A phosphorus-31 nuclear magnetic resonance spectroscopic study of complexes of zinc with some phosphine oxides, sulfides, and selenides

1983 ◽  
Vol 61 (8) ◽  
pp. 1800-1805 ◽  
Author(s):  
Philip A. W. Dean ◽  
Geetha K. Carson
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Spectroscopic Study ◽  
Mixed Oxide ◽  
Ligand Exchange ◽  
Nmr Spectra ◽  
Zinc Complexes ◽  
Phosphine Oxides ◽  
Cadmium Complexes ◽  
Slow Exchange

Zn(SbF6)2 in liquid SO2 has been shown to act as an acceptor towards a variety of phosphine oxides, sulfides, and selenides, forming complexes which have been characterized in solution using 31P nmr. Slow-exchange 31P nmr spectra are reported for the complexes ZnLn2+ (n = 6, L2 = Ph2P(O)CH2P(O)Ph2 or L3 = (Ph2P(O)(CH2)2)2P(O)Ph; n = 4, L2 = Ph2P(E)CH2P(E)Ph2 (E = O, S, or Se) or bidentate (Ph2P(E)CH2)3CMe (E = S or Se), or L = (C6H11)3PE (E = O, S, or Se) or R3PE (E = S or Se, R = Ph or o-C6H4Me); n = 3, L3 = (Ph2P(E)(CH2)2)2P(E)Ph (E = S or Se) or L = R3PE (E = S or Se, R = C6H11, Ph, or o-C6H4Me); n = 2, L = R3PE (E = S or Se, R = o-C6H4Me or, perhaps, C6H11); n = 1 (possibly), L = (o-C6H4Me)3PS), and partial spectra for [Zn(SeP(C6H11)3)x(SP(C6H11)3)n−x]2+ (n = 3 or 4). No evidence was found for the mixed oxide-chalcogenide species [Zn(EP(C6H11)3)x(OP(C6H11)3)4−x]2+. In most cases the 31P nmr spectra are very similar to those reported earlier for the corresponding cadmium complexes. However, in most instances where comparison could be made it was found that the rate of intermolecular ligand exchange was less for the zinc complexes than for their cadmium counterparts. (Complexes with (Ph2P(O)(CH2)2)2P(O)Ph and Ph2P(O)(CH2)2P(O)Ph2 arc exceptional in being more labile for zinc than cadmium.)

A 113Cd nuclear magnetic resonance study of some complexes of cadmium with phosphine oxides, sulfides, and selenides

1981 ◽  
Vol 59 (23) ◽  
pp. 3221-3225 ◽  
Author(s):  
Philip A. W. Dean
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Phosphine Oxide ◽  
Nmr Spectra ◽  
Nuclear Magnetic Resonance Study ◽  
Phosphine Oxides ◽  
Cd Spectra ◽  
Magnetic Resonance Study ◽  
Slow Exchange ◽  
Reduced Temperature

113Cd(AsF6)2 has been synthesized from 113CdO by treatment in SO2 with PF5 then AsF5. From the 113Cd-enriched salt have been prepared [Cd(EPR3)4]2+ (E = O, R = C6H11; E = S or Se, R = Ph), [Cd(SP(C6H11)3)x(SeP(C6H11)n−x]2+ (n = 4, x = 0–4; n = 3, x = 0–3), [Cd(EP(o-C6H4Me)3)n]2+ (E = S, n = 4 or 2; E = Se, n = 3 or 2), [Cd(Ph2P(O)(CH2)nP(O)Ph2)3]2+ (n = 1 or 2), and [Cd(Ph2P(O)((CH2)2P(O)Ph2)2)2]2+ in liquid SO2. The reduced temperature slow exchange 31P and 113Cd nmr spectra have been measured and are discussed. The 31P nmr are as expected from previous work on complexes containing 113Cd at natural abundance except that several values of 2J(113Cd—O—31P) have been measured. From the 113Cd spectra the most important shielding sequences observed are [Formula: see text] for [Cd(EP(C6H11)3)4]2+, δ2:1 < δ3:1 < δ4:1 for [Cd(EPR3)n]2+ (E = S or Se, n = 1–4, constant R), and [Formula: see text] for the various phosphine oxide complexes studied.The synthesis of SO2-insoluble Cd(SbF6)2•3(OP(C6H11)3) is reported.

Nuclear Magnetic Resonance and Infrared Spectroscopic Study of N-Vinyl Compounds

1968 ◽  
Vol 22 (3) ◽  
pp. 161-164 ◽  
Author(s):  
William R. Landis ◽  
Theodore D. Perrine
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Spectroscopic Study ◽  
Infrared Spectra ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Infrared Spectroscopic Study ◽  
Resultant Data ◽  
Vinyl Group ◽  
Nuclear Magnetic

The nuclear magnetic resonance and infrared spectra of five N-vinyl compounds and the corresponding N-ethyl compounds have been observed in order to obtain detailed information about the N-vinyl group. Resultant data indicate that one might prove the presence of N-vinyl by two characteristic infrared maxima in the region of 1390 to 1300 cm−1. The NMR spectra of the N-vinyl protons conform to the expected ABX pattern. The chemical shifts do not permit differentiation from other vinyl types.

scholarly journals P052 Nuclear magnetic resonance metabolomic profiling of IBD patients under anti-TNF treatment. Are the pathways network deregulated?

2020 ◽  
Vol 14 (Supplement_1) ◽  
pp. S160-S160
Author(s):  
S Notararigo ◽  
M Martin-Pastor ◽  
J E Dominguez Munoz ◽  
M Barreiro-de Acosta
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nmr Spectra ◽  
Mononuclear Cells ◽  
High Rate ◽  
Resonance Spectroscopy ◽  
Serum Samples ◽  
Spectral Window ◽  
Metabolomic Study ◽  
Nuclear Magnetic

Abstract Background The deregulation of immune system cell response implies loss of T-cell apoptosis, high rate of proinflammatory cytokines production and subsequent exacerbate activation of TNF-α pathway. The use of biologic antibody decrease inflammation rate and symptoms, but it remains unclear if it has a direct effect on the pathways activation/inactivation on peripheral blood mononuclear cells (PBMCs). The aim of this study is evaluate the role of nuclear magnetic resonance spectroscopy (NMR) applied to the metabolomic study of serum samples isolated from fresh blood from inflammatory bowel disease (IBD) patients under IFX treatment to understand the activated/inactivated pathways of PBMCs. Methods A case–control study was performed. Inclusion criteria were IBD patients under IFX treatment. Blood samples were obtained in Crohn’s disease (CD) and ulcerative colitis (UC) patients before IFX and in healthy controls (CTRL). CD patients were divided into subgroups according to the gut affected, in Ileocolic (IC), ileum and colon. NMR samples of the serum were collected and measured according to Standard Operation Procedures. Three types of NMR spectra were measured for each serum sample (1Hnoepresat, 1Hcpmgpresat and 1HDfilterpresat). The signal in each NMR spectrum was integrated in a series of equidistant little portion of the spectrum called buckets of a constant width of 0.04 ppm, covering the complete 1H NMR spectral window from −5 to 14 ppm. Buckets in regions depleted from signal at the two extremes of the spectrum were discarded as well as those in the proximity of the water peak at ca. 4.7 ppm which was affected by the presaturation. The vectors corresponding to a number of samples of two or more groups can be rapidly analysed using Multivariant Statistical Analysis methods. Results Twenty-two IBD patients (12 CD and nine UC) were included, 10 CTRL were also included. The metabolomic analyses of the NMR spectra of the serum of the different patients and control groups by the fingerprinting and targeting profiling strategies provided OPLS-DA statistical models (Figure 1) that permitted the successful classification of certain groups of samples which are summarised in Table 1. Conclusion The results of this pilot NMR metabolomic study of serum samples of IBD found a series of spectral fingerprints that are able to discriminate between groups of patients CTRL and CD, which underlines its potential use for the diagnosis of the disease.

The metal nuclear magnetic resonance spectra of some tin(II) and lead(II) complexes with polydentate phosphines

1983 ◽  
Vol 61 (8) ◽  
pp. 1795-1799 ◽  
Author(s):  
Philip A. W. Dean
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nmr Spectra ◽  
Narrow Range ◽  
Chemical Shifts ◽  
Nuclear Magnetic Resonance Spectra ◽  
Magnetic Resonance Spectra ◽  
Nuclear Magnetic

The previously reported 1:1 complexes formed in MeNO2, between M(SbF6)2 (M = Sn or Pb) and Ph2P(CH2)2PPh2, PhP[(CH2)2PPh2]2, MeC(CH2PPh2)3, P[(CH2)2PPh2]3, and [Formula: see text] have been studied by metal (119Sn or 207Pb) nmr. The metal chemical shifts span the comparatively narrow range of −586 to −792 ppm and 60 to −269 ppm, relative to the resonance of MMe4, for 119Sn and 207Pb nmr, respectively. The implications of these data regarding the denticity of the ligand in M(P[(CH2)2PPh2]3)2+ are discussed, and a comparison with the metal nmr spectra of related stannous and plumbous complexes is made.

Nuclear magnetic resonance characterization of the ring conformations of monosubstituted derivatives of 1,3-dioxa-5,6-benzocycloheptene

1983 ◽  
Vol 61 (1) ◽  
pp. 109-115 ◽  
Author(s):  
R. St-Amour ◽  
M. St-Jacques
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Substituent Effects ◽  
Steric Effects ◽  
Slow Exchange ◽  
Conformational Properties ◽  
Derivatives Of ◽  
Ring Conformations ◽  
Twist Boat

The conformational properties of 2-alkyl (Me, Et, i-Pr, and t-Bu) and 2-phenyl derivatives of 1,3-dioxa-5,6-benzocycloheptene (1) were studied by 13C dnmr. Analysis of slow exchange spectra at 100.6 MHz indicates that all derivatives except tert-butyl exist in an equilibrium of chair (major) and twist-boat (minor) conformations. Substituent effects on the position of the equilibrium are rationalized in terms of steric effects.

Anesthetic-membrane interaction: A 2H nuclear magnetic resonance study of the binding of specifically deuterated tetracaine and procaine to phosphatidylcholine

1984 ◽  
Vol 62 (2-3) ◽  
pp. 178-184 ◽  
Author(s):  
Eric C. Kelusky ◽  
Ian C. P. Smith
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Local Anesthetics ◽  
Nuclear Magnetic Resonance Study ◽  
Weakly Bound ◽  
Slow Exchange ◽  
H Nmr ◽  
Line Shapes ◽  
Acyl Chains ◽  
Nuclear Magnetic

The binding of the local anesthetics tetracaine and procaine with multilamellar dispersions of egg phosphatidylcholine has been studied by 2H nuclear magnetic resonance (NMR). The 2H-NMR line shapes of specifically deuterated local anesthetics are found to be very dependent on the attainment of a true equilibrium. The equilibrium could be most properly reached by the use of repeated freeze–thaw–vortex cycles. The data for tetracaine are consistent with the three-site exchange model proposed earlier. Tetracaine is in slow exchange between a strongly bound site and a weakly bound site and in fast exchange between the weakly bound site and free in solution. The slow exchange rate is estimated, from temperature and dilution studies, to be approximately 1.5 × 103 s−1 at pH 5.5 and slightly faster at pH 9.5. Comparisons of the quadrupole splittings with those seen for our earlier work in egg phosphatidylethanolamine suggest that the location of the strongly bound site in phosphatidylcholine is dependent on the anesthetic charge. This is in contrast to egg phosphatidylethanolamine, where molecular shapes appear to be the determining factor for the location of the anesthetic. Procaine bound very weakly to the model membranes, to yield only a broad resonance and no quadrupole splitting. It appears that procaine, unlike tetracaine, is not bound by the ordered acyl chains.

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