A study of the interactions between carboplatin and blood plasma proteins using size exclusion chromatography coupled to inductively coupled plasma mass spectrometry

To study the carboplatin–protein interaction, a sensitive method using size exclusion chromatography coupled to inductively coupled plasma mass spectrometry (SEC–ICP–MS) was developed. The complexes formed between plasma proteins and carboplatin were monitored and identified with this method. Composite blood plasma samples from patients who were undergoing chemotherapy were analyzed, and carboplatin was found to bind plasma proteins. In addition, blank plasma samples were spiked with carboplatin and were analyzed as a time course study, and the results confirmed that carboplatin formed complexes with plasma proteins, primarily albumin and γ-globulin. To further substantiate the study, these two proteins were incubated with carboplatin. The binding between carboplatin and these proteins was then characterized qualitatively and quantitatively. In addition to a one-to-one binding of Pt to protein, protein aggregation was observed. The kinetics of the binding process of carboplatin to albumin and γ-globulin was also studied. The initial reaction rate constant of carboplatin binding to albumin was determined to be 0.74 M⁻¹ min⁻¹, while that for γ-globulin was 1.01 M⁻¹ min⁻¹, which are both lower than the rate constant of the cisplatin–albumin reaction previously reported.     

Crystal thickness distributions from melting homopolymers or random copolymers

Differential scanning calorimetry (DSC) can be used to infer the distribution of lamellar crystal thickness l. For homopolymers, the relation between melting temperature T and thickness is described by the Gibbs relation. In this case the weight distribution function of thickness g(l) ∝ P(T)(T − T)², where P(T) is DSC power and T is the melting temperature of an infinitely thick crystal. Copolymer melting is affected by the concentration of noncrystallizable comonomer in the melt as well as lamellar thickness. Unknown melt composition in copolymers with nonequilibrium crystallinity makes determination of the correct distribution g(l) from DSC impossible. An approximate distribution g₂(l) ∝ P(T)(T − T)² is proposed, where T is based on Flory's equilibrium crystallization theory. This approximate distribution is most accurate when crystallinity is small, that is, near the upper end of the melting range. Results are reported for polyethylene homopolymer and model ethylene–butene random copolymers. Corrections were not made for distortion of the DSC endotherms by thermal lag or by melting and recrystallization; these experiments are primarily to illustrate the effect of analysis in terms of an incorrect g₃(l) ∝ P(T). Average crystal thicknesses are about 20 nm for polyethylene and 5 nm for the copolymers. Distributions are characterized by l_w /l_n ≤ 1.1 in all cases. Width of the melting range is not a reliable indicator of the breadth of the thickness distribution. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3131–3140, 1999     

Asymmetric epoxidation of cis-alkenes mediated by iminium salts: highly enantioselective synthesis of levcromakalim

[reaction: see text] A range of cis-substituted olefins has been epoxidized with a new dihydroisoquinolinium salt catalyst, using tetraphenylphosphonium monoperoxysulfate as the stoichiometric oxidant, giving ee's of up to 97%. The reaction has been used as the key step in an enantioselective synthesis of the antihypertensive agent levcromakalim.     

Problems associated with interferences in the analysis of serum for polychlorinated biphenyls

During a recent survey to determine serum concentrations of polychlorinated biphenyls (PCBs) among people living around New Bedford, MA, U.S.A., an unidentified contaminant precluded the quantification of some early eluting Webb and McCall peaks. Loss of data is estimated to have reduced reported serum levels by 12%. Efforts to identify the contaminant by gas chromatography with an electron-capture detector, a Hall electrolytic condutivity detector, and mass spectrometer were not successful. Researchers ascertained, however, that the contaminant is not a PCB, it does not contain halogens, but it may contain phthalates. Vacutainer tubes and closures for serum storage bottles are suspected sources of contamination.     

Ice structuring proteins - a new name for antifreeze proteins

Antifreeze proteins (AFPs) have been reported in the academic literature for many years, and are increasingly arousing interest in the technical and popular media, particularly because of their potential applications. However, the term "antifreeze" does not always accurately describe their natural function, or their application in frozen systems, where they do not prevent freezing, but control the size, shape and aggregation of ice crystals. We survey the properties and applications of AFPs and propose a more generally applicable name based on the fact that all AFPs bind to ice and consequently influence crystal growth and interactions: "Ice Structuring Proteins".     

Amidrazones V. thermolysis of N1-benzyl-substituted amidrazone ylides

Thermolysis of 1,1-dimethyl-1-benzyl-2-(iminophenylmethyl)hydrazinium hydroxide inner salt gave dimethylamine, 2,4,6-triphenyl-s-triazine and 2,4,6-triphenyl-1,2-dihydro-s-triazine.     

Chain dimensions in plastically deformed semicrystalline polymers

The effect of plastic deformation on the chain dimensions of polymers in the semicrystalline state was investigated using linear hydrogenated polybutadiene (HPB), a model ethylene/butene-1 copolymer having about 40% crystallinity at room temperature. Dilute blends of deuterium-labeled chains with various molecular weights (20,000 ≤ M ≤ 214,000) in the same unlabeled matrix (M = 95,000) were uniaxially stretched at 25°C to extension ratios of α = 2.4 and 4.4. Radius of gyration normal to the stretch direction R_⊥ was measured for the labeled chains by small-angle neutron scattering. The molecular extension ratio inferred from these data α_m = R/R was significantly smaller than α for short chains (M < 50,000) but increased to the affine range α_m = α for M > 100,000. This variation in α_m/α closely parallels the molecular weight dependence of mechanical strength and ductility in HPB over the same range.     

The electrical and optical properties of amorphous germanium-gallium alloys

The paper extends an earlier study of the far infrared properties of a series of evaporated amorphous GeGa alloys. The results of temperature dependent dc resistivity and near infrared and visible optical experiments are presented. Since the properties of amorphous films are dependent on the preparation conditions, a technique has been developed in which four samples of varying composition are prepared in the same evaporation. The far infrared data indicate that a significant fraction of Ga atoms dissolve in a-Ge with four-fold coordination. However, there is also indirect evidence of mixed valence.     

Determining spin through quantum azimuthal-angle correlations

Determining the spin of new particles is critical in identifying the true theory among various extensions of the Standard Model at the next generation of colliders. Quantum interference between different helicity amplitudes was shown to be effective when the final state is fully reconstructible. However, many interesting new physics processes allow only for partial reconstruction. In this Letter, we show how the interference effect can be unambiguously extracted even in processes that have two-fold ambiguity, by considering the correlation between two decay planes in e⁺e⁻$e^{+}{e}^{-}$ collisions.