Stability of mixed PEO-thiol SAMs for biosensing applications

The secret of a successful affinity biosensor partially hides in the chemical interface layer between the transducer system and the biological receptor molecules. Over the past decade, several methodologies for the construction of such interface layers have been developed on the basis of the deposition of self-assembled monolayers (SAMs) of alkanethiols on gold. Moreover, mixed SAMs of polyethylene oxide (PEO) containing thiols have been applied for the immobilization of biological receptors. Despite the intense research in the field of thiol SAMs, relatively little is known about their biosensing properties in correlation with their long-term stability. Especially the impact of the storage conditions on their biosensing characteristics has not been reported before to our knowledge. To address these issues, we prepared mixed PEO SAMs and tested their stability and biosensing performance in several storage conditions, i.e., air, N2, ethanol, phosphate buffer, and H2O. The quality of the SAMs was monitored as a function of time using various characterization techniques such as cyclic voltammetry, contact angle, grazing angle Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. In addition, the impact of the different storage conditions on the biosensor properties was investigated using surface plasmon resonance. Via the latter technique, the receptor immobilization, the analyte recognition, and the nonspecific binding were extensively studied using the prostate specific antigen as a model system. Our experiments showed that very small structural differences in the SAM can have a great impact in their final biosensing properties. In addition it was shown that the mixed SAMs stored in air or N2 are very stable and retain their biosensor properties for at least 30 days, while ethanol appeared to be the worst storage medium due to partial oxidation of the thiol headgroup. In conclusion, care must be taken to avoid SAM degradation during storage to retain typical SAM characteristics, which is very important for their general use in many proposed applications.     

Errors involved in the existing B-term expressions for the longitudinal diffusion in fully porous chromatographic media Part I: computational data in ordered pillar arrays and effective medium theory

Numerically solving the effective diffusion in a simplified representation of a chromatographic bed, it was found that the B-term expressions that have up to now been used in the literature, and which can all be reduced to either Deff=(gamma mDm+k'gamma sDs)/(1+k') or Deff=(gamma meDm+k'Dpart)/(1+k'), can no longer be considered to be unconditionally valid. This could be demonstrated by showing that the simulated diffusion data are in agreement with the mathematically sound effective medium theory (EMT), whereas the B-term expressions used up to now in literature are in conflict with the EMT, a theory that is widely accepted in all other fields of science. It is also shown that the use of the existing B-term expressions can lead to very large measurement errors (up to a 100% and more) for the determination of the stationary phase diffusion coefficient gamma sDs from peak parking experiments. The representation of the B-term diffusion should in the future hence be based on the Deff expressions that can be derived from the EMT. These are physically sound and are also more accurate than the classical B-term expressions used up to now.     

On the 3-dimensional effects in etched chips for high performance liquid chromatography-separations

In an attempt to quantify the potential of photolithographically etched micro-pillar arrays as a perfectly ordered alternative for the packed bed of spheres, the additional band broadening originating from the top and bottom plate has been investigated using computational fluid dynamics simulations. These calculations provide insight in the theoretical expectations that can be made for the experimental work that is currently being conducted by a number of groups. The calculations show that the additional band broadening contribution can be expected to go through a transient regime as a function of the axial distance along the array. In its fully developed regime and in the most relevant velocity range, the top and bottom wall contribution almost doubles the band broadening compared to the band broadening in a perfectly ordered array of non-porous, non-retentive pillars without top and bottom wall. Compared to the band broadening in an array of porous, retentive pillars on the other hand, the top and bottom wall-effect can be expected to become negligible. A simplified, phenomenological model yielding a first principles prediction of both the transient and the steady-state top and bottom wall band broadening as a function of the inter-pillar distance and the pillar height is proposed and shows good qualitative agreement with the exact calculations.     

A ranking model in uncertain, imprecise and multi-experts contexts: The application of evidence theory

We consider ranking problems where the actions are evaluated on a set of ordinal criteria. The evaluation of each alternative with respect to each criterion may be imperfect and is provided by one or several experts. We model each imperfect evaluation as a basic belief assignment (BBA). In order to rank the BBAs characterizing the performances of the actions according to each criterion, a new concept called RBBD and based on the comparison of these BBAs to ideal or nadir BBAs is proposed. This is performed using belief distances that measure the dissimilarity of each BBA to the ideal or nadir BBAs. A model inspired by Xu et al.’s method is also proposed and illustrated by a pedagogical example.     

Solvothermal synthesis, crystal structure, and properties of lanthanide-organic frameworks based on thiophene-2,5-dicarboxylic acid

A series of lanthanide-organic framework coordination polymers, {[La(2)(TDC)(2)(NO(3))(H(2)O)(4)](OH)·5H(2)O}(n) (1) and [Ln(TDC)(NO(3))(H(2)O)](n) (TDC = thiophene- 2, 5- dicarboxylic acid; Ln = Nd(2), Sm(3), Eu(4), Gd(5), Tb(6), Dy(7), Ho(8), Er(9), Yb(10)) have been synthesized by solvothermal reaction and characterized by elemental analysis, FT-IR, TG analysis, single-crystal X-ray diffraction and power X-ray diffraction. The single-crystal X-ray diffraction analysis results show that 1 displays a 3-D porous framework with (3,7)-connected {4(10).6(11)}{4(3)} topology. The compounds 2-10 crystallized in the same P2(1)/c space group and exhibits a (3,6)-connected {4.6(2)}(2){4(2).6(10).8(3)} topology, Right-handed and left-handed helical chains coexist in the 2-D layer structure. The luminescence properties of 2-10 and the magnetic properties of 5,7,8,9 were investigated.     

Thiol-promoted catalytic synthesis of diphenolic acid with sulfonated hyperbranched poly(arylene oxindole)s

Acid-catalyzed condensation of levulinic acid and phenol into high yields of diphenolic acid (>50%) is possible with a combination of sulfonated hyperbranched polymers and thiol promotors, either added as a physical mixture or bound to the polymer by ion-pairing.     

Hydrothermal synthesis, crystal structure and properties of Ni(II)-4f complexes based on 1H-benzimidazole-5,6-dicarboxylic acid

Nine novel heterometallic coordination polymers [Ln(2)Ni(Hbidc)(2)(SO(4))(2)(H(2)O)(8)](n) (Ln = Pr (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6), Ho (7), Er (8), Yb (9), H(3)bidc = 1H-benzimidazole-5,6-dicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, FT-IR, TG analysis and single crystal X-ray diffraction. X-ray analysis revealed that all complexes present almost identical three-dimensional (3D) structures with PtS-type topology. Complexes 1-7 are all isomorphous, and the structure variation of polymers 8 and 9 is induced by the lanthanide contraction effect. In additional, the luminescence properties of complexes 2, 3 and 5-7, and the magnetic properties of complexes 4 and 6-8 were investigated.     

The generalized Krawtchouk polynomials and the fifth Painlevé equation

We study the recurrence coefficients of the orthogonal polynomials with respect to a semi-classical extension of the Krawtchouk weight. We derive a coupled discrete system for these coefficients and show that they satisfy the fifth Painlevé equation when viewed as functions of one of the parameters in the weight.     

Millimeter/submillimeter mixing based on the nonlinear plasmon response of two-dimensional electron systems

The nonlinear plasmon response of a two-dimensional electron system with an incorporated defect to monochromatic and bichromatic microwave radiation has been investigated. The operation of an electronic device (mixer) based on the plasmon response with a record operational speed has been demonstrated and analyzed. It has been found that the system response time is no more than τ = 25 ps. It has been shown that the nonlinear response of the system is caused by a new physical mechanism of nonlinearity induced by the presence of an inhomogeneity in the electron system.