Temperature-induced changes in the EPR spectrum of the magnetic center in kaolin

Studies of kaolin have revealed an effect characterized by an unusual temperature-induced change of the EPR spectrum of the Fe3+ ion, which is the magnetic probe in kaolin-clay. At low temperature (T=4.2 K) a resonance line with an effective g-value g1=4.13 +/- 0.16 is observed. At high temperature (T=288 K) one observes a resonance line with the effective g-value g2=2.15 +/- 0.1. The transition from the low- to high-temperature spectrum is gradual and it is accompanied by a redistribution of the absorption intensity. The observed properties of the temperature dependence of the EPR spectrum are characteristic of systems with a multiminimum potential.     

Site-specific conjugation of ScFvs antibodies to nanoparticles by bioorthogonal strain-promoted alkyne-nitrone cycloaddition

Particularly suitable: An N-terminal serine mutant of anti-HER2 scFv antibody was conjugated to polymer-coated magnetofluorescent nanoparticles by strain-promoted alkyne-nitrone cycloaddition. The resulting nanoparticles (see scheme) proved effective in targeting and labeling HER2-positive breast cancer cells.     

Hydrosilylation of alkynes by Ni(CO)3-stabilized silicon(II) hydride

Not copy and paste: Although β-diketiminato ligands have been employed for the stabilization of Ge(II) and Sn(II) hydrides, the corresponding Si(II) hydride is not accessible. However, coordination of silicon(II) to a {Ni(CO)(3)} fragment allowed the isolation of the first Si(II) hydride metal complex 1. This complex was used for the first silicon(II)-based and Ni(0)-mediated, stereoselective hydrosilylation of alkynes. R = phenyl, tolyl.     

Cyanation of Aryl Bromides with K4[Fe(CN)6] Catalyzed by Dichloro[bis{1‐(dicyclohexylphosphanyl)piperidine}]palladium,a Molecular Source of Nanoparticles,and the Reactions Involved in the Catalyst‐Deactivation Processes

Dichloro[bis{1‐(dicyclohexylphosphanyl)piperidine}]palladium [(P{(NC₅H₁₀)(C₆H₁₁)₂})₂PdCl₂] ( 1 ) is a highly active and generally applicable C? C cross‐coupling catalyst. Apart from its high catalytic activity in Suzuki, Heck, and Negishi reactions, compound 1 also efficiently converted various electronically activated, nonactivated, and deactivated aryl bromides, which may contain fluoride atoms, trifluoromethane groups, nitriles, acetals, ketones, aldehydes, ethers, esters, amides, as well as heterocyclic aryl bromides, such as pyridines and their derivatives, or thiophenes into their respective aromatic nitriles with K₄[Fe(CN)₆] as a cyanating agent within 24 h in NMP at 140 °C in the presence of only 0.05 mol % catalyst. Catalyst‐deactivation processes showed that excess cyanide efficiently affected the molecular mechanisms as well as inhibited the catalysis when nanoparticles were involved, owing to the formation of inactive cyanide complexes, such as [Pd(CN)₄]^2?, [(CN)₃Pd(H)]^2?, and [(CN)₃Pd(Ar)]^2?. Thus, the choice of cyanating agent is crucial for the success of the reaction because there is a sharp balance between the rate of cyanide production, efficient product formation, and catalyst poisoning. For example, whereas no product formation was obtained when cyanation reactions were examined with Zn(CN)₂ as the cyanating agent, aromatic nitriles were smoothly formed when hexacyanoferrate(II) was used instead. The reason for this striking difference in reactivity was due to the higher stability of hexacyanoferrate(II), which led to a lower rate of cyanide production, and hence, prevented catalyst‐deactivation processes. This pathway was confirmed by the colorimetric detection of cyanides: whereas the conversion of β‐solvato‐α‐cyanocobyrinic acid heptamethyl ester into dicyanocobyrinic acid heptamethyl ester indicated that the cyanide production of Zn(CN)₂ proceeded at 25 °C in NMP, reaction temperatures of >100 °C were required for cyanide production with K₄[Fe(CN)₆]. Mechanistic investigations demonstrate that palladium nanoparticles were the catalytically active form of compound 1 .     

Combined muta- and semisynthesis: a powerful synthetic hybrid approach to access target specific antitumor agents based on ansamitocin P3

Access of four new tumor specific folic acid/ansamitocin conjugates is reported that relies on a synthetic strategy based on the combination of mutasynthesis and semisynthesis. Two bromo‐ansamitocin derivatives were prepared by mutasynthesis or by a modified fermentation protocol, respectively, that served as starting point for the semisynthetic introduction of an allyl amine linker under Stille conditions. A sequence of standard coupling steps introduced the pteroic acid/glutamic acid/cysteine unit to the modified ansamitocins. All new derivatives, including those that are expected to be generated after internalization of the folic acid/ansamitocin conjugates into the cancer cell and reductive cleavage of the disulfide linkage showed good to strong antiproliferative activity (IC₅₀ <10 nM ) for different cancer cell lines. Finally, the four conjugates were exposed to two cancer cell lines [cervix carcinoma, KB‐3‐1 (FR+) and lung carcinoma, A‐459 (FR?)], the latter devoid of the membrane‐bound folic acid receptor (FR?). All four conjugates showed strong antiproliferative activity for the FR+ cancer cell line but were inactive against the FR? cell line. The synthetic strategy pursued is based on the combination of mutasynthesis and semisynthesis and proved to be powerful for accessing new ansamitocin derivatives that are difficult to prepare by total synthesis.     

AFM diagnostics of graphene-based quantum Hall devices

In this paper we present the results of morphological, mechanical and electrical investigation of the properties of prepared graphene flakes and graphene-based quantum Hall devices. AFM imaging allowed us to identify the local imperfections and unintentional modifications of the graphene sheets which had caused severe deterioration of the device electrical performance. Utilizing the NanoSwing imaging method, based on the time-resolved tapping mode, we could observe non-homogeneities of the structural and mechanical properties. We also diagnosed the device under working conditions by Kelvin probe microscopy and detected its local electric field distribution.     

Efficient γ-amino-proline-derived cell penetrating peptide-superparamagnetic iron oxide nanoparticle conjugates via aniline-catalyzed oxime chemistry as bimodal imaging nanoagents

Aniline-catalyzed oxime chemistry was employed to conjugate a γ-amino-proline-derived cell penetrating peptide to superparamagnetic iron oxide nanoparticles (SPIONs). Internalization of the novel nanoconjugate into HeLa cells was found to be remarkably higher compared to the analogous TAT-SPION conjugate.     

Rossinone-related meroterpenes from the Antarctic ascidian Aplidium fuegiense

The chemical analysis of the ascidian Aplidium fuegiense resulted in the isolation of three novel meroterpenoids 2–4, structurally related to the main co-occurring known rossinone B (1). The structures of the new compounds were determined by interpretation of spectroscopic data. Compounds 1–4 were found to be selectively localized in the viscera of the ascidian.     

Preparation of the Speech-LanguagePathologist Specializing in Voice: An Educational Survey

This study investigates the academic and clinical preparation a speech-language pathologist receives in the area of voice. The purpose is to determine how to structure continuing education and specialty training in vocology, defined as the science and practice of voice habilitation. Surveys were sent to the graduate programs in speech-language pathology accredited by the American Speech-Language-Hearing Association (ASHA) in 1994, and again in 1999. Results from the 1994 survey indicated that students received limited information and clinical experience in handling typical voice cases. Although most programs required a voice disorders course, fewer mandated coursework in normal voice production or clinical experience with voice patients. The follow-up survey showed that the educational environment in 1999 is similar to that in 1994. It is evident that the programs are in compliance with the Educational Training Board model developed by ASHA for basic clinical competence, but no structure for specialty training has yet emerged.     

Effect of Temperature on Shear‐Induced Anisotropic Structure in Polymer Clay Hydrogels

Summary: Shear‐induced orientation of nanoparticles in poly(ethylene oxide)/Laponite RD hydrogels has been investigated by small angle neutron scattering (SANS). As temperature is reduced, anisotropy develops at lower shear rates. The two‐correlation length Debye–Anderson–Brumberger (DAB) model provides a good fit to the experimental data. The deduced short‐range correlation length (≈5 nm) is observed to increase with shear. The long‐range correlation length (≈50 nm) shows a strong directional dependence, and decreases when shear is applied. The relative contribution of long‐range order to the SANS intensity is observed to increase with shear and decrease with temperature.

SANS anisotropy |(I_y − I_x)/(I_y + I_x)| as a function of shear rate and q at 2 °C.