Clocking the melting transition of charge and lattice order in 1T-TaS2 with ultrafast extreme-ultraviolet angle-resolved photoemission spectroscopy

We use time- and angle-resolved photoemission spectroscopy with sub-30-fs extreme-ultraviolet pulses to map the time- and momentum-dependent electronic structure of photoexcited 1T-TaS(2). This compound is a two-dimensional Mott insulator with charge-density wave ordering. Charge order, evidenced by splitting between occupied subbands at the Brillouin zone boundary, melts well before the lattice responds. This challenges the view of a charge-density wave caused by electron-phonon coupling and Fermi-surface nesting alone, and suggests that electronic correlations play a key role in driving charge order.     

Simultaneous chromatography and electrophoresis: two-dimensional planar separations

Single-dimension separations are routinely coupled in series to achieve two-dimensional separations, yet little has been done to simultaneously exploit multiple dimensions during separation. In this work, simultaneous chromatography and electrophoresis is introduced and evaluated for its potential to achieve two-dimensional separations. In simultaneous chromatography and electrophoresis, chromatography occurs via capillary action while an orthogonal electric field concurrently promotes electrophoresis in a second dimension. A novel apparatus with a dual solvent reservoir was designed to apply the concurrent electric field. Various compounds were used to characterize the apparatus and technique, i.e., vitamins, amino acids, and dyes. Improved separation is reported with equivalent analysis times in comparison to planar chromatography alone. The feasibility of simultaneously employing chromatography and electrophoresis in two dimensions is discussed.

Counting Dyck Paths by Area and Rank

The set of Dyck paths of length 2n inherits a lattice structure from a bijection with the set of noncrossing partitions with the usual partial order. In this paper, we study the joint distribution of two statistics for Dyck paths: area (the area under the path) and rank (the rank in the lattice). While area for Dyck paths has been studied, pairing it with this rank function seems new, and we get an interesting (q, t)-refinement of the Catalan numbers. We present two decompositions of the corresponding generating function: One refines an identity of Carlitz and Riordan; the other refines the notion of γ-nonnegativity, and is based on a decomposition of the lattice of noncrossing partitions due to Simion and Ullman. Further, Biane’s correspondence and a result of Stump allow us to conclude that the joint distribution of area and rank for Dyck paths equals the joint distribution of length and reflection length for the permutations lying below the n-cycle (12· · ·n) in the absolute order on the symmetric group.     

Fused Lasso Additive Model

We consider the problem of predicting an outcome variable using p covariates that are measured on n independent observations, in a setting in which additive, flexible, and interpretable fits are desired. We propose the fused lasso additive model (FLAM), in which each additive function is estimated to be piecewise constant with a small number of adaptively chosen knots. FLAM is the solution to a convex optimization problem, for which a simple algorithm with guaranteed convergence to a global optimum is provided. FLAM is shown to be consistent in high dimensions, and an unbiased estimator of its degrees of freedom is proposed. We evaluate the performance of FLAM in a simulation study and on two datasets. Supplemental materials are available online, and the R package flam is available on CRAN.     

Direct formation of beta-glycosides of N-acetyl glycosamines mediated by rare earth metal triflates

A direct, mild and efficient protocol for the preparation of beta-glycosides of N-acetyl glucosamine (GlcNAc) and N-acetyl galactosamine (GalNAc) has been developed using peracetylated beta-GlcNAc and beta-GalNAc as donors. All rare Earth metal triflate promoters screened were found to promote glycosylation with Sc(OTf)(3) being superior in terms of reaction rate. Simple alcohol glycosylation was found to proceed smoothly in refluxing dichloromethane, whereas higher temperatures under microwave conditions were needed to attain acceptable yields with less reactive, carbohydrate based glycosyl acceptors. The protocol developed was applied to provide the first example of direct chemical formation of a disaccharide using both GlcNAc as a glycosyl donor and acceptor. The alpha-acetate donor was found to be significantly less reactive than the corresponding beta-anomer necessitating higher reaction temperatures under which glycoside anomerisation was found to occur. It was established, that the anomerisation only took place in the presence of both Sc(OTf)(3) and acetic acid.     

Ultrafast N-H vibrational dynamics of cyclic doubly hydrogen-bonded homo- and heterodimers

Hydrogen-bonded interfaces are essential structural elements in biology. Furthermore, they can mediate electron transport by coupling the electron to proton transfer within the interface. The specific hydrogen-bonding configuration and strength have a large impact on the proton transfer, which exchanges the hydrogen-bonded donor and acceptor species (i.e., NH...O --> N...HO). Modulations of the hydrogen-bonding environment, such as the hydrogen-bond stretch and twist modes, affect the proton-transfer dynamics. Here, we present transient grating and echo peak shift measurements of the NH stretch vibrations of four doubly hydrogen-bonded cyclic dimers in their electronic ground state. The equilibrium vibrational dynamics exhibit strong coherent modulations that we attribute to coupling of the high-frequency NH vibration to the low-frequency interdimer stretch and twist modes and not to interference between multiple Fermi resonances that dominate the substructure of the linear spectra.     

Efficient synthesis of N-2-aryl-1,2,3-triazole fluorophores via post-triazole arylation

Efficient post-triazole regioselective N-2 arylation was developed from C-4, C-5 disubstituted-1,2,3-NH-triazoles. Three different approaches had been investigated, including S(N)Ar, Cu(I) catalyzed aryl amidation and Cu(II) mediated boronic acid coupling. The N-2-aryl triazoles were successfully synthesized with excellent yields. The structures were characterized by X-ray crystallography and some N-2-triazole products gave strong fluorescence with various emission controlled by the C-5 groups.     

Realization of a salt bridge-free microfluidic reference electrode

We report on the design of a microfluidic electrochemical cell with a true Ag/AgCl reference electrode that does not rely on a physical barrier or salt bridge, but instead takes advantage of slow diffusion times in micro-channels. The device concept is demonstrated in PDMS using the Ir(+IV)/Ir(+III) redox couple as an example. A scaling analysis provides limits of operation for the device.     

1,2,3-triazole: unique ligand in promoting iron-catalyzed propargyl alcohol dehydration

A 1,2,3-traizole-promoted iron(III)-catalyzed propargyl alcohol dehydration was developed for the synthesis of conjugated enynes. The desired conjugated enynes were prepared in good to excellent yields (up to 95%) with a large substrate scope and excellent stereoselectivity (only Z-isomers).