Frictional dynamics of fluorine-terminated alkanethiol self-assembled monolayers

The frictional dynamics of fluorine-terminated alkanethiol (S(CH2)8CF3) self-assembled monolayers (SAMs) on gold are studied using molecular dynamics simulations. The simulations treat the interactions between two SAMs on flat surfaces. The structure and frictional behavior are investigated as a function of applied pressure (200 MPa to 1 GPa) for a shear velocity of 2 m/s and compared to methyl-terminated alkanethiol SAMs. The maximum adhesive pressure between the SAMs is 220 MPa for both end groups. In agreement with experiments on the molecular scale, the shear stress and the coefficient of friction for CF3-terminated alkanethiols are larger than for CH3-terminated alkanethiols. The main source for the difference is primarily the tighter packing of the fluorinated terminal group resulting in a higher degree of order. The molecular scale coefficient of friction is correlated with the degree of order among all the systems.     

Evidence for a bound HeH2 halo molecule by diffraction from a transmission grating

The HeH2 van der Waals complex has been identified in a molecular beam produced by a cryogenic (T0=24.7 K) free jet expansion of a 1% H2 mixture in 99% 4He gas. The weakly bound HeH2 complexes in the beam are identified via their first order diffraction angles after passing through a 100 nm period transmission grating. An electron impact mass spectrometer analysis of the diffraction patterns is used to discriminate against ion fragments of the constituent gas clusters.     

A finite temperature linear tetrahedron method for electronic structure calculations of periodic systems

A finite-temperature linear tetrahedron method for electronic structure calculations of periodic systems is developed. When compared to widely used simple temperature broadening, the number of k points necessary for accurate integration at finite temperatures is reduced. The utility of the method is demonstrated with benchmark calculations on 1D, 2D, and 3D systems.     

Facile oxidative addition of N-C and N-H bonds to monovalent rhodium and iridium

An investigation of room-temperature oxidative addition of N-C and N-H bonds to RhI and IrI in solution and in the solid state is presented. The rigid, product-adapted framework of the pincer bis(ortho-phosphinoaryl)amine (PNP) ligand may contribute to the ease of the N-C and N-H cleavage. The migration of Me from N of the coordinated amine moiety to Rh proceeds with near-zero entropy of activation in solution. In the solid state, this transformation is a crystal-to-crystal reaction, transforming only one of the two independent molecules of (PN(Me)P)RhCl into (PNP)Rh(Me)Cl.     

Bubble dynamics in double-stranded DNA

We report the first measurement of the dynamics of bubble formation in double-stranded DNA. Fluctuations of fluorescence of a synthetic DNA construct, internally tagged with a fluorophore and a quencher, are monitored by fluorescence correlation spectroscopy. The relaxation dynamics follow a multistate relaxation kinetics, with a characteristic time scale of 50 microseconds. A simple model of bubble dynamics based on constant zipping-unzipping rates is proposed to account for our experimental data. The role of different secondary structures stabilizing the open bubble is tested.     

Elastic wave thermal fluctuations,ultrasonic waveforms by correlation of thermal phonons

It is widely recognized that acoustic degrees of freedom coupled to a thermal bath have amplitudes which fluctuate with a mean square proportional to temperature; this is the basis for the Debye theory of the heat capacity of insulating solids. It is shown here that these elastic wave thermal phonons have correlation functions identical to the system's ultrasonic Green's function, and furthermore that thermal noise in ultrasonic detectors should have correlation functions equivalent to conventional waveforms obtained by active transmission and reception. This suggests the possibility of doing ultrasonics without a source. Theory for the identity is presented, and several room temperature laboratory confirmations are conducted in the frequency range 0.1-1.0 MHz. The thermal nature of the origin of these correlations is established by comparing their strength with theoretical expectations. Applications are discussed.     

Specific Interaction of Coproporphyrin I with Antibodies in Water and Reverse Micelles: Dimerization of Antibodies Affects Antigen Binding Site

The antigen-antibody interaction between coproporphyrin I and anti-coproporphyrin antibodies was studied by a fluorescence method in water and a reverse micellar system: n-octane/Aerosol OT. Coproporphyrin fluorescence was quenched, and coproporphyrin emission maximum was shifted to the long-wavelength region after binding to the antibodies or Fab-fragments. The mechanism of this quenching is static, most probably, by a tryptophan residue (or maybe lysine or methionine). Apparent dynamic quenching, in this case, arises from protein backbone motion. A special kind of antibody Fab-Fab dimerization was proposed.     

Unprecedented conversion of triethylamine and disulfur dichloride into a thienopentathiepin and a heptathiocane

[reaction: see text] In a remarkable cascade reaction, triethylamine is converted into the thienopentathiepin 2a and the heptathiocane 3a by a preequilibrated solution of disulfur dichloride and DABCO in chloroform.     

Size ramsey numbers of stars versus 4‐chromatic graphs

We investigate the asymptotics of the size Ramsey number î(K_1,nF), where K_1,n is the n‐star and F is a fixed graph. The author 11 has recently proved that r?(K_1,n,F)=(1+o(1))n² for any F with chromatic number χ(F)=3. Here we show that r?(K_1,n,F)≤ n²+o(n²), if χ (F) ≥ 4 and conjecture that this is sharp. We prove the case χ(F)=4 of the conjecture, that is, that r?(K_1,n,F)=(4+o(1))n² for any 4‐chromatic graph F. Also, some general lower bounds are obtained. © 2003 Wiley Periodicals, Inc. J Graph Theory 42: 220–233, 2003