Synthesis and structure of benzimidazo[1,2-c][1,2,3]thiadiazoles: first examples of a novel ring system

(1-Amino-1H-benzimidazol-2-yl)methanol 1 with thionyl chloride at reflux afforded 3-chlorobenzimidazo[1,2-c][1,2,3]thiadiazole 4, which reacted with various nucleophiles to give different products depending on the nature of the solvent. The structures of 4 and di(benzimidazo[1,2-c][1,2,3]thiadiazol-3-yl)sulfide 8 were confirmed by single-crystal X-ray analysis.     

An efficient algorithm for accelerating the convergence of oscillatory series,useful for computing the polylogarithm and Hurwitz zeta functions

This paper sketches a technique for improving the rate of convergence of a general oscillatory sequence, and then applies this series acceleration algorithm to the polylogarithm and the Hurwitz zeta function. As such, it may be taken as an extension of the techniques given by Borwein’s “An efficient algorithm for computing the Riemann zeta function” by Borwein for computing the Riemann zeta function, to more general series. The algorithm provides a rapid means of evaluating Li _s (z) for general values of complex s and a kidney-shaped region of complex z values given by ∣z ²/(z–1)∣<4. By using the duplication formula and the inversion formula, the range of convergence for the polylogarithm may be extended to the entire complex z-plane, and so the algorithms described here allow for the evaluation of the polylogarithm for all complex s and z values. Alternatively, the Hurwitz zeta can be very rapidly evaluated by means of an Euler–Maclaurin series. The polylogarithm and the Hurwitz zeta are related, in that two evaluations of the one can be used to obtain a value of the other; thus, either algorithm can be used to evaluate either function. The Euler–Maclaurin series is a clear performance winner for the Hurwitz zeta, while the Borwein algorithm is superior for evaluating the polylogarithm in the kidney-shaped region. Both algorithms are superior to the simple Taylor’s series or direct summation. The primary, concrete result of this paper is an algorithm allows the exploration of the Hurwitz zeta in the critical strip, where fast algorithms are otherwise unavailable. A discussion of the monodromy group of the polylogarithm is included.      

Carrier envelope phase stabilization of a Yb:KGW laser amplifier

In this paper we report on the active stabilization of the carrier envelope phase (CEP) of a Yb:KGW chirped pulse amplifier laser system seeded by a Yb-doped solid-state Kerr-lens mode-locked oscillator. The regenerative amplifier delivers 180 fs CEP stable pulses of 30 μJ-1 mJ energy at a repetition rate tunable from 1 to 200 kHz. The bandwidth of the feedback loop was extended by a factor of 5 using a specially designed high-pass filter, which resulted in a dramatic decrease of CEP jitter below 0.45 rad after the amplifier.     

Quantitative and sensitive detection of rare mutations using droplet-based microfluidics

Somatic mutations within tumoral DNA can be used as highly specific biomarkers to distinguish cancer cells from their normal counterparts. These DNA biomarkers are potentially useful for the diagnosis, prognosis, treatment and follow-up of patients. In order to have the required sensitivity and specificity to detect rare tumoral DNA in stool, blood, lymph and other patient samples, a simple, sensitive and quantitative procedure to measure the ratio of mutant to wild-type genes is required. However, techniques such as dual probe TaqMan(?) assays and pyrosequencing, while quantitative, cannot detect less than ～1% mutant genes in a background of non-mutated DNA from normal cells. Here we describe a procedure allowing the highly sensitive detection of mutated DNA in a quantitative manner within complex mixtures of DNA. The method is based on using a droplet-based microfluidic system to perform digital PCR in millions of picolitre droplets. Genomic DNA (gDNA) is compartmentalized in droplets at a concentration of less than one genome equivalent per droplet together with two TaqMan(?) probes, one specific for the mutant and the other for the wild-type DNA, which generate green and red fluorescent signals, respectively. After thermocycling, the ratio of mutant to wild-type genes is determined by counting the ratio of green to red droplets. We demonstrate the accurate and sensitive quantification of mutated KRAS oncogene in gDNA. The technique enabled the determination of mutant allelic specific imbalance (MASI) in several cancer cell-lines and the precise quantification of a mutated KRAS gene in the presence of a 200,000-fold excess of unmutated KRAS genes. The sensitivity is only limited by the number of droplets analyzed. Furthermore, by one-to-one fusion of drops containing gDNA with any one of seven different types of droplets, each containing a TaqMan(?) probe specific for a different KRAS mutation, or wild-type KRAS, and an optical code, it was possible to screen the six common mutations in KRAS codon 12 in parallel in a single experiment.     

Improved scheme for selection of potentially optimal hyper-rectangles in <Emphasis FontCategory="NonProportional">DIRECT</Emphasis>

We consider a box-constrained global optimization problem with a Lipschitz-continuous objective function and an unknown Lipschitz constant. The well known derivative-free global-search DIRECT (DIvide a hyper-RECTangle) algorithm performs well solving such problems. However, the efficiency of the DIRECT algorithm deteriorates on problems with many local optima and when the solution with high accuracy is required. To overcome these difficulties different regimes of global and local search are introduced or the algorithm is combined with local optimization. In this paper we investigate a different direction of improvement of the DIRECT algorithm and propose a new strategy for the selection of potentially optimal rectangles, what does not require any additional parameters or local search subroutines. An extensive experimental investigation reveals the effectiveness of the proposed enhancements.     

Light Engineering and Silicon Diffractive Optics Assisted Nonparaxial Terahertz Imaging

The art of light engineering unveils a world of possibilities through the meticulous manipulation of photonic properties such as intensity, phase, and polarization. Precision control over these properties finds application in a variety of fields spanning communications, light–matter interactions, laser direct writing, and imaging. Terahertz (THz) range, nestled between microwaves and infrared light, stands out for its remarkable ability to propagate with minimal losses in numerous dielectric materials and compounds, making THz imaging a powerful tool for noninvasive control and inspection. In this study, a rational framework for the design and optimal assembly of nonparaxial THz imaging systems is established. The research is centered on lensless photonic systems composed solely of high-resistivity silicon-based nonparaxial elements such as the Fresnel zone plate, the Fibonacci lens, the Bessel axicon, and the Airy zone plate, all fabricated using laser ablation technology. Through a comprehensive examination through illumination engineering and scattered light collection from raster-scanned samples in a single-pixel detector scheme, the imaging systems are evaluated via diverse metrics including contrast, resolution, depth of field, and focus. These findings chart an exciting course toward the development of compact and user-friendly THz imaging systems where sensors and optical elements seamlessly integrate into a single chip.     

A variant of the bruylants reaction. Synthesis of 4-heteroaryl-4-anilinopiperidines.

Imines can be generated in situ from -aminonitriles and efficiently trapped by a variety of lithiated heterocycles. This variation of the Bruylants reaction has proven to be a general method for the synthesis of -heteroaryl secondary amines.     

Synthesis of bromocyclopropylpyridines via the Sandmeyer reaction

The reactions of 2-amino-5-cyclopropylpyridine with organic nitrites in the presence of copper(II) halides in various organic solvents were investigated. Optimal reaction conditions for the Sandmeyer reaction were developed and successfully applied to the synthesis of useful building blocks, bromo and chlorocyclopropylpyridines. Aminocyclopropylpyridines were synthesized in high yields from the corresponding aminobromopyridines under standard Suzuki coupling conditions.     

Reflection Absorption Infrared Spectroscopy Characterization of SAM Formation from 8-Mercapto-N-(phenethyl)octanamide Thiols with Phe Ring and Amide Groups

Multifunctional amide-containing self-assembled monolayers (SAMs) provide prospects for the construction of interfaces with required physicochemical properties and distinctive stability. In this study, we report the synthesis of amide-containing thiols with terminal phenylalanine (Phe) ring functionality (HS(CH₂)₇CONH(CH₂)₂C₆H₅) and the characterization of the formation of SAMs from these thiols on gold by reflection absorption infrared spectroscopy (RAIRS). For reliable assignments of vibrational bands, ring deuterated analogs were synthesized and studied as well. Adsorption time induced changes in Amide-II band frequency and relative intensity of Amide-II/Amide-I bands revealed two-state sigmoidal form dependence with a transition inflection points at 2.2 ± 0.5 and 4.7 ± 0.5 min, respectively. The transition from initial (disordered) to final (hydrogen-bonded, ordered) structure resulted in increased Amide-II frequency from 1548 to 1557 cm⁻¹, which is diagnostic for a strongly hydrogen-bonded amide network in trans conformation. However, the lateral interactions between the alkyl chains were found to be somewhat reduced when compared with well-ordered alkane thiol monolayers.