« Les Drois d'armes », compilation exécutée en 1481, sous la direction de Gille, roi d'armes de Maximilien d'Autriche, comte de Flandres.

Contient : 1 « Petit Traittié de noblesse, composé par JAQUES DE VALERE, en langue d'Espaigne, et nagaires translaté en françois par maistre HUGUES DE SALVE, prevost de Furnes » ; 2 « Les.XII. Chappitres du blason d'armes » ; 3 « Traittié de l'office d'armes et de noblesse », contenant le cérémonial observé pour l'élection d'un empereur, d'un roi, d'un duc, d'un comte, etc ; 4 « La Maniere de faire champ à outrance, selon l'ordonnance faite par les roys d'Angleterre », par « THOMAS, duc de Clocestre, connestable d'Angleterre », dédié à Richard II ; 5 « Les Ordonnances aux gaiges de batailles, en champ fermé, selon la coutume de France », ordonnance de Philippe le Bel, 1306 ; 6 « La premiere Institution des roys d'armes et heraulx, et des seremens et promesses qu'ilz font à leur creation » ; 7 « La Manieré de faire tournois et behours » ; 8 « L'Ordonnance que soloient anciennement faire les parens des nobles hommes trespassez » ; 9 « Les Ordonnances et solennitez qui furent faictes aux obseques de feu de noble memoire monseigneur Gyrard de Mortaigne, seigneur des Pierres et de Caurines », mort en 1411

« Recolectoire de plusieurs livres et traictez de philozophie », compilation de traités, extraits, fragments d'anciens alchimistes, tels que BERNARD DE TREVES, ALBERT LE GRAND, ARNAULD DE VILLENEUVE, RAYMOND LULLE, etc., augmenté de recettes, formules et sophistications, par « PHILIPUS DE LA LENDE ».

Commençant par : « Ce present recolectoire ay voulu dedier et retirer... » et finissant par : «... et noli revelare quam magnum archanum est in ista arte. Philippus de La Lende » .

Compilation d'histoire ancienne.

Contient : Histoire des premiers temps de l'Assyrie et de la Grèce, d'après Orose, 1, IV et suiv. « Devant ce que Rome fust fondée ne commenchié[e], ne estorée M et CCC. ans... » ; Roman de Thèbes, en prose. « Uns roi estoit adone à Thebes, riches et puissans, Laius... » ; « La vraie ystore de la cité de Troye. Peleus ot I. frere, qui ot a non Euison... » Imité du De excidio Trojæ de Darès

FT-IR and MAS NMR analysis of montmorillonite K10 supported MF2 reagents and their activity as catalysis /

ZnF2, CdF2, and CUF2 have been adsorbed onto the surface of montmorillonite K10, and the infrared and 19F, 27 AI, and 29Si MAS NMR spectra of the reagents over a range of loadings have been obtained. CUF2 was observed to attack the Si02 layer and form the complex CuSiF6, Zn F2 tends to attack the aluminium oxide layer, in which Zn isomorphously replaces AI, and forms AIF3 and AIF4 - complexes. All the spectroscopic evidence ruled out the formation of any AI-F and/or Si-F free species as CdF2 is adsorbed on the surface of montmorillonite K10. The reactivity of MF2-K10 reagents towards Friedel-Crafts benzylation of benzene with benzyl chloride varied from one reagent to another. ZnF2-K10 was observed to be the most reactive and CUF2 was the least reactive.

Extracting Ramachandran torsional angle distributions from 2D NMR data using Tikhonov regularization /

Solid state nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for studying structural and dynamical properties of disordered and partially ordered materials, such as glasses, polymers, liquid crystals, and biological materials. In particular, twodimensional( 2D) NMR methods such as ^^C-^^C correlation spectroscopy under the magicangle- spinning (MAS) conditions have been used to measure structural constraints on the secondary structure of proteins and polypeptides. Amyloid fibrils implicated in a broad class of diseases such as Alzheimer's are known to contain a particular repeating structural motif, called a /5-sheet. However, the details of such structures are poorly understood, primarily because the structural constraints extracted from the 2D NMR data in the form of the so-called Ramachandran (backbone torsion) angle distributions, g{^,'4)), are strongly model-dependent. Inverse theory methods are used to extract Ramachandran angle distributions from a set of 2D MAS and constant-time double-quantum-filtered dipolar recoupling (CTDQFD) data. This is a vastly underdetermined problem, and the stability of the inverse mapping is problematic. Tikhonov regularization is a well-known method of improving the stability of the inverse; in this work it is extended to use a new regularization functional based on the Laplacian rather than on the norm of the function itself. In this way, one makes use of the inherently two-dimensional nature of the underlying Ramachandran maps. In addition, a modification of the existing numerical procedure is performed, as appropriate for an underdetermined inverse problem. Stability of the algorithm with respect to the signal-to-noise (S/N) ratio is examined using a simulated data set. The results show excellent convergence to the true angle distribution function g{(j),ii) for the S/N ratio above 100.

Chelated fluoroboron cations : synthesis and multinuclear nmr studies

The preparation of chelated difluoroboron cations (DD)BF2+, where DD is a saturated polydentate tertiary-amine or polydentate aromatic ligand, has been systematically studied by using multinuclear solution and solid state nuclear magnetic resonance spectroscopy and fast atom bombardment mass spectrometry. Three new methods of synthesis of (DD)BF2+ cations are reported, and compared with the previous method of reacting a chelating donor with Et20.BF3. The methods most effective for aromatic donors such as 1,1O-phenanthroline are ineffective for saturated polydentate tertiary-amines like N,N,N' ,Nil ,Nil-pentamethyldiethylenetriamine. Polydentate tertiary-amine donors that form 5-membered rings upon bidentate chelation were found to chelate effectively when the BF2 source contained two leaving groups (a heavy halide and a Lewis base such as pyridine =pyr or isoxazole =ISOX), i.e., pyr.BF2X (X = CI or Br), ISOX.BF2X and (pyr)2BF2+. Those that would form 6membered rings upon chelation do not chelate by any of the four methods. Polydentate aromatic ligands chelate effectively when the BF2 source contained a weak Lewis base, e.g., ISOX.BF3, ISOX.BF2X and Et20.BF3. Bidentate chelation by polydentate tertiaryamine and aromatic donors leads to nmr parameters that are significantly different then their (D)2BF2+ relatives (D =monod~ntate t-amines or pyridines). The chelated haloboron cations (DD)BFCI+, and (DD)BFBr+ were generated from D.BFX2 adducts for all ligands that form BF2+ cations above. In addition, the (DD)BCI2+ and (DD)BBr2+ cations were formed from D.BX3 adducts by the chelating aromatic ligands, except for the aromatic ligand 1,8-bis(dimethylamino)naphthalene, which formed only the (DD)BF2+ cation, apparently due to its extreme steric hindrance. Chelation by a donor is a two-step reaction. For polydentate tertiary-amine ligands, the two rates appear to be very dependent on the two possible leaving groups on the central boron atom. The order of increasing ease of displacement for the donors was: pyr < Cl < Br < ISOX. The rate of chelation by polydentate aromatic ligands appears to be dependent on the displacement of the first ligand from the boron. The order of increasing ease of displacement for the donors was: pyr < CI < ISOX ~ Br < Et20.

NMR studies of mixed tetrahaloborates and some related boron trihalide complexes /|nGary John Schrobilgen. -- 260 St. Catharines, Ont. : [s. n.],

Nuclear magnetic resonance spectroscopy has been used to study donor-acceptor complexes of boron trifluoride with several ureas, tetramethylthiourea, tetramethylselenourea, and tetramethylquanidine as well as adducts of tetramethyl- -urea with BF2Cl, BFC1 2 , and BC1 3 - A large number of mixed tetrahaloborate ions, including some of the ternary ones such as BF2CIBr-,have been obtained by ligand exchange reactions and studied by NMR techniques. The bonding in these ions is of the same inherent interest as the bonding in the isoelectronic tetrahalomethanes which have been the subject of many detailed studies and have been involved in a controversy concerning the existence of and the nature of "fluorine hyperconjugation" or C-F P1T- Pn bonding_ Ligand exchange reactions also gave rise to the difluoroboron cation, (TMU)20BF2+o The difluoroboron cation has been observed in solutions of TMU-BF3 , and has been proposed as a possible intermediate for fluorine exchange reactions in BF3 adducts.

NMR studies of the exchange reactions of CH3CN.BX3 with excess CH3CN /|nJoseph Fogelman. -- 260 St. Catharines, Ont. : [s. n.],

Exchange reactions between molecular complexes and excess acid or base are well known and have been extensively surveyed in the literature(l). Since the exchange mechanism will, in some way involve the breaking of the labile donor-acceptor bond, it follows that a discussion of the factors relating to bonding in molecular complexes will be relevant. In general, a strong Lewis base and a strong Lewis acid form a stable adduct provided that certain stereochemical requirements are met. A strong Lewis base has the following characteristics (1),(2) (i) high electron density at the donor site. (ii) a non-bonded electron pair which has a low ionization potential (iii) electron donating substituents at the donor atom site. (iv) facile approach of the site of the Lewis base to the acceptor site as dictated by the steric hindrance of the substituents. Examples of typical Lewis bases are ethers, nitriles, ketones, alcohols, amines and phosphines. For a strong Lewis acid, the following properties are important:( i) low electron density at the acceptor site. (ii) electron withdrawing substituents. (iii) substituents which do not interfere with the close approach of the Lewis base. (iv) availability of a vacant orbital capable of accepting the lone electron pair of the donor atom. Examples of Lewis acids are the group III and IV halides such (M=B, AI, Ga, In) and MX4 - (M=Si, Ge, Sn, Pb). The relative bond strengths of molecular complexes have been investigated by:- (i) (ii) (iii) (iv) (v] (vi) dipole moment measurements (3). shifts of the carbonyl peaks in the IIIR. (4) ,(5), (6) .. NMR chemical shift data (4),(7),(8),(9). D.V. and visible spectrophotometric shifts (10),(11). equilibrium constant data (12), (13). heats of dissociation and heats of reactions (l~), (16), (17), (18), (19). Many experiments have bben carried out on boron trihalides in order to determine their relative acid strengths. Using pyridine, nitrobenzene, acetonitrile and trimethylamine as reference Lewis bases, it was found that the acid strength varied in order:RBx3 > BC1 3 >BF 3 • For the acetonitrile-boron trihalide and trimethylamine boron trihalide complexes in nitrobenzene, an-NMR study (7) showed that the shift to lower field was. greatest for the BB~3 adduct ~n~ smallest for the BF 3 which is in agreement with the acid strengths. If electronegativities of the substituents were the only important effect, and since c~ Br ,one would expect the electron density at the boron nucleus to vary as BF3

Polytypism and Silicon carbide : a solid state nuclear magnetic resonance study

A survey of predominantly industrial silicon carbide has been carried out using Magic Angle Spinning nuclear magnetic resonance (MAS nmr); a solid state technique. Three silicon carbide polytypes were studied; 3C, 6H, and 15R. The 13C and 29 Si MAS nmr spectra of the bulk SiC sample was identified on the basis of silicon (carbon) site type in the d iff ere n t pol Y t Y pes • Out to 5.00 A fro mac en t r a lsi 1 i con (0 r carbon) atom four types of sites were characterized using symmetry based calculations. This method of polytype analysis was also considered, in the prelminary stages, for applications with other polytypic material; CdBr 2 , CdI 2 , and PbI 2 " In an attempt to understand the minor components of silicon carbide, such as its surface, some samples were hydrofluoric acid washed and heated to extreme temperatures. Basically, an HF removable species which absorbs at -110 ppm (Si0 2 ) in the 29 Si MAS nmr spectrum is found in silicon carbide after heating. Other unidentified peaks observed at short recycle delays in some 29 Si MAS nmr spectra are considered to be impurities that may be within the lattice. These components comprise less than 5% of the observable silicon. A Tl study was carried out for 29 Si nuclei in a 3C ii polytype sample, using the Driven Equilibrium Single-Pulse Observation of T1 (DESPOT) technique. It appears as though there are a number of nuclei that have the same chemical shift but different T1 relaxation times. The T1 values range from 30 seconds to 11 minutes. Caution has to be kept when interpreting these results because this is the first time that DESPOT has been used for solid samples and it is not likely in full working order. MAS nmr indicates that the 13C and 29 Si ~sotropic chemical shifts of silicon carbide appear to have a reciprocal type of relationship_ Single crystal nmr analysis of a 6H sample is accordance with this finding when only the resultant isotropic shift is considered. However, single crystal nmr also shows that the actual response of the silicon and carbon nuclear environment to the applied magnetic field at various angles is not at all reciprocal. Such results show that much more single crystal nmr work is required to determine the actual behavior of the local magnetic environment of the SiC nuclei.

Simultaneous extraction of order parameters and orientational distribution fuctions from 31[superscript]P NMR spectra of magnetically partially oriented phospholipid bilayers

Order parameter profiles extracted from the NMR spectra of model membranes are a valuable source of information about their structure and molecular motions. To al1alyze powder spectra the de-Pake-ing (numerical deconvolution) ~echnique can be used, but it assumes a random (spherical) dist.ribution of orientations in the sample. Multilamellar vesicles are known to deform and orient in the strong magnetic fields of NMR magnets, producing non-spherical orientation distributions. A recently developed technique for simultaneously extracting the anisotropies of the system as well as the orientation distributions is applied to the analysis of partially magnetically oriented 31p NMR spectra of phospholipids. A mixture of synthetic lipids, POPE and POPG, is analyzed to measure distortion of multilamellar vesicles in a magnetic field. In the analysis three models describing the shape of the distorted vesicles are examined. Ellipsoids of rotation with a semiaxis ratio of about 1.14 are found to provide a good approximation of the shape of the distorted vesicles. This is in reasonable agreement with published experimental work. All three models yield clearly non-spherical orientational distributions, as well as a precise measure of the anisotropy of the chemical shift. Noise in the experimental data prevented the analysis from concluding which of the three models is the best approximation. A discretization scheme for finding stability in the algorithm is outlined

NMR characterization of chlorhexidine in lipid-based formulations /

A mixture of Chlorhexidine digluconate (CHG) with glycerophospholipid 1,2-dimyristoyl- <^54-glycero-3-phospocholine (DMPC-rf54) was analysed using ^H nuclear magnetic resonance. To analyze powder spectra, the de-Pake-ing technique was used. The method is able to extract simultaneously both the orientation distribution function and the anisotropy distribution function. The spectral moments, average order parameter profiles, and longitudinal and transverse relaxation times were used to explore the structural phase behaviour of various DMPC/CHG mixtures in the temperature range 5-60°C.

A29 NMR spin-lattice relaxation study of paramagnetics -doped orthosilictes

A ~si MAS NMR study of spin-lattice relaxation behaviour in paramagnetic-doped crystalline silicates was undertaken, using synthetic magnesium orthosilicate (forsterite) and synthetic zinc orthosilicate (willemite) doped with 0.1% to 20% of Co(II), Ni(II), or CU(II), as experimental systems. All of the samples studied exhibited a longitudinal magnetization return to the Boltzmann distribution of nuclear spin states which followed a stretched-exponential function of time: Y=exp [- (tjTn) n], O

Bis-and tris (amidine) fluoroboron cations and related systems studies by Multinuclear NMR and fast atom bombardment mass spectometry

The formation and the isolation of fluoroboron salts, (D2BF2+)(PF6-), (DD'BF2+)(PF6-) and (D3BF2+)(PF6-)2, have been carried out. 1,8-Diazabicyclo [5,4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4,3,O]non-5-ene (DBN), extremely strong organic bases, were introduced into the fluoroboron cation systems and induced a complicated redistribution reaction in the D/BF3/BC13 systems. The result was the formation of all BFnCI4-n-, D.BFnCI3-n and fluoroboron cation species which were detected by 19p and 11B NMR spectrometry. The displacement reaction of CI- from these D.BFnCI3-n (n = 1 and 2) species by the second entering ligand is much faster than in other nitrogen donor containing systems which have been previously studied. Tetramethylguanidine, oxazolines and thiazolines can also produce similar reactions in D/BF3/BCI3 systems, but no significant BFnC4-n- species were observed. As well as influences of their basicity and their steric hindrance, N=C-R(X) (X = N, 0 or S) and N=C( X)2 (X = N or S) structures of ligands have significant effects on the fonnationof fluoroboron cations and the related NMR parameters. D3BF2+ and some D2BF2+ show the expected inertness, but (DBU)2BF2+ shows an interestingly high reactivity. (D2BF2+)(X-) formed from weak organic bases such as pyridine can react with stronger organic bases and form DD'BF2+ and D'2BF2+ in acetone or nitromethane. Fast atom bombardment mass spectrometry is doubly meaningful to this work. Firstly, FABMS can be directly applied to the complicated fluoroboron cation containing solution systems as an excellent complementary technique to multinuclear NMR. Secondly, the gas-phase ion substitution reaction of (D2BF2+)(PF6-) with the strong organic bases is successfully observed in a FABMS ion source when the B-N bond is not too strong in these cations.

A compilation of the messages and papers of the Presidents, 1789-1902,

UANL