Stable aqueous nanoparticle film assemblies with covalent and charged polymer linking networks

The construction of highly stable and efficiently assembled multilayer films of purely water soluble gold nanoparticles is reported. Citrate-stabilized nanoparticles (CS-NPs) of average core diameter of 10 nm are used as templates for stabilization-based exchange reactions with thioctic acid to form more robust aqueous NPs that can be assembled into multilayer films. The thioctic acid stabilized nanoparticles (TAS-NPs) are networked via covalent and electrostatic linking systems, employing dithiols and the cationic polymer poly(L-lysine), respectively. Multilayer films of up to 150 nm in thickness are successfully grown at biological pH with no observable degradation of the NPs within the film. The characteristic surface plasmon band, an optical feature of certain NP film assemblies that can be used to report the local environment and core spacing within the film, is preserved. Growth dynamics and film stability in solution and in the air are examined, with poly(L-lysine) linked films showing no evidence of aggregation for at least 50 days. We believe these films represent a pivotal step toward exploring the potential of aqueous NP film assemblies as a sensing apparatus.     

Expanding the scope of trialkylborane/water-mediated radical reactions

The dehalogenation of alkyl iodides, as well as the chemoselective deoxygenation of a secondary alcohol in the presence of various alkyl and aryl halides, can be accomplished employing a trialkylborane/air/water system.     

Multifunctional core-shell nanoparticles: discovery of previously invisible biomarkers

Many low-abundance biomarkers for early detection of cancer and other diseases are invisible to mass spectrometry because they exist in body fluids in very low concentrations, are masked by high-abundance proteins such as albumin and immunoglobulins, and are very labile. To overcome these barriers, we created porous, buoyant, core-shell hydrogel nanoparticles containing novel high affinity reactive chemical baits for protein and peptide harvesting, concentration, and preservation in body fluids. Poly(N-isopropylacrylamide-co-acrylic acid) nanoparticles were functionalized with amino-containing dyes via zero-length cross-linking amidation reactions. Nanoparticles functionalized in the core with 17 different (12 chemically novel) molecular baits showed preferential high affinities (K(D) < 10(-11) M) for specific low-abundance protein analytes. A poly(N-isopropylacrylamide-co-vinylsulfonic acid) shell was added to the core particles. This shell chemistry selectively prevented unwanted entry of all size peptides derived from albumin without hindering the penetration of non-albumin small proteins and peptides. Proteins and peptides entered the core to be captured with high affinity by baits immobilized in the core. Nanoparticles effectively protected interleukin-6 from enzymatic degradation in sweat and increased the effective detection sensitivity of human growth hormone in human urine using multiple reaction monitoring analysis. Used in whole blood as a one-step, in-solution preprocessing step, the nanoparticles greatly enriched the concentration of low-molecular weight proteins and peptides while excluding albumin and other proteins above 30 kDa; this achieved a 10,000-fold effective amplification of the analyte concentration, enabling mass spectrometry (MS) discovery of candidate biomarkers that were previously undetectable.     

SERS approach for Zn(II) detection in contaminated soil

Soil contamination by metals is a common problem encountered in many industrialized countries. In this work we present a new approach for heavy metals detection by using surface-enhanced Raman scattering (SERS) spectroscopy. Zn(II) can be clearly determined by SERS in contaminated soil by using 4-(2-pyridylazo) resorcinol (PAR) as chelating molecule for the metal ion. The SERS spectra of PAR, of its metal chelates and of the soil extract-PAR mixture were recorded using a hydroxylamine reduced silver colloid. An excellent match of the PAR-contaminated soil extracts SERS spectrum to the Zn(PAR)₂ SERS spectrum can be observed, demonstrating the presence of Zn(II) in the soil probes. Density functional theory (DFT) based calculations were also performed for a reliable assignment of SERS spectra.     

Experimental investigation into the interference aerodynamics of two slender bodies in close proximity

Aerodynamic interference between high-speed slender bodies can detrimentally affect the force and moment characteristics. This is investigated through a wind tunnel study using pressure sensitive paint and force measurements on a receiver body placed adjacent to a generator body. The aim of this paper is to understand both the force and moment changes as well as the underlying aerodynamics of the interference loads which are induced by the disturbance flowfield. The impact of receiver incidence and the strength of the disturbance field are also assessed. The observed interference loads primarily depend on a complex balance of static pressure footprints and tend to be bespoke to each configuration. As a result, overall trends are difficult to extract, but in general the magnitude of the interference loads increases when the receiver is at incidence and also when the strength of the imposed disturbance flowfield increases.     

On functions convex in the direction of the real axis with a fixed second coefficient

In the paper we consider the class Γ of analytic and univalent functions f in the unit disk Δ, normalized by f(0) = f′(0) − 1 = 0, having real coefficients and such that f(Δ) is convex in the direction of the real axis. We are especially interested in some subclasses of Γ. The most important of them is Γ(c) consisting of those functions which have the second coefficients of the Taylor expansion fixed and equal to c. We obtain the Koebe set for this class as well as for the classes Γ⁺(c) and Γ⁻(c) of functions which are in some sense convex in the direction of positive and negative axes respectively.     

PHOSPHORORGANISCHE VERBINDUNGEN 851 SYNTHESE UND ANWENDUNG OPTISCH AKTIVER TERTIÄRER PHOSPHINE ALS CO-KATALYSATOREN DER HOMOGENHYDRIERUNG MIT RHODIUM-PHOSPHIN-KOMPLEXEN

Abstract

Die Darstellung der optisch aktiven Methyl-n-propyl(bzw.-isopropyl)arylphosphine 1 bis 8 wird beschrieben. Hierbei ist Aryl: p-Methoxyphenyl (1 und 2), p-Dimethylaminophenyl (3 und 4), o-Methoxyphenyl (5 und 6), o-Dimethyl-aminophenyl (7) und o-Aminophenyl (8).

Die Phosphine 1 bis 8 werden als optisch aktive Co-Katalysatoren bei der Homogenhydrierung von α- und ß-Methylzimtsäureethylester, der α-Acetaminoacrylsäure und der α-Acetaminozimtsäure mit Rhodium-Phosphinkomplexen eingesetzt und jeweils die optische Induktion bestimmt. Folgende Ergebnisse (Vgl. die Tabellen 1 bis 4) wurden erhalten:

1) Die CH₃O-Gruppe und N(CH₃)₂-Gruppe verändern unabhängig von ihrer Stellung die optische Induktion bei der Homogenhydrierung von α- und ß-Methylzimtsäureethylester nur unwesentlich im Vergleich zu den entsprechenden Methyl-n-propyl (bzw.-isopropyl)-phenylphosphinen.

2) Bei der Homogenhy drierung von α-Acetaminoacrylsäure und α-Acetaminozimtsäure üben para-ständige OCH₃- und (CH₃)₂N-Gruppen in den optisch aktiven Co-Katalysatoren (Verbindungen 1 bis 4) keinen Einfluß auf die Höhe der optischen Induktion aus.

3) In ortho-Stellung verknüpfte OCH₃- und (CH₃)₂N-Gruppen (Verbindungen 5 bis 7) führen jedoch bei der Homogenhydrierung von α-Acetaminoacrylsäure und α-Acetaminozimtsäure zu einer beachtlichen Erhöhung der optischen Induktion. Bei α-Acetaminozimtsäure und 7 als Co-Katalysator beträgt die optische Induktion 80%! Hierbei übertrifft die (CH₃)₂N-Gruppe die CH₃O-Gruppe an Wirksamkeit.

4) Methyl-n-propyl-o-aminophenylphosphin 8 ist als Co-Katalysator unbrauchbar, da es offenbar durch Wechsel-wirkung der NH₂-Gruppe mit Rhodium die Koordinierung des prochiralen Olefins mit dem Komplex unterdrückt.

5) Eine experimentell begründete Deutung für das Zusammenwirken der am Aufbau der Homogenkatalysatoren beteiligten Komponenten konnte nicht gegeben werden.

Tabelle 5 zeigt die Abhängigkeit der Hydriergeschwindigkeit von Art und Stellung der Substituenten im Phenylrest. Die Hydriergeschwindigkeit ist bei den induktionsstarken Co-Katalysatoren 5 bis 7 deutlich vermindert.

The preparation of the optically active methyl-n-propyl(isopropy) aryl phosphines 1 ± 8 is described, whereby the aryl group is p-methoxyphenyl (1, 2), p-dimethylaminophenyl (3, 4), o-methoxyphenyl (5, 6), o-dimethylaminophenyl (7) and o-aminophenyl (8).

The phosphines 1–8 were used as chiral co-catalysts at the rhodium complex in the homogeneous hydrogenation of α- and ß-methyl cinnamic acids, α-acetaminoacrylic acid and α-acetaminocinnamic acid. The optical induction in the products was measured. The following results (see Tables 1–4) were obtained:

1) The methoxy and dimethylamino groups, independent of their site, have only negligible influence on the optical yield in the reduction of α- and ß-methylcinnamic acids compared with the parent methyl-propylphenylphosphine.

2) In the hydrogenation of acetaminoacrylic acid and α-acetaminocinnamic acid, para methoxy- or dimethylamino groups (compounds 1–4) show likewise no special influence on the optical yield.

3) Ortho methoxy or dimethylamino groups (compounds 5–7), however, result in a measurable increase in optical yield in the reduction of α-acetaminoacrylic- and α-acetaminocinnamic acids. In the case of compound 7 with α-acetaminocinnamic acid, an optical purity of 80% was obtained! The dimethylamino group is in this case more effective than the methoxy group.     

PHOSPHORORGANISCHE VERBINDUNGEN 1171, EINE NEUE METHODE ZUM NACHWEIS DER FUNKTIONELLEN GRUPPEN: OH,NH2 UND SH DURCH AUSLOSUNG VON FLUORESZENZ

Abstract

Covalently with a fluorescence support linked nitroarylester groups quench the fluorescence. The substitution of the fragment with the quenching group by an other functional group initiates fluorescence. If this substitution reaction is chemoselective, a reagent for the selective detection of a special functional group is available.

The non fluorescent compounds 1a and 1b are OH-(resp. F^(-)) selective; the compounds 5 and 7 are NH-selective and the compounds 8 and 9 are SH-selective. Dansyl-nitroimidazolide 7a discriminates between neutral and basic α-amino acids.     

Wavelet compression of integral operators arising from boudary-domain integral method

The boundary-domain integral method uses Green's functions to write integral representations of partial differential equations. Since Green's functions are non-local, the systems of linear equations arising from the discretization of integral representations are fully populated. Several algorithms have been proposed, which yield a data-sparse approximation of these systems, such as the fast multipole method, adaptive cross approximation and among others, wavelet compression. In the framework of solving the Navier-Stokes equations in velocity-vorticity form one may utilize the boundary-domain integral method for the solution of the kinematics equation to calculate the boundary vorticity values. Since the kinematics equation is a Poisson type equation, usually its integral representation is written with the Green's function for the Laplace operator. In this work, we introduce a false time into the equation and parabolize its nature. Thus, a time-dependent Green's function may be used. This provides a new parameter, the time step, which can be set to control the Green's function. The time-dependent Green's function is a global function, but by carefully choosing the time step, its behaviour is almost local. This makes it a good candidate for wavelet compression, yielding much better compression ratios at a given accuracy than when using the Green's function for the Laplace operator. However, as false time is introduced, several time steps must be solved in order to reach a converged solution. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)