Tandem diazonium salt electroreduction and click chemistry as a novel, efficient route for grafting macromolecules to gold surface

Bis-alkynylated oligoethyleneglycol (OEG) and a monopropargyl-functionalized perfluorinated ethylene glycol (FEG) were clicked to azide-functionalized gold surface (Au–N₃) at room temperature via the well known 1,3 cycloaddition click chemical reaction. The Au–N₃ substrate was obtained by nucleophilic attack of NaN₃ on gold substrates modified by the electrochemical reduction of the , ⁺N₂–C₆H₄–CH₂Br diazonium salt. This electrochemical process yields aryl layer-modified gold of the type Au–C₆H₄–CH₂Br (hereafter Au–Br). The untreated and modified gold plates were examined by XPS, PMIRRAS and contact angle measurements. XPS brought evidence for electrografting aryl layers by the detection of Br3d; azide functionalization by the increase of the N/Br atomic ratio; and click reaction of OEG with Au–N₃ by the increase of O/N ratio. In addition, the perfluorinated plate (Au-FEG) exhibited F1s and characteristic C1s peaks from -(CF₂)₇- chain and terminal CF₃. Infra red spectroscopy (PMIRRAS) evidenced (i) grafting N₃ to Au–Br; (ii) characteristic stretching bands, from ethylene glycol units, C–O–C (1100–1300 cm⁻¹); CF₂ (1000–1100 cm⁻¹) and CF₃ (1100–1350 cm⁻¹) from FEG grafts; and (iii) suppression of alkynyl bands from OEG and FEG after surface click chemistry. More importantly, PMIRRAS results support an important bridging of the bispropargyl oligoethylene glycol at the gold surface. Water drop contact angles were found to be 48.7° and 83.0° for Au-OEG and Au-FEG, respectively, therefore highlighting the control over the hydrophilic/hydrophobic character of the clicked substrate.This work shows that clicking macromolecules to grafted, diazonium salt-derived aryl layers is a novel, simple and valuable approach for designing robust, functional surface organic coatings.     

Study of Preferential Solvation in Binary Mixtures by Means of Frequency-Domain Fluorescence Spectroscopy

The preferential solvation of 8-N,N-(dimethylamino)-11H-indeno[2,1-a]pyrene, Py(S)DMA, in its transient charge transfer (CT) state in binary solvents such as toluene/DMSO liquid mixtures was studied by means of frequency-domain fluorometry. The data obtained were considered within the following kinetic scheme: the preferential solvation was described by the system of consecutive reversible reactions of which each step is associated with the absorption of one DMSO molecule in the first solvation shell of the fluoresent Py(S)DMA dipolar CT molecule. The rate constants of the first two reversible elementary processes (i.e., the decay of solvation complexes of Py(S)DMA with one and two polar molecules, k _–1 = 1.1 10⁹ s^–1 and k _–2 = 1.4 10⁹ s^–1) were determined.     

The distribution of Lyapunov exponents: Exact results for random matrices

Simple exact expressions are derived for all the Lyapunov exponents of certainN-dimensional stochastic linear dynamical systems. In the case of the product of independent random matrices, each of which has independent Gaussian entries with mean zero and variance 1/N, the exponents have an exponential distribution asN. In the case of the time-ordered product integral of exp[N ^–1/2 dW], where the entries of theN×N matrixW(t) are independent standard Wiener processes, the exponents are equally spaced for fixedN and thus have a uniform distribution as N.John S. Guggenheim Memorial Fellow. Research supported in part by NSF Grant MCS 80-19384     

Upon the utility of spherical harmonic expansions in the evaluation of cluster integrals

A novel procedure for the analytic evaluation of cluster integrals is given. By means of a result of Silverstone and Moats which transforms the spherical harmonic expansion of a function around a given point into a new spherical harmonic expansion around a displaced point, a 3N-dimensional cluster integral forN point particles (N > 2) may be reduced to 2N+1 trivial integrals andN– 1 interesting integrals, an improvement over the usual reduction to six trivial integrals and3N–6 nontrivial integrals. For hard spheres, theN–1 integrals involve only a series of simple polynomials taken between linear algebraic bounds.This work was supported in part by the National Science Foundation under Grant No. CHE79-20389.     

Accurate Measurement of H–H Residual Dipolar Couplings in Proteins

A method for accurately measuring H^N–H^α residual dipolar couplings is described. Using this technique, both the sign and magnitude of the coupling can be determined easily. Residual dipolar coupling between H^N(i)–H^α(i) and H^N(i)–H^α(i-1) were measured for the FK506 binding protein complexed to FK506. The experimental values were in excellent agreement with predictions based on an X-ray crystal structure of the protein/ligand complex, suggesting that these residual dipolar couplings will provide accurate structural constraints for the refinement of protein structures determined by NMR.     

C Chemical Shift and C–N Dipolar Coupling Tensors Determined by C Rotary Resonance Solid-State NMR

This work explores the utility of simple rotary resonance experiments for the determination of the magnitude and orientation of ¹³C chemical shift tensors relative to one or more ¹³C–¹⁴N internuclear axes from ¹³C magic-angle-spinning NMR experiments. The experiment relies on simultaneous recoupling of the anisotropic ¹³C chemical shift and ¹³C–¹⁴N dipole–dipole coupling interactions using 2D rotary resonance NMR with RF irradiation on the ¹³C spins only. The method is demonstrated by experiments and numerical simulations for the ¹³C^α spins in powder samples of -alanine and glycine with ¹³C in natural abundance. To investigate the potential of the experiment for determination of relative/absolute tensor orientations and backbone dihedral angles in peptides, the influence from long-range dipolar coupling to sequential ¹⁴N spins in a peptide chain (¹⁴N_i–¹³C^α_i–¹⁴N_i+1 and ¹⁴N_i+1–¹³C′_i–¹⁴N_i three-spin systems) as well as residual quadrupolar–dipolar coupling cross-terms is analyzed numerically.     

Convergence of spherical harmonic expansions for the evaluation of hard-sphere cluster integrals

ForN particles (N>2), by means of a spherical harmonic expansion of Silverstone and Moats, a 3N-dimensional cluster may be reduced to 2N+1 trivial integrals andN–1 interesting integrals. For hard spheres, theN–1 interesting integrals are products of polynomials integrated between binomial bounds. With simple clusters, closed forms are obtained; for more complex clusters, infinite series inl (ofY _lm ) appear. It is here shown for representative cases that these series converge exponentially rapidly, the leading pair of terms accounting for all but a few tenths of a percent of the total cluster integral.     

One-dimensional Ising chain with competing interactions: Exact results and connection with other statistical models

We study the ground state properties of a one-dimensional Ising chain with a nearest-neighbor ferromagnetic interactionJ ₁, and akth neighboranti-ferromagnetic interactionJ _k . WhenJ _k/J₁=–1/k, there exists a highly degenerate ground state with a residual entropy per spin. For the finite chain with free boundary conditions, we calculate the degeneracy of this state exactly, and find that it is proportional to the (N+k–1)th term in a generalized Fibonacci sequence defined by,F _N ^(k) =F _N–1 ^(k) +F _N–k ^(k) . In addition, we show that this one-dimensional model is closely related to the following problems: (a) a fully frustrated two-dimensional Ising system with a periodic arrangement of nearest-neighbor ferro- and antiferromagnetic bonds, (b) close-packing of dimers on a ladder, a 2× strip of the square lattice, and (c) directed self-avoiding walks on finite lattice strips.Work partially supported by grants from AFOSR and ARO.     

Trapping of random walks on the line

Several features of the trapping of random walks on a one-dimensional lattice are analyzed. The results of this investigation are as follows: (1) The correction term to the known asymptotic form for the survival probability ton steps is O(( ₂n)^–1/3), where =–ln(1–c), andc is the trap concentration. (2) The short time form for the survival probability is found to be exp[–a(c)n ^1/2], wherea(c) is given in Eq. (21). (3) The mean-square displacement of a surviving random walker is found to go liken ^2/3for largen. (4) When the distribution of trap-free regions is changed so that very large regions are much rarer than for ideally random trap placement the asymptotic survival probability changes its dependence onn. One such model is studied.     

Are random walks random?

Random walks have been created using the pseudo-random generators in different computer language compilers (BASIC, PASCAL, FORTRAN, C++) using a Pentium processor. All the obtained paths have apparently a random behavior for short walks (2¹⁴ steps). From long random walks (2³³ steps) different periods have been found, the shortest being 2¹⁸ for PASCAL and the longest 2³¹ for FORTRAN and C++, while BASIC had a 2²⁴ steps period. The BASIC, PASCAL and FORTRAN long walks had even (2 or 4) symmetries. The C++ walk systematically roams away from the origin. Using deviations from the mean-distance rule for random walks, d² ∝ N, a more severe criterion is found, e.g. random walks generated by a PASCAL compiler fulfills this criterion to N < 10 000.     

The probability of intersection of independent random walks in four dimensions

LetS ₁ andS ₂ be independent simple random walks of lengthn inZ ⁴ starting at 0 andx ₀ respectively. If |x ₀|₂n, it is shown that the probability that the paths intersect is of order (logn)^–1. Ifx ₀=0, it is shown that the probability of no intersection of the paths decays no faster than (logn)^–1 and no slower than (logn)^–1/2. It is conjectured that (logn)^–1/2 is the actual decay rate.Research supported by National Science Foundation grant MCS-8002758     

Current noise and long time tails in biased disordered random walks

We calculate the mean velocity and the velocity correlation function for a random walk with a uniform bias on a disordered chain. We find a new long time tail in the velocity correlation function due to the combined effects of the bias and of the disorder in the site variables. This long time tail persists to a low-frequency cutoff inversely proportional to the square of the bias. By associating the velocity correlation function with the spectrum of current fluctuations, we calculate the excess low-frequency current noise associated with this long time tail. The spectrum of current fluctuations goes as(I ²/N)f ^–1/2, whereI is the DC current,N is the number of charge carriers, andf is the frequency. The possible connection to 1/f noise is discussed. The calculation is done by a perturbation expansion in the strength of the disorder, but is shown to be exact to all orders for weak enough bias.Supported by a fellowship of the German Academic Exchange Service (DAAD).Supported by the National Science Foundation through Grant No. DMR-8108328 and through the Cornell Materials Science Center.     

Special frequencies and Lifshitz singularities in binary random harmonic chains

We consider a one-dimensional chain of coupled harmonic oscillators; the mass of each atom is a random variable taking only two values (M or 1). We investigate the integrated density of statesH(²) near special frequencies: a given frequency _s with rational wavelength becomes special if the mass ratioM exceeds a certain critical valueM _c . We show thatH has essential singularities of the typesH _sg exp(–C ₁ ¦²– _s ² ¦^–1/2) or exp(–C ₂¦²– _s ² ¦^–1), according to the value ofM and the sign of (²– _s ² ). The Lifshitz singularity at the band edge is analyzed in the same way. In each case, the constantC ₁ orC ₂ is evaluated explicitly and compared with a vast amount of numerical work. All these exponential singularities are modulated by periodic amplitudes. The properties of the eigenfunctions with frequencies close to the special values are also discussed, and are illustrated by numerical data.     

Correlation inequalities and the Kosterlitz-Thouless transition for anisotropic rotators

I give a proof of the Kosterlitz-Thouless transition for sufficiently anisotropic (J _zJ _x ^–1 =J _zJ _y ^–1 <2q ^–(JKT)^–J) two-dimensionalN-component rotators (N 3). The method is based on Wells' inequality and is related to mean field Gaussian inequalities.     

Volume and grain boundary diffusion of implanted 113Sn in aluminium

Volume and grain boundary diffusion of ¹¹³Sn in aluminium was investigated with the radiotracer method. The implantation technique was used for tracer deposition to avoid problems of tracer hold-up caused by the oxide layer always present on aluminium. The diffusion penetration was chosen large enough to permit serial sectioning of samples with the aid of a microtome.The temperature dependence of the volume diffusivity was determined as D(T)=4.54×10^–5×exp[–(114.5±1.2)kJmol^–1/RT] m ² s ^–1. This confirms previous measurements from our group which already showed that Sn is the fastest foreign metal diffusor so far investigated in aluminium.Grain boundary diffusion of ¹¹³Sn in Al polycrystals was measured in the type-B kinetic regime. The grain boundary diffusion product P=sD _gb (s=segregation factor, =grain boundary width, D _gb=grain boundary diffusivity) was found to be strongly affected by the impurity content of aluminium. For Al polycrystals of 99.9992% nominal purity we obtained P _5N(T)=1.08×10^–8exp [–(96.9±7.5) kJ mol^–1/RT] m³ s^–1 and for less pure Al polycrystals of 99.99% nominal purity P _4N(T)=3.0×10^–10 exp [–(90.1±4.2) kJ mol^–1/RT] m³ s^–1 was determined. The grain boundary diffusion product in the purer material is more than one order of magnitude higher than in the less pure material. Very likely this is an effect of co-segregation of non-diffusant impurities into the grain boundaries.     

Polymer chain in a quenched random medium: slow dynamics and ergodicity breaking

The Langevin dynamics of a self-interacting chain embedded in a quenched random medium is investigated by making use of the generating functional method and one-loop (Hartree) approximation. We have shown how this intrinsic disorder causes different dynamical regimes. Namely, within the Rouse characteristic time interval the anomalous diffusion shows up. The corresponding subdiffusional dynamical exponents have been explicitly calculated and thoroughly discussed. For the larger time interval the disorder drives the center of mass of the chain to a trap or frozen state provided that the Harris parameter, (Δ/b ^d)N ^{2 - νd}≥1, where Δ is a disorder strength, b is a Kuhnian segment length, N is a chain length and ν is the Flory exponent. We have derived the general equation for the non-ergodicity function f (p) which characterizes the amplitude of frozen Rouse modes with an index p = 2πj/N. The numerical solution of this equation has been implemented and shown that the different Rouse modes freeze up at the same critical disorder strength Δ _c ∼ N ^{- γ} where the exponent γ ≈ 0.25 and does not depend from the solvent quality. Received 17 December 2002 Published online 23 May 2003 RID="a" ID="a"e-mail: vilgis@mpip-mainz.mpg.de     

Exact solutions for electromagnetic waves in inhomogeneous media

Exact solutions of the wave equation for the propagation of electromagnetic waves in some inhomogeneous media are found. The first solution corresponds to the barometric model of the atmosphere, whose index of refraction can be expressed by the formulaN ²(z)=1+(N ₀ ² -1) exp (–z/z ₀). The other cases correspond toN ²(z)=1+(N ₀ ² -1) ch^–2(z) andN ²(z)=a-b. [1+exp(z/L)]^–1.Dedicated to Academician Vladimír Hajko on the occasion of his 65th birthday.     

One- and two-dimensional C–H/N–H dipolar correlation experiments under fast magic-angle spinning for determining the peptide dihedral angle φ

A recently proposed ¹³C–¹H recoupling sequence operative under fast magic-angle spinning (MAS) [K. Takegoshi, T. Terao, Solid State Nucl. Magn. Reson. 13 (1999) 203–212.] is applied to observe ¹³C–¹H and ¹⁵N–¹H dipolar powder patterns in the ¹H–¹⁵N–¹³C–¹H system of a peptide bond. Both patterns are correlated by ¹⁵N-to-¹³C cross polarization to observe one- or two-dimensional (1D or 2D) correlation spectra, which can be simulated by using a simple analytical expression to determine the H–N–C–H dihedral angle. The 1D and 2D experiments were applied to N-acetyl[1,2-¹³C,¹⁵N] -valine, and the peptide φ angle was determined with high precision by the 2D experiment to be ±155.0°±1.2°. The positive one is in good agreement with the X-ray value of 154°±5°. The 1D experiment provided the value of φ=±156.0°±0.8°.     

A determination of the Avogadro Constant

We have determined Avogadro's constantN _A using a direct method. The result ofN _A =6.0221363×10²³ mol^–1 differs from the most recent CODATA value of 6.0221367×10²³ mol^–1 by only 0.07 ppm, the relative uncertainties being 1.1. ppm and 0.6 ppm, respectively. The value was derived from the determination of the lattice parameter, the density and the molar mass of a silicon single crystal. It will be possible in the future to further reduce the uncertainties of measurement by the procedure described here.     

Absence of continuous symmetry breaking in a one-dimensional n−2 model

For a one-dimensional array ofS ^N–1 spins (N 2) with isotropic pair interactions (and more general systems) with J(j–i) obeying sup_n[n^–1 ₁ ⁿ j ²|J(j)|]<, we prove that every equilibrium state is invariant under the natural action ofSO(N). In particular, there is no long-range order of the conventional type. Included is the caseJ(n)=n ^–2.Research partially supported by U.S.N.S.F. Grant No. MCS-78-01885.S. Fairchild Scholar at Caltech. On leave from Departments of Mathematics and Physics, Princeton University, Princeton, New Jersey 08544.