Lessons learned by opening and operating an independent restaurant: A Case study

This case study looks at what it takes to create a start-up business in the restaurant industry; with the intention to find out what pitfalls and potential mistakes an individual should be aware of in order to have a successful operation. The details are based on the researchers\u27 education, industry experience, and other people\u27s research and knowledge that are found throughout the restaurant industry. This case study will help others understand what to expect when opening a new restaurant, and possibly some challenges that could be avoided when creating their own restaurant. There are lessons to be learned from this study, and recommendations will be given so that others will not make the same mistakes as The Glass Onion

Spectroscopic and Computational Studies of the Physical Properties and Reactivities of Peroxomanganese(III) Complexes

A wide range of MnIII intermediates were generated and studied using various spectroscopic techniques, including electronic absorption, magnetic circular dichroism (MCD), variable-temperature, variable-field (VTVH) MCD, electron paramagnetic resonance (EPR), and X-ray absorption. Computational methods, such as density functional theory (DFT), time-dependent DFT (TD-DFT), and multi-reference ab initio calculations, were used to complement and aid in the interpretation of the spectroscopic data. Specifically, this combined spectroscopic/computational approach was employed to systematically investigate the geometric and electronic structure of a series of peroxomanganese(III) (MnIII-O2) intermediates supported by tridentate, tetradentate, and pentadentate ligands. This work has afforded new insight into the steric and electronic effects of the supporting ligand on the physical properties and reactivity of manganese species. The most significant results made in these studies are summarized below. MnIII-O2 adducts have been postulated as important intermediates in small molecule oxidation catalysts and manganese containing enzymes. A series of tetradentate dipyridyl- (or diquinolinyl-) diazacycloalkane ligands were synthesized to systematically probe the effects of steric and electronic perturbations on the properties of MnII and MnIII-O2complexes. In the initial study, a set of four [MnII(L7py2R)]2+ complexes, supported by the tetradentate 1,4-bis(2-pyridylmethyl)-1,4-diazepane ligand and derivatives with pyridine substituents in the five (R = 5-Br) and six-positions (R = 6-Me and 6-MeO), were synthesized. Treatment of these MnII precursors with H2O2 or KO2 at -40 oC resulted in the formation of MnIII-O2 complexes [MnIII(O2(L7py2R)]+ differing only in the identity of the pyridine ring substituent. The electronic structures of two of these complexes, [MnIII(O2(L7py2R)]+ and [MnIII(O2(L7py26-Me)]+, were examined with our combined spectroscopic/computational approach. While these complexes exhibit similar ground state parameters, their low-temperature MCD spectra revealed significant shifts in electronic transition energies that are correlated to differences in Mn-O2 interactions among these complexes. These results indicate that the [MnIII(O2(L7py2H)]+ complex exhibits symmetric Mn-Operoxo bond lengths, consistent with a side-on bound peroxo ligand. In contrast, the peroxo ligand of the [MnIII(O2(L7py26-Me)]+ complex is bound in a more end-on fashion, with asymmetric Mn-Operoxo distances. This difference in binding mode can be rationalized either in terms of the greater electron-donating abilities of the methyl-appended pyridines or by steric interactions between the peroxo ligand with the substituent at the six position. To distinguish between steric and electronic effects, additional MnII complexes were generated with pyridine derivatives with substituents in the four-position (R = 4-Me and 4-Cl), with different numbers of atoms in the diazacycloalkane backbone (n = 6, 7, 8), and with the type of N-ligand donor changed from a pyridine to a quinoline ligand. Spectroscopic analysis of these MnIII-O2 intermediates revealed a significant shift in the lowest-energy electronic transition when a bulky functional group is on the six position of the pyridine rings. These results indicate that the MnIII-O2 complexes lacking substituents at the six positions of the pyridine rings (L7py2H, L8py2H, L7py24-Me and L7isoq2) exhibit symmetric Mn-Operoxo bond lengths, consistent with a side-on bound peroxo ligand. The peroxo ligand of the complexes with a substituent at the six position (L7py26-Me, L7q2, and L8py26-Me) exhibit asymmetric Mn-Operoxo bond lengths, consistent with a more end-on bound peroxo ligand. This difference in binding mode can be rationalized by steric clash of the peroxo ligand with the 6-substituent at the six positions. To determine the effects of small ligand perturbations on the reactivity of the peroxo group, the more thermally stable MnIII-O2 complexes were reacted with cyclohexanecarboxaldehyde, a model substrate used to probe the relative nucleophilicities of peroxo metal species. Surprisingly, the rate of deformylation did not correlate with the expected nucleophilicity of the MnIII-O2 unit, as the inclusion of methyl substituents on the pyridines affords slower deformylation rates. It was proposed that adding methyl-substituents to the pyridines, or increasing the number of carbons on the diazacycloalkane backbone, sterically hinders nucleophilic attack of the peroxo ligand on the carbonyl carbon of the aldehyde. With small ligand perturbations causing large modulations of the Mn-Operoxo bond lengths, additional MnIII-O2 complexes, supported by aminopyridyl pentadentate ligands, were evaluated in collaboration with Dr. Elodie Anxolabéhère-Mallart (Laboratoire d'Electrochimie Moléculaire, Université Paris). Two MnIII-O2 complexes supported by pentadentate ligands, N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine (mL52) and N-methyl-N,N',N'-tris((1-methylimidazolyl)methyl)ethane-1,2-diamine (imL52) were examined with the spectroscopic/computational method to probe the geometric and the electronic structure. The electronic absorption spectra of these MnIII-O2 complexes (intense broad feature in the range of 15 000 cm-1 to 18 000 cm-1 with a weak shoulder at ~23 000 cm-1) are uniquely different compared to analogous tetradentate ligands (weak broad feature ~ 15 500 cm-1 with an intense absorption feature at ~ 22 000 cm-1). The combined spectroscopic/computational approach was allowed for unambiguous assignment of the structure of these complexes because, although several MnIII-O2 binding modes are possible, each mode should have a unique set of spectral properties. The possible modes are either a seven-coordinate, side-on MnIII-O2species; a six-coordinate, end on MnIII-O2 species; or a six-coordinate, side-on MnIII-O2 adduct with a dissociated N donor from the ligand. This spectroscopic/computational approach revealed that MnIII-O2 complexes supported by pentadentate ligands are stabilized by a six-coordinate environment, with one of the pyridine/imidazole groups dissociated and with a side-on peroxo binding mode. With the observed trend that MnIII-O2 adducts are stabilized by a six-coordinate environment, an additional MnIII-O2 complex supported by a tridentate ligand was synthesized to evaluate its coordination environment and its electronic structure. A bulky scorpionate-based ligand, tris(3,5-diphenylpyrazolyl)borate (TpPh2) was designed to stabilize a MnIII-O2 complex at room temperature. We proposed that the bulky phenyl groups should shield the peroxo ligand and may form a weak hydrogen bonding network, thereby stabilizing a MnIII-O2 intermediate, allowing for characterization by XRD, which the instability of the other intermediates had precluded. The MnII XRD structure revealed a six coordinate complex with the TpPh2 ligand in a facially coordinating geometry, with three solvent molecules completing the coordination sphere. Treatment of this MnII complex with H2O2 or KO2 at room temperature resulted in the formation of a MnIII-O2 complex that is stable for several days at ambient conditions. The increase stability allowed for the isolation of single needle crystals for XRD analysis. The XRD structure confirmed the assignment of this species as a MnIII-O2 adduct (Mn-O and O-O of 1.86 and 1.43 Å) and revealed a distorted six-coordinate octahedral complex with one solvent molecule completing the coordination sphere. The geometric and electronic structure of this MnIII-O2 complex was characterized by using the combined spectroscopic/computational approach

Captive Soul: A Work for String Quartet in Four Movements

Captive Soul is a work for string quartet in four movements. It was written in part to fulfill the requirements for the Master’s degree in Music Composition and is the primary subject of this thesis. Inspiration for the work was drawn from the composer’s own experiences. The composition was completed in March 2005 by James R. Geiger using a M-Audio Keystation 49-E, a Macintosh G3 computer, and an Edirol SoundCanvas SC-88ST tone module. The notation of the score was completed in April 2005 using Finale 2003 from Coda Software. It is approximately seventeen minutes and thirty seconds (17’30”) in duration. The purpose of this study is to place the composition in historical perspective, examine its structural elements within the context of similar genres, and explain the compositional procedures used. In particular, the study of Captive Soul will involve a discussion of elements such as form, melody, harmony, rhythm, and texture in the work and the similar use of these elements in works by prominent composers of the twentieth century. The compositions to be examined are: String Quartet No.2, String Quartet No. 3, and Symphony No. 3 “Liturgique” by Arthur Honegger, Petite Symphonie Concertante and Etudes for String Orchestra by Frank Martin, and Lyric Suite for String Quartet by Alban Berg

How to estimate the differential acceleration in a two-species atom interferometer to test the equivalence principle

We propose a scheme for testing the weak equivalence principle (Universality of Free Fall) using an atom-interferometric measurement of the local differential acceleration between two atomic species with a large mass ratio as test masses. A apparatus in free fall can be used to track atomic free-fall trajectories over large distances. We show how the differential acceleration can be extracted from the interferometric signal using Bayesian statistical estimation, even in the case of a large mass and laser wavelength difference. We show that this statistical estimation method does not suffer from acceleration noise of the platform and does not require repeatable experimental conditions. We specialize our discussion to a dual potassium/rubidium interferometer and extend our protocol with other atomic mixtures. Finally, we discuss the performances of the UFF test developed for the free-fall (0-g) airplane in the ICE project (\verb"http://www.ice-space.fr"

An Observation on the Protoplasmic Connections Through Sieve Plates

Author Institution: Department of Botany and Plant Pathology, The Ohio State University, Columbus 10wo electron micrographs of paradermal sections of veins of the leaves of Beta vulgaris are presented. The micrographs show the endoplasmic reticulum from one sieve cell passing through the sieve plate and into the adjacent sieve cell. This is evidently an unusual condition in this materia

Dietary bioactive lipid compounds rich in menthol alter Interactions among members of ruminal microbiota in sheep

This study aimed to investigate the effects of two practically relevant doses of menthol-rich plant bioactive lipid compounds (PBLC) on fermentation, microbial community composition, and their interactions in sheep rumen. Twenty-four growing Suffolk sheep were divided into three treatments and were fed hay ad libitum plus 600 g/d of concentrate containing no PBLC (Control) or PBLC at low dose (80 mg/d; PBLC-L) or high dose (160 mg/d; PBLC-H). After 4 weeks on the diets, samples of ruminal digesta were collected and analyzed for short-chain fatty acid (SCFA), ammonia, and microbiota; microbiota being analyzed in the solid and the liquid digesta fractions separately. Ruminal SCFA and ammonia concentrations were not affected by the PBLC treatments. The microbiota in the solid fraction was more diverse than that in the liquid fraction, and the relative abundance of most taxa differed between these two fractions. In the solid fraction, phylogenetic diversity increased linearly with increased PBLC doses, whereas evenness (lowest in PBLC-L) and Simpson diversity index (greatest in PBLC-H) changed quadratically. In the liquid fraction, however, the PBLC supplementation did not affect any of the microbial diversity measurements. Among phyla, Chloroflexi (highest in PBLC-L) and unclassified_bacteria (lowest in PBLC-L) were altered quadratically by PBLC. Lachnospiraceae, Bacteroidaceae (increased linearly), BS11 (increased in PBLC-L), Christensenellaceae (decreased in PBLC treatments), and Porphyromonadaceae (increased in PBLC treatments) were affected at the family level. Among genera, Butyrivibrio increased linearly in the solid fraction, YRC22 increased linearly in the liquid fraction, whereas Paludibacter increased and BF311 increased linearly with increasing doses of PBLC in both fractions. The PBLC treatments also lowered methanogens within the classes Thermoplasmata and Euryarchaeota. Correlation network analysis revealed positive and negative correlations among many microbial taxa. Differential network analysis showed that PBLC supplementation changed the correlation between some microbial taxa and SCFA. The majority of the predicted functional features were different between the solid and the liquid digesta fractions, whereas the PBLC treatments altered few of the predicted functional gene categories. Overall, dietary PBLC treatments had little influence on the ruminal fermentation and microbiota but affected the associations among some microbial taxa and SCFA

Plasmachemical Synthesis of Carbon Suboxide

A nonthermal carbon monoxide plasma is known to produce a solid deposition which is thought to be a polymer of carbon suboxide (C3O2); however there are very few investigations of this deposition in the literature. This thesis contains an analysis of the theoretical thermodynamics and kinetics of carbon suboxide formation as well as experimental results. The theoretical analysis suggests that carbon suboxide may be an equilibrium product even at ambient conditions but favors lower temperatures; furthermore if solid carbon is considered to be kinetically limited, and therefore not a product, then carbon suboxide is more likely to be a product under these pseudo-equilibrium conditions. Experimentally, solid films were produced in a dielectric barrier discharge (DBD) containing pure carbon monoxide. Optical emission spectroscopy was used to analyze the plasma and models of the emission spectra were created to determine the plasma temperatures. Deposition rates were determined to be on the order of 0.2 mg/min at a power of about 10W; it is expected however that these conditions are not optimized. The overall kinetics of carbon suboxide was analyzed and optimal conditions for operation can be estimated. Characterization of the solid depositions were carried out using Solid State Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), Electrospray Ionization Mass Spectroscopy (ESI-MS), and Matrix-assisted Laser Desorption Ionization Mass Spectroscopy (MALDI-MS). The characteristics of the film are very comparable to hydrolyzed carbon suboxide polymer suggesting that carbon suboxide polymer were in fact created in the carbon monoxide plasma at atmospheric conditions