 (la, R = R' = Me; lb, R = Me, R' = Pr) with M-X compounds (M =Ti, Zr, Rh, Ir, Pd, Pt; X = Cl, OMe) have been investigated. The titanacyclobutanes have been found to react as sources of (η^5-C_5H_5)_2TiCH_2, giving (η^5-C_5H_5)_2Ti(μ –CH_2)(μ-X)ML_n (L_n = ancillary ligands) products. Several such complexes have been isolated as crystalline solids; however, only (η^5-C_5H_5_2Ti(μ-CH_2)(μ-X)Rh(η^4-l,5-cyclooctadiene) is stable in solution at 25°C. The complex η^5-C_5H_5)_2iTi(μ-CH_2)(μ-Cl)Ti(η^5-C_5Me_5)Cl was found to react with CO to form the bridging ketene complex (η^5-C_5H_5)_2Ti-μ, η^2(C,O)-(OCCH_2)Ti(η^5-C_5Me_5)Cl_2

Confinement and Processing Can Alter the Morphology and Periodicity of Bottlebrush Block Copolymers in Thin Films

Bottlebrush block copolymers (BBCPs) are intriguing architectural variations on linear BCPs with highly tunable structure. Confinement can have a significant impact on polymer assembly, giving rise to changes in morphology, assembly kinetics, and properties like the glass transition. Given that confinement leads to significant changes in the persistence length of bottlebrush homopolymers, it is reasonable to expect that BBCPs will see significant changes in their structure and periodicity relative to the bulk morphology. Understanding how confinement influences assembly will be important for designing BBCPs for thin film applications including membranes, integrated photonic structures, and potentially BCP lithography. In order to study the effects of confinement on BBCP conformation and morphology, a blade coating was used to prepare films with continuous variation in film thickness. Unlike thin films of linear BCPs, islands/holes were not observed, and instead mixtures of parallel and perpendicular morphologies emerge after annealing. The lamellar periodicity (L₀) of the morphologies is found to be thickness dependent, increasing L₀ with decreasing film thickness for blade coated films. Films coated out of tetrahydrofuran (THF) resulted in a single well-defined lamellar periodicity, verified through atomic force microscopy (AFM) and grazing incidence small-angle X-ray scattering (GISAXS), which increases dramatically from the bulk value (30.6 nm) and continues to increase as the film thickness decreases. The largest observed L₀ was 65.5 nm, and this closely approaches the estimated upper limit of 67 nm corresponding to a fully extended backbone in a bilayer arrangement. Films coated out of propylene glycol methyl ether acetate (PGMEA) resulted in a mixture of perpendicular lamellae and a smaller, likely cylindrical morphology. The lamellar portion of the film shows the same thickness dependence as the lamellae observed in the THF coated films. The scaling of the lamellar L₀ with respect to film thickness follows predictions for confined semiflexible polymers with weak excluded volume interactions and can be related to models for confinement of DNA. Spin coated films shows the same reduction in periodicity, although at very different film thicknesses. This result suggests that the material has shallow free-energy barriers to transitioning between different L₀ and morphologies, a property that could be taken advantage of for patterning diverse structures with a single material

Improved Ruthenium Catalysts for Z-Selective Olefin Metathesis

Several new C–H-activated ruthenium catalysts for Z-selective olefin metathesis have been synthesized. Both the carboxylate ligand and the aryl group of the N-heterocyclic carbene have been altered and the resulting catalysts evaluated using a range of metathesis reactions. Substitution of bidentate with monodentate X-type ligands led to a severe attenuation of metathesis activity and selectivity, while minor differences were observed between bidentate ligands within the same family (e.g., carboxylates). The use of nitrato-type ligands in place of carboxylates afforded a significant improvement in metathesis activity and selectivity. With these catalysts, turnover numbers approaching 1000 were possible for a variety of cross-metathesis reactions, including the synthesis of industrially relevant products

Tuning the formal potential of ferrocyanide over a 2.1 V range

We report the synthesis and characterization of homoleptic borane adducts of hexacyanoferrate(II). Borane coordination blueshifts d–d transitions and CN IR and Raman frequencies. Control over redox properties is established with respect to borane Lewis acidity, reflected in peak anodic potential shifts per borane of +250 mV for BPh_3 and +350 mV for B(C_6F_5)_3. Electron transfer from [Fe(CN-B(C_6F_5)_3)_6]^(4−) to photogenerated [Ru(2,2′-bipyridine)_3]^(3+) is very rapid, consistent with voltammetry data. Coordination by Lewis acids provides an avenue for selective modification of the electronic structures and electrochemical properties of cyanometalates