Writing with DNA and protein using a nanopipet for controlled delivery

We present a new, general method for the controlled deposition of biological molecules on surfaces, based on a nanopipet operating in ionic solution. The potential applied to the pipet tip controls the flux of biological molecules from the pipet, allowing fine control of the delivery rate. We used the ion current to control the distance of the pipet from the surface of a glass slide and deposited the fluorescently labeled DNA or protein G at a defined location onto the surface. Features of 830 nm size were obtained by depositing the biotinylated DNA onto a streptavidin surface; 1.3 mum size spots were obtained by depositing protein G onto a positively charged glass surface.     

Chiral Phosphinophenyloxazolines Bearing Alkoxymethyl Substituents: Synthesis and Application in the Palladium Catalyzed Allylic Substitution Reactions

The chiral phosphine‐oxazoline ligands 3 and 4 bearing 4‐alkoxymethyl substituents on the oxazoline ring with (R)‐configuration were prepared from L‐serine methyl ester in 66% and 33% yields, respectively. Along this synthetic pathway, the β‐hydroxylamides derived from L‐serine methyl ester and 2‐halobenzoyl chlorides were expediently converted to the corresponding oxazolines by using diethylaminosulfur trifluoride as the activation agent. Potassium diphenylphosphide was the reagent of choice for replacing the bromine atom on the phenyl ring, giving the desired oxazoline‐phosphine ligands 3 and 4 . Together with [Pd(η³‐allyl)Cl]₂, ligands 3 and 4 induced an enantioselective allylic substitution reaction of 1,3‐diphenyl‐2‐pro‐penyl acetate by dimethyl malonate. Although ligands 3 and 4 exhibit the (R)‐configuration, differing from the (S)‐configuration of Pfaltz‐Helmchen‐Williams phosphine‐oxazoline ligands, all these ligands led to the same enantiotopic preference in the allylic substitution reaction. To facilitate the recovery and reuse of the phosphine‐oxazoline ligand, immobilization on Merrifield resin was attempted, albeit in low loading.     

Redetermination of (6R,7S,9S,11S)‐(–)‐sparteinium monoperchlorate

The structure of the title compound, C₁₅H₂₇N₂⁺·ClO₄^?, consists of a monoprotonated sparteinium cation and a perchlorate anion. The two tertiary N atoms of the cation, one perchlorate O atom and a H atom form a bifurcated hydrogen bond, the four hydrogen‐bonding atoms being nearly in the same plane.     

Detailed analysis of α,ω-bis(4-hydroxybutyl) poly(dimethylsiloxane) using GPC-MALDI TOF mass spectrometry

In this study the prepolymer alpha,omega-bis(4-hydroxybutyl) poly(dimethylsiloxane), used in the formulation of oxygen permeable films, is evaluated by gel permeation chromatography (GPC) combined with matrix assisted laser desorption ionization (MALDI) time of flight (TOF) mass spectrometry (MS). Two unexpected mass distributions are observed in the mass spectra. Reaction schemes for the formation of these distributions are proposed. A solution phase trimethylsilane end group modification was performed on the prepolymer to determine whether the unexpected mass distributions occur as impurities from synthesis or as artifacts from the MS process. Evaluation of the TMS modified prepolymer indicates the unexpected mass distributions indeed occur as impurities from the synthetic procedure. Average molecular weight values are determined by traditional GPC, direct MALDI-TOF MS, and GPC-MALDI-TOF MS methods and the results are compared.     

A polystyrene-supported triflating reagent for the synthesis of aryl triflates

An insoluble polystyrene-supported triflating reagent has been prepared by suspension co-polymerization of N-(4-vinylphenyl)trifluoromethanesulphonimide, styrene and the JandaJel^® cross-linker. This reagent, in the presence of triethylamine, allows for the efficient synthesis of aryl triflates from a wide range of phenols in a process that permits the desired product to be isolated from the reaction mixture in essentially pure form via several filtration and concentration operations. Adding to the utility of this reagent is its ability to be easily recovered, regenerated and reused. Both soluble and insoluble bifunctional polymers containing trialkylamine moieties in addition to triflimide groups were also prepared and examined as triflating reagents. Unfortunately these reagents afforded only modest yields of the desired products in representative reactions.     

Dioxygen Affinities and Catalytic Oxidation Performance of Cobalt (II)Complexes with N-Aryl Hydroxamic Acid

It is well known that the study on biomimetic oxygen carriers not only has important theoretic significance to discover the mechanism of reversible bonding, activating oxygen as well as the oxidation reaction in organism, but also has potential application in separating oxygen from air and realizing the high efficiency and selectivity of catalytic oxidation reaction under a mild condition1. Metal- porphyrin and metal- phthalol- gaunine have been extensively used as biomimetic oxygen carriers u…     

A simple and efficient one step synthesis of 1,3,4-oxadiazoles utilizing polymer-supported reagents and microwave heating

1,3,4-Oxadiazoles can be rapidly and efficiently synthesized from a variety of carboxylic acids and acid hydrazides in one simple step. The use of commercially available PS-PPh₃ resin combined with microwave heating delivered the product 1,3,4-oxadiazoles in high yields and purities.     

Facile Total Synthesis of (±)‐Nimbiol

A facile total synthesis of (±)‐nimbiol 1 has been achieved. In order to decrease the dioxo byproduct 2a , an improved oxidation system of CrO₃/H₂O/HOAc/NaOAc was used.     

Sensitivity in Supramolecular Architectures of Polyaromatic Salts Containing Two Singly‐Pimerized Bipyridines

Three novel supramolecular arrays of zigzag polyaromatic salts are reported. Both the conformation and disposition of the dications are subjected to various noncovalent interactions. Thus, the presence or absence of the π‐π interacting enclathrated molecules, the efficient packing and the involved hydrogen bonding interactions of anions, as well as the increased hydrophobic property of the dications themselves exert influence.     

Characterization of organometallic coordinative cluster compounds of silver by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was successfully applied to characterize the organosilver coordinative cluster compounds, silver phenylacetylide and three silver thiolates, namely, silver tertiary butylthiolate, silver 2,6-dimethylbenzenethiolate, and silver 2, 6-dichlorobenzenethiolate. Samples and dithranol matrix were finely dispersed in 1:1 tetrahydrofuran (THF)/chloroform (CHCl(3)) mixed solvent. In most cases the monomer units remained intact during ionization, and the oligomeric molecular ions were produced through silver cationization, with a general molecular ion formula [nM + Ag](+). This was further verified by the relative abundances of the isotopic peaks within the molecular ion clusters, which were in close agreement with those theoretically calculated for nM cationized with one silver ion. In the case of silver 2, 6-dichlorobenzenethiolate, in addition to the dominant [nM + Ag](+) peaks, weak peaks corresponding to the successive losses of hydrogen chloride molecules were observed. Copyright 2000 John Wiley & Sons, Ltd.