The indirect spectrophotometric determination of the sulphate ion with 2-aminoperimidine

A new spectrophotometric determination of the sulphate ion is described which uses 2-aminoperimidine hydrochloride as a precipitating reagent. The excess of the reagent is measured at 305 nm. The procedure deals with sulphate in the range 4–120 p.p.m., and relies on simple calibration. The relative standard deviation for 50 p.p.m. of sulphate is 3.7%. The interference of 100 p.p.m. of phosphate, fluoride and nitrate is only slight in the determination of 50 p.p.m. of sulphate. The method is recommended for the determination of sulphate in rain and surface waters.     

Arylthallium trifluoroacetates carbon-13 and fluorine-19 nuclear magnetic resonance: The substituent effect of the bis(trifluoroacetato)- thallium(III) group

¹³C NMR data for a series of arylthallium trifluoroacetates (ArTlX₂, X = OCOCF₃) are reported and assigned. The range of carbon—thallium couplings to be expected, the dependence on the disposition of coupled nuclei, and chemical shift effects are discussed. The Tl(OCOCF₃)₂ group is shown to be a powerful electron withdrawing group, from both the ¹³C data and ¹⁹F substituent chemical shifts of the p-fluorophenyl derivative.     

Evaluation of protocols for reproducible electrospray in-source collisionally induced dissociation on various liquid chromatography/mass spectrometry instruments and the development of spectral libraries

Mass spectral libraries provide a tool for identifying unknown compounds using both molecular weight and fragmentation information. Mass spectrometers with electrospray ionisation (ESI) and atmospheric chemical ionisation (ApCI) sources have the capability to produce data of this type using in-source collisionally induced dissociation (CID), and in-source CID libraries can be created. Due to the variation in electrospray source design from different instrument manufacturers, the production of reproducible in-source CID spectra that can be used in libraries for all instrument types is not a trivial task. To date, the evaluation of the production of in-source CID libraries has tended to focus on similar instruments from one manufacturer. The studies have also tended to focus on specific compound classes, with a limited molecular weight range.This report describes the findings from the investigation of protocols for the creation of mass spectral libraries using ESI in-source CID on six instruments from four different manufacturers. The overall goal was to create a spectral library for the identification of unknowns. The library could then be applied across all manufacturers' electrospray instruments.Two different experimental protocols were attempted. The first used a tuning compound to establish standard ESI source conditions, with fixed fragmentation potentials. The second involved the attenuation of the [M + H](+) ion to a known degree. A diverse range of compounds (pharmaceutical, photographic, pesticides) was tested to establish the reproducibility of the spectra on the six instruments. Both protocols produced spectra on the various instruments that in many cases were very similar. In other examples, the spectra differed not only in their relative ion abundances, but also in terms of the spectral content. Important observations regarding the effect of ion source design are also reported.The degree of spectral reproducibility was calculated off-line by comparing the five most abundant ions (20% for each ion that matches) from each spectrum on each instrument. This approach was adopted, as we do not possess a software package that met our requirements for spectral comparison. Match factors (% fit) were calculated by comparing each spectrum against the spectra recorded for the same compound and then for all other compounds, on each instrument. The % fit values derived by the off-line approach gave a clear view of the spectral reproducibility from instrument to instrument and also discriminated the spectra of the various compounds from each other. The applicability of this approach was tested using a blind trial in which several compounds were presented as unknowns, their in-source CID spectra recorded and the five-ion approach used for identification.     

Synthesis of luminescent gold(I) and gold(III) complexes with a triphosphine ligand

We have synthesized and characterized a series of trinuclear gold(I) complexes [(AuX)(3)(mu-triphos)] (triphos = bis(2-diphenylphosphinoethyl)phenylphosphine; X = Cl 1, Br 2, I 3, C(6)F(5) 4) and di- and trinuclear gold(III) complexes [[Au(C(6)F(5))(3)](n)(mu-triphos)] (n = 2 (5), 3 (6)). The crystal structure of 6 [[Au(C(6)F(5))(3)](3)(mu-triphos)] has been determined by X-ray diffraction studies, which show the triphosphine in a conformation resulting in very long gold-gold distances, probably associated with the steric requirements of the tris(pentafluorophenyl)gold(III) units. Complex 6 crystallizes in the triclinic space group P(-1) with a = 12.7746(16) A, b = 18.560(2) A, c = 21.750(3) A, alpha = 98.215(3) degrees, beta = 101.666(3) degrees, gamma = 96.640(3) degrees, and Z = 2. Chloride substitutions in complex 1 afford trinuclear gold(I) complexes [(AuX)(3)(mu-triphos)] (X = Fmes (1,3,5-tris(trifluoromethyl)phenyl) 7, p-SC(6)H(4)Me 8, SCN 9) and [Au(3)Cl(3)(-)(n)()(S(2)CNR(2))(n)(mu-triphos)] (R = Me, n = 3 (10), 2 (12), 1 (14); R = CH(2)Ph, n = 3 (11), 2 (13), 1 (15)). The luminescence properties of these complexes in the solid state have been studied; at low temperature most of them are luminescent, including the gold(III) derivative 6, with the intensity and the emission maxima being clearly influenced by the nature and the number of the ligands bonded to the gold centers.     

Chiroptical properties of n-nitrosopyrrolidines and n-nitrosamino acids : Implications for the nitrosamine sector rule

CD data for a variety of N-nitrosamino acids and N-nitrosopyrrolidines are presented. The effects of nitrosamino group conformation, pyrrolidine ring geometry, different perturbing substituents, and especially intramolecular H-bonding upon the n → π^* CD band are discussed. Stereochemical conclusions can be made with confidence in many cases, although no sector diagram, as yet published, successfully correlates all the available chiroptical data in this series of compounds. However, a negative CD band due to the π → π* transition was observed tor all N-nitrosamines having the L-proline configuration at C-2, regardless of nitroso group conformation; it is suggested that this band be used whenever possible for stereochemical correlations.     

Detection of a biomarker for Alzheimer's disease from synthetic and clinical samples using a nanoscale optical biosensor

A nanoscale optical biosensor based on localized surface plasmon resonance (LSPR) spectroscopy has been developed to monitor the interaction between the antigen, amyloid-beta derived diffusible ligands (ADDLs), and specific anti-ADDL antibodies. Using the sandwich assay format, this nanosensor provides quantitative binding information for both antigen and second antibody detection that permits the determination of ADDL concentration and offers the unique analysis of the aggregation mechanisms of this putative Alzheimer's disease pathogen at physiologically relevant monomer concentrations. Monitoring the LSPR-induced shifts from both ADDLs and a second polyclonal anti-ADDL antibody as a function of ADDL concentration reveals two ADDL epitopes that have binding constants to the specific anti-ADDL antibodies of 7.3 x 10(12) M(-1) and 9.5 x 10(8) M(-1). The analysis of human brain extract and cerebrospinal fluid samples from control and Alzheimer's disease patients reveals that the LSPR nanosensor provides new information relevant to the understanding and possible diagnosis of Alzheimer's disease.     

The PLAC1-homology region of the ZP domain is sufficient for protein polymerisation

Background  

Hundreds of extracellular proteins polymerise into filaments and matrices by using zona pellucida (ZP) domains. ZP domain proteins perform highly diverse functions, ranging from structural to receptorial, and mutations in their genes are responsible for a number of severe human diseases. Recently, PLAC1, Oosp1-3, Papillote and CG16798 proteins were identified that share sequence homology with the N-terminal half of the ZP domain (ZP-N), but not with its C-terminal half (ZP-C). The functional significance of this partial conservation is unknown.     

Synthesis and stereochemical assignment of 7-arylidene and 7-heteroarylidene morphinan-6-ones

A number of (E)-7-arylidenenaltrexones were synthesized by azeotropic distillation of water from a benzene solution of naltrexone and an aromatic aldehyde (benzaldehyde, 4-chloro- and 4-fluorobenzaldehyde, 3-and 4-pyridinecarboxaldehyde and 1-methyl-2-imidazolecarboxaldehyde) using piperidine as a catalyst. In addition, (E)-7-benzylidenenaloxone was prepared by the previously published Claisen-Schmidt condensation using sodium hydroxide in methanol. The stereochemistry of these arylidene derivatives 3–9 was determined to be (E) by means of nuclear Overhauser enhancement experiments. The ¹³C nmr spectra of (E)- 3–9 are recorded in deuteriochloroform and those of the hydrochlorides in deuteriodimethyl sulfoxide.     

Organometallic Reactions and Syntheses : Volume 6, E. I. Becker and M. Tsutsui,ed., Plenum Publishing Corporation., New York/ London, 1977, xii + 314 pages $47.40

The (Me₃Si)₃C group causes very large steric hindrance to nucleophilic displacement at a silicon atom to which it is attached, and (Me₃Si)₃CSiMe₂Cl is even less reactive than t-Bu₃SiCl towards base. The compounds (Me₃Si)₃CSiMe₂X (X = Cl, Br, or I) are cleaved by MeOH/MeONa to give (Me₃Si)₂CHSiMe₂OMe, possibly via the silaolefin (Me₃Si)₂ CSiMe₂, and the correspondLug (Me₃Si)₃ CSiPh₂X compounds undergo the analogous reaction even more readily. The halides (Me₃Si)₃CSiR₂X (X = Cl or Br) and (Me₃Si)₃CSiCl₃ do not react with boiling alcoholic silver nitrate, but the iodides (Me₃Si)₃CSiR₂I are rapidly attacked.