Dendritic rhodium catalyst precursors for the hydroformylation of olefins

The hydroformylation reaction is the transition-metal catalysed addition of CO/H2 to olefins, resulting in linear and/or branched aldehydes. This reaction is in accordance with Green Chemistry principles, as it operates with 100% atom efficiency and uses renewable feedstocks such as olefins from the Fischer-Tropsch process. Rhodium is the metal of choice when designing catalysts for hydroformylation, owing to its good catalytic activity under mild reaction conditions. The strategy of appending bulky ligands has often been employed to enhance catalytic activity and selectivity. Dendritic wedges are promising to the field of catalysis, as one branch may possess multiple surface terminal groups and the other branch may consist of a mononuclear metal centre. This method differs to classical approaches whereby multinuclear effects are explored to enhance the catalyst activity. The purpose of this study was to synthesize and characterise a series of Fréchet dendrons bearing rhodium Schiff-base moieties at the focal point, and investigate their potential as catalyst precursors in the hydroformylation of olefins. A series of Fréchet dendrons with methyl ester groups at the periphery were prepared. The N,O-salicylaldimine and N,P-iminophosphine Schiff-base ligands were synthesized and consequently coupled to the Fréchet dendrons to yield a new class of Fréchet dendrons with N,O-salicylaldimine or N,P-iminophosphine ligands at the focal point. Complexes of these ligands were synthesized to form a new series of neutral rhodium(I) metallodendrons. Complexation of the N,O-salicylaldimine Fréchet dendrons with the metal-precursor [Rh(μ-Cl)(η 2 :η2 -COD)]2 (where COD = 1,5-cyclooctadiene) afforded the Rh(I)-COD metallodendrons. The Rh(I)-COD metallodendrons were reacted under a carbon monoxide atmosphere to yield a new series of dicarbonyl Rh(I) metallodendrons. The bridge splitting reaction between the N,P-iminophosphine Fréchet dendrons and [Rh(μ-Cl)(CO)2]2 afforded the carbonyl-chloride Rh(I) metallodendrons. The Fréchet dendron ligands and rhodium metallodendrons were fully characterised using an array of spectroscopic (1H, 13C{1H}, 31P{1H} NMR, FT-IR spectroscopy) and analytical (elemental analysis and mass spectrometry) techniques. Single crystal X-ray diffraction confirmed the proposed molecular structure and square-planar geometry around the metal centre for the zeroth generation analogues of the N,O-salicylaldimine and N,P-iminophosphine rhodium metallodendrons. The Rh(I) Schiff-base metallodendrons were applied as catalyst precursors in the hydroformylation of various olefins. All of the catalyst precursors were active in the hydroformylation of 1-octene. The N,O-salicylaldimine metallodendrons displayed good to excellent conversion (78 – 100%), good chemoselectivity (66 – 95%) and moderate regioselectivity (51 – 67%). In contrast, the N,P-iminophosphine metallodendrons displayed low conversion (4 – 8%), good chemoselectivity (76 – 80%) and good regioselectivity (64 – 68%) under the hydroformylation conditions. Notably, the increase in dendron size (G0 – G2) resulted in an increase in the chemoselectivity towards aldehydes. Hydroformylation reactions were conducted using various olefin substrates. These include 1-octene, styrene, 7-tetradecene, methyl oleate, triolein, D-limonene and R-citronellal. The model precursor was active in the hydroformylation of these substrates. More importantly, conversions obtained were promising for styrene (100%), D-limonene (90%), 1-octene (86%), methyl oleate (78%), 7-tetradecene (73%) and triolein (52%). The regioselectivity for the internal olefins ranged between 85 – 98%. These results are particularly promising for tandem-catalytic processes. Mercury drop experiments performed on the zeroth generation analogues of the N,O-salicylaldimine-COD, N,O-salicylaldimine-dicarbonyl and N,P-iminophosphine chloro-carbonyl rhodium(I) metallodendrons displayed suppressed activity in the presence of mercury

Drag and Shape Analysis of Fiberglass Particles

Settling tests were performed on particles of NUKON fiberglass to relate the drag coefficient of the particles to the Reynolds number of the particles. A new method was developed to measure fiberglass particles. The projected area, projected perimeter, and average height of the particles are measured using this method. The measurements are used to calculate the measured drag coefficient and measured Reynolds number for the particles. Data collected was compared to previous studies that focused on the settling of sand grains. A predictive correlation that was developed for sand grains was applied towards the particles of fiberglass. Tests were run with dyed particles of fiberglass as a means of flow visualization. The results from these visualization tests were compared with results from the free settling of disks

Enhancing SAMPI Personnel Evaluation Procedures

Science and Mathematics Program Improvement (SAMPI) exclusively using WMU Human Resources “Performance Management Program Annual Review Form” for staff annual performance reviews. Form provides annual opportunity for SAMPI staff and Director to meet and discuss past performance and future development plans. Experiences with staff performance reviews and ALA convinced me of need for additional procedures to develop team trust and encourage staff buy-i

Easiness Amplification and Uniform Circuit Lower Bounds

We present new consequences of the assumption that time-bounded algorithms can be "compressed" with non-uniform circuits. Our main contribution is an "easiness amplification" lemma for circuits. One instantiation of the lemma says: if n^{1+e}-time, tilde{O}(n)-space computations have n^{1+o(1)} size (non-uniform) circuits for some e > 0, then every problem solvable in polynomial time and tilde{O}(n) space has n^{1+o(1)} size (non-uniform) circuits as well. This amplification has several consequences: * An easy problem without small LOGSPACE-uniform circuits. For all e > 0, we give a natural decision problem, General Circuit n^e-Composition, that is solvable in about n^{1+e} time, but we prove that polynomial-time and logarithmic-space preprocessing cannot produce n^{1+o(1)}-size circuits for the problem. This shows that there are problems solvable in n^{1+e} time which are not in LOGSPACE-uniform n^{1+o(1)} size, the first result of its kind. We show that our lower bound is non-relativizing, by exhibiting an oracle relative to which the result is false. * Problems without low-depth LOGSPACE-uniform circuits. For all e > 0, 1 < d < 2, and e < d we give another natural circuit composition problem computable in tilde{O}(n^{1+e}) time, or in O((log n)^d) space (though not necessarily simultaneously) that we prove does not have SPACE[(log n)^e]-uniform circuits of tilde{O}(n) size and O((log n)^e) depth. We also show SAT does not have circuits of tilde{O}(n) size and log^{2-o(1)}(n) depth that can be constructed in log^{2-o(1)}(n) space. * A strong circuit complexity amplification. For every e > 0, we give a natural circuit composition problem and show that if it has tilde{O}(n)-size circuits (uniform or not), then every problem solvable in 2^{O(n)} time and 2^{O(sqrt{n log n})} space (simultaneously) has 2^{O(sqrt{n log n})}-size circuits (uniform or not). We also show the same consequence holds assuming SAT has tilde{O}(n)-size circuits. As a corollary, if n^{1.1} time computations (or O(n) nondeterministic time computations) have tilde{O}(n)-size circuits, then all problems in exponential time and subexponential space (such as quantified Boolean formulas) have significantly subexponential-size circuits. This is a new connection between the relative circuit complexities of easy and hard problems

On the (Non) NP-Hardness of Computing Circuit Complexity

The Minimum Circuit Size Problem (MCSP) is: given the truth table of a Boolean function f and a size parameter k, is the circuit complexity of f at most k? This is the definitive problem of circuit synthesis, and it has been studied since the 1950s. Unlike many problems of its kind, MCSP is not known to be NP-hard, yet an efficient algorithm for this problem also seems very unlikely: for example, MCSP in P would imply there are no pseudorandom functions. Although most NP-complete problems are complete under strong "local" reduction notions such as poly-logarithmic time projections, we show that MCSP is provably not NP-hard under O(n^(1/2-epsilon))-time projections, for every epsilon > 0. We prove that the NP-hardness of MCSP under (logtime-uniform) AC0 reductions would imply extremely strong lower bounds: NP notsubset P/poly and E notsubset i.o.-SIZE(2^(delta * n)) for some delta > 0 (hence P = BPP also follows). We show that even the NP-hardness of MCSP under general polynomial-time reductions would separate complexity classes: EXP != NP cap P/poly, which implies EXP != ZPP. These results help explain why it has been so difficult to prove that MCSP is NP-hard. We also consider the nondeterministic generalization of MCSP: the Nondeterministic Minimum Circuit Size Problem (NMCSP), where one wishes to compute the nondeterministic circuit complexity of a given function. We prove that the Sigma_2 P-hardness of NMCSP, even under arbitrary polynomial-time reductions, would imply EXP notsubset P/poly

A Template Analysis of Intimate Partner Violence Survivors’ Experiences of Animal Maltreatment: Implications for Safety Planning and Intervention

This study explores the intersection of intimate partner violence (IPV) and animal cruelty in an ethnically diverse sample of 103 pet-owning IPV survivors recruited from community-based domestic violence programs. Template analysis revealed five themes: (a) Animal Maltreatment by Partner as a Tactic of Coercive Power and Control, (b) Animal Maltreatment by Partner as Discipline or Punishment of Pet, (c) Animal Maltreatment by Children, (d) Emotional and Psychological Impact of Animal Maltreatment Exposure, and (e) Pets as an Obstacle to Effective Safety Planning. Results demonstrate the potential impact of animal maltreatment exposure on women and child IPV survivors’ health and safety

Effectiveness of wilderness therapy

This paper examines the literature in the field of Wilderness Therapy in order to evaluate the current state of research, and the basic format of how Wilderness Therapy works. The theoretical base of Wilderness Therapy is discussed to provide conceptual framework and describe how the therapy could be launched into mainstream therapy. The techniques of Wilderness Therapy are explained for better understanding of how the therapy works. In conclusion, Wilderness Therapy appears to be a viable alternative for the treatment of emotional and behavioral problems amongst adolescents and adults. Recommendations for the future are for more research and better understanding of how Wilderness Therapy can be used

The Insoluble Carbonaceous Material of CM Chondrites as Possible Source of Discrete Organics During the Asteroidal Aqueous Phase

The larger portion of the organic carbon in carbonaceous chondrites (CC) is present as a complex and heterogeneous macromolecular material that is insoluble in acids and most solvents (IOM). So far, it has been analyzed only as a whole by microscopy (TEM) and spectroscopy (IR, NMR, EPR), which have offered and overview of its chemical nature, bonding, and functional group composition. Chemical or pyrolytic decomposition has also been used in combination with GC-MS to identify individual compounds released by these processes. Their value in the recognition of the original IOM structure resides in the ability to properly interpret the decomposition pathways for any given process. We report here a preliminary study of IOM from the Murray meteorite that combines both the analytical approaches described above, under conditions that would realistically model the IOM hydrothermal exposure in the meteorite parent body. The aim is to document the possible release of water and solvent soluble organics, determine possible changes in NMR spectral features, and ascertain, by extension, the effect of this loss on the frame of the IOM residue. Additional information is included in the original extended abstract

Soldier Power Operational Benefit Analysis

An operational benefit analysis of military small unit power (SUP) equipment is presented in detail.  SUP equipment is designed to improve power generation, conservation, and overall power management strategies for dismounted military units.  The operational benefit analysis examines four tactical scenarios and considers a naïve power management strategy and a SUP enabled power management strategy.  The major findings and conclusions discussed in this paper include: specific conservation and generation strategies for select dismounted tactical scenarios; the importance of proper solar blanket employment; identification of a capability gap between 100W and 1000W in the power generation spectrum; the benefits of using conformal batteries; and the impact of inefficient PRC 154 battery swaps in the naïve case

Relations and Equivalences Between Circuit Lower Bounds and Karp-Lipton Theorems

A frontier open problem in circuit complexity is to prove P^{NP} is not in SIZE[n^k] for all k; this is a necessary intermediate step towards NP is not in P_{/poly}. Previously, for several classes containing P^{NP}, including NP^{NP}, ZPP^{NP}, and S_2 P, such lower bounds have been proved via Karp-Lipton-style Theorems: to prove C is not in SIZE[n^k] for all k, we show that C subset P_{/poly} implies a "collapse" D = C for some larger class D, where we already know D is not in SIZE[n^k] for all k. It seems obvious that one could take a different approach to prove circuit lower bounds for P^{NP} that does not require proving any Karp-Lipton-style theorems along the way. We show this intuition is wrong: (weak) Karp-Lipton-style theorems for P^{NP} are equivalent to fixed-polynomial size circuit lower bounds for P^{NP}. That is, P^{NP} is not in SIZE[n^k] for all k if and only if (NP subset P_{/poly} implies PH subset i.o.- P^{NP}_{/n}). Next, we present new consequences of the assumption NP subset P_{/poly}, towards proving similar results for NP circuit lower bounds. We show that under the assumption, fixed-polynomial circuit lower bounds for NP, nondeterministic polynomial-time derandomizations, and various fixed-polynomial time simulations of NP are all equivalent. Applying this equivalence, we show that circuit lower bounds for NP imply better Karp-Lipton collapses. That is, if NP is not in SIZE[n^k] for all k, then for all C in {Parity-P, PP, PSPACE, EXP}, C subset P_{/poly} implies C subset i.o.-NP_{/n^epsilon} for all epsilon > 0. Note that unconditionally, the collapses are only to MA and not NP. We also explore consequences of circuit lower bounds for a sparse language in NP. Among other results, we show if a polynomially-sparse NP language does not have n^{1+epsilon}-size circuits, then MA subset i.o.-NP_{/O(log n)}, MA subset i.o.-P^{NP[O(log n)]}, and NEXP is not in SIZE[2^{o(m)}]. Finally, we observe connections between these results and the "hardness magnification" phenomena described in recent works