Single-shot dynamics of dual-comb generation in a polarization-multiplexing fiber laser.

Dual optical frequency combs have been a recurrent case of study over the last decade due to their wide use in a variety of metrology applications. Utilizing a single cavity laser to generate a dual comb reduces system complexity and facilitates suppression of common noise. However, a dual-comb regime in single cavity lasers tends to be more unstable and difficult to achieve. Therefore, having a better understanding about the way they are generated could improve and automate their generation and control. In this paper, we investigate the build-up dynamics and collision of dual comb in a polarization-multiplexing ring-cavity fiber laser using DFT (Dispersive Fourier Transform) method. We observe a bunch of meta-stable short-lived mode-locking states before the laser entered the dual-comb mode-locking state. The energy level of this short-lived initial pulses determines its evolution. If it decreases too much, the pulse will eventually collapse while if it stays above certain level, it will be successfully generated. The results presented in this paper increase the understanding of dual-comb generation inside a single cavity laser and may contribute in future attempts to increase the stabilization of this regime.

Synthesis of Levulinic Acids From Muconic Acids in Hot Water.

Levulinic acid is a key biorenewable platform molecule. Its current chemical production from sugars is plagued by limited yields, char formation and difficult separations. An alternative and selective route starting from muconic acid via simple heating in water at high temperature (180 °C) has been developed. Muconic acid can be obtained from sugars or catechol fermentation. Chemical oxidation of catechol is another possibility which advantageously can also be applied on substituted catechols, hereby providing substituted muconic acids. When applying the disclosed hydrothermal protocol on these substrates hitherto unknown substituted levulinic acids were accessed. In particular, 3-propyllevulinic acid has been synthesized from 4-propylcatechol, prepared from pine wood. This propylated derivative has been used for the synthesis of a 3-propyllevulinate diester, i.e. butane-1,4-diyl bis(4-oxo-3-propylpentanoate), via esterification with 1,4-butanediol. The diester showed superior performance as plasticizer in comparison to the corresponding levulinate diester in both PVC (polyvinyl chloride) and PLA (polylactic acid). It plasticizes equally effective as the notorious commercial phthalate-based benchmark DEHP (di-2-ethylhexyl phthalate) in PVC.

Polarization attractors driven by vector soliton rain.

Soliton rain is a bunch of small soliton pulses slowly drifting near the main pulse having the period of a round trip. For Er-doped fiber laser mode-locked by carbon nanotubes, for the first time, we demonstrate both experimentally and theoretically a new type of polarization attractors controllable by vector soliton rain. With adjusting the pump power, vector soliton rain takes the form of pulses with rotating states of polarization which enable transforming slowly evolving trajectories on the Poincaré sphere from the double-scroll spiral to the circle. The obtained results on controlling complex multisoliton dynamics can be of interest in laser physics and engineering with potential applications in spectroscopy, metrology, and biomedical diagnostics.

Selective Nickel-Catalyzed Hydrodeacetoxylation of Aryl Acetates.

Acetate serves as a renewable and easily installed leaving group for selective deoxygenation of phenolics (ArOH). Ni-catalyzed hydrodeacetoxylation of aryl acetates (Ar-OAc) with HBpin in a green carbonate solvent selectively delivers the corresponding deoxygenated arenes (ArH). The method is also applicable to highly challenging guaiacyl and syringyl acetates, leaving -OMe groups intact without arene reduction. Renewable 4-propylguaiacol obtained from pine can also be transformed without significant loss in yield versus oil derived feedstock. The observed chemoselectivity for Ar-OAc versus ArO-Ac bond cleavage was rationalized based on mechanistic experiments and DFT calculations. ArOH side-product formation is attributed to direct competitive Ni-catalyzed reduction of the C=O bond. Hydrodeacyloxylation of a set of aryl alkanoates featured interesting chemoselectivity with a dramatic influence of the length and structure of the alkyl chain on catalysis.

Brønsted Acid Catalyzed Tandem Defunctionalization of Biorenewable Ferulic acid and Derivates into Bio-Catechol.

An efficient conversion of biorenewable ferulic acid into bio-catechol has been developed. The transformation comprises two consecutive defunctionalizations of the substrate, that is, C-O (demethylation) and C-C (de-2-carboxyvinylation) bond cleavage, occurring in one step. The process only requires heating of ferulic acid with HCl (or H2 SO4 ) as catalyst in pressurized hot water (250 °C, 50 bar N2 ). The versatility is shown on a variety of other (biorenewable) substrates yielding up to 84 % di- (catechol, resorcinol, hydroquinone) and trihydroxybenzenes (pyrogallol, hydroxyquinol), in most cases just requiring simple extraction as work-up.

Rogue bioelectrical waves in the brain: the Hurst exponent as a potential measure for presurgical mapping in epilepsy.

OBJECTIVE: Brain electromagnetic activity in patients with epilepsy is characterized by abnormal high-amplitude transient events (spikes) and abnormal patterns of synchronization of brain rhythms that accompany epileptic seizures. With the aim of improving methods for identifying epileptogenic sources in magnetoencephalographic (MEG) recordings of brain data, we applied methods previously used in the study of oceanic 'rogue waves' and other freak events in complex systems. APPROACH: For data from three patients who were awaiting surgical treatment for epilepsy, we used a beamformer source model to produce volumetric maps showing areas with a high proportion of spikes that could be classified as 'rogue waves', and areas with high Hurst exponent (HE). The HE describes the extent to which a system is exhibiting persistent behavior, may predict the likelihood of freak events. These measures were compared with the more standard measure of kurtosis, which has been shown to be a reliable method for localizing interictal spikes. MAIN RESULTS: There was partial concordance between the three different volumetric maps indicating that each measure provides different information about the underlying brain data. The HE, when combined with a simple connectivity analysis based on phase slope index (PSI), was able to identify the probable epileptogenic zone in all three patients, despite very different patterns of abnormal activity. The differences between distributions of high HE and high kurtosis values indicates that while spikes are propagated through cortex from the epileptogenic zone, the persistent dynamical conditions under which the spikes are generated may not be propagated in a similar way. Finally, the patterns of persistent activity, indicating a departure from 'healthy criticality' in brain networks may explain the wide range of social and cognitive impairments that are seen in epilepsy patients. SIGNIFICANCE: The HE is a potentially useful addition to the clinician's battery of measures which may be used convergently to guide surgical intervention.

Carbamate Synthesis Using a Shelf-Stable and Renewable C1 Reactant.

4-Propylcatechol carbonate is a shelf-stable, renewable C1 reactant. It is easily prepared from renewable 4-propylcatechol (derived from wood) and dimethyl carbonate (derived from CO2 ) using a reactive distillation system. In this work, the 4-propylcatechol carbonate is used for the two-step synthesis of carbamates under mild reaction conditions. In the first step, 4-propylcatechol carbonate is treated with an alcohol at 50-80 °C in the presence of a Lewis acid catalyst, such as Zn(OAc)2 ⋅2 H2 O. With liquid alcohols, no solvent is used and with solid alcohols 2-methyltetrahydrofuran is used as solvent. In the second step, the alkyl 2-hydroxy-propylphenyl carbonate intermediates obtained react with amines at room temperature in 2-methyltetrahydrofuran, forming the target carbamates and the byproduct 4-propylcatechol, which can be recycled into a carbonate reactant.

Fiber echo state network analogue for high-bandwidth dual-quadrature signal processing.

All-optical platforms for recurrent neural networks can offer higher computational speed and energy efficiency. To produce a major advance in comparison with currently available digital signal processing methods, the new system would need to have high bandwidth and operate both signal quadratures (power and phase). Here we propose a fiber echo state network analogue (FESNA) - the first optical technology that provides both high (beyond previous limits) bandwidth and dual-quadrature signal processing. We demonstrate applicability of the designed system for prediction tasks and for the mitigation of distortions in optical communication systems with multilevel dual-quadrature encoded signals.

Concise Xanthine Synthesis through a Double-Amidination Reaction of a 6-Chlorouracil with Amidines using Base-Metal Catalysis.

A new and concise route towards xanthines through a double-amidination reaction is described; consecutive intermolecular C-Cl and intramolecular oxidative C-H amidination. N-uracil amidines are obtained through SN AE on a 6-chlorouracil with amidines. Direct Cu-catalyzed oxidative C-H amidination on these N-uracil amidines yields polysubstituted xanthines. Sustainable oxidants, tBu2 O2 or O2 , can be used in this oxidase-type reaction. The protocol allows for the introduction of N1, N3, N7, and C8 substituents during the xanthine-scaffold construction, thus avoiding post-functionalization steps. Both 6-chlorouracils and amidines are readily available commercially or through synthesis.

Vector self-pulsing in erbium-doped fiber lasers.

Insight into instabilities of fiber laser regimes leading to complex self-pulsing operations is an opportunity to unlock the high power and dynamic operation tunability of lasers. Though many models have been suggested, there is no complete covering of self-pulsing complexity observed experimentally. Here, I further generalized our previous vector model of erbium-doped fiber laser and, for the first time, to the best of my knowledge, map tunability of complex vector self-pulsing on Poincare sphere (limit cycles and double scroll polarization attractors) for laser parameters, e.g., power, ellipticity of the pump wave, and in-cavity birefringence. Analysis validated by extensive numerical simulations demonstrates good correspondence to the experimental results on complex self-pulsing regimes obtained by many authors during the last 20 years.

Amine Activation: Synthesis of N-(Hetero)arylamides from Isothioureas and Carboxylic Acids.

A novel method for N-(hetero)arylamide synthesis based on rarely explored amine activation, rather than classical acid activation, is reported. The activated amines are easily prepared using a three-component reaction with commercial reagents. The new method shows a broad scope including challenging amides not (efficiently) accessible via classical protocols.

Isolator-free switchable uni- and bidirectional hybrid mode-locked erbium-doped fiber laser.

An Erbium-doped fibre ring laser hybrid mode-locked with single-wall carbon nanotubes (SWNT) and nonlinear polarisation evolution (NPE) without an optical isolator has been investigated for various cavity conditions. Precise control of the state of polarisation (SOP) in the cavity ensures different losses for counter-propagating optical fields. As the result, the laser operates in quasi-unidirectional regime in both clockwise (CW) and counter-clockwise (CCW) directions with the emission strengths difference of the directions of 22 dB. Furthermore, by adjusting the net birefringence in the cavity, the laser can operate in a bidirectional generation. In this case, a laser pumped with 75 mW power at 980 nm generates almost identical 790 and 570 fs soliton pulses with an average power of 1.17 and 1.11 mW. The operation stability and pulse quality of the soliton pulses in both unidirectional regimes are highly competitive with those generated in conventional ring fibre lasers with isolator in the cavity. Demonstrated bidirectional laser operation can find vital applications in gyroscopes or precision rotation sensing technologies.

Iodide-Catalyzed Synthesis of Secondary Thiocarbamates from Isocyanides and Thiosulfonates.

A new method for the synthesis of secondary thiocarbamates from readily available isocyanides and thiosulfonates with broad functional group tolerance is reported. The reaction proceeds under mild reaction conditions in isopropanol and is catalyzed by inexpensive sodium iodide.

2,6-Di(arylamino)-3-fluoropyridine Derivatives as HIV Non-Nucleoside Reverse Transcriptase Inhibitors.

New non-nucleoside reverse transcriptase inhibitors (NNRTI), which are similar in structure to earlier described di(arylamino)pyrimidines but featuring a 2,6-di(arylamino)-3-fluoropyridine, 2,4-di(arylamino)-5-fluoropyrimidine, or 1,3-di(arylamino)-4-fluorobenzene moiety instead of a 2,4-disubstituted pyrimidine moiety, are reported. The short and practical synthesis of novel NNRTI relies on two sequential Pd-catalyzed aminations as the key steps. It is demonstrated through direct comparison with reference compounds that the presence of a fluorine atom increases the in vitro anti-HIV activity, both against the wild type virus and drug-resistant mutant strains.

Stereochemistry of the Brivaracetam Diastereoisomers.

The stereochemistry of all four stereoisomers of brivaracetam was determined using vibrational circular dichroism (VCD) spectroscopy. By comparing experimentally obtained VCD spectra and computationally simulated ones, the absolute configurations can be confidently assigned without prior knowledge of their relative stereochemistry. Neither the corrected mean absolute errors analysis of the nuclear magnetic resonance (NMR) data, nor the matching of experimental and calculated infrared spectra allowed the diastereoisomers to be distinguished. VCD spectroscopy itself suffices to establish the absolute configurations of all diastereoisomers. The relative stereochemistry could also be statistically confirmed by matching experimental and computed NMR spectra using the CP3 algorithm. The combination of VCD and NMR is recommended for molecules bearing more than one chiral center, as the relative configurations obtained from NMR serve as an independent check for those established with VCD. Analysis of the calculated VCD spectra reveals that the localized NH2 scissoring mode at around 1600 cm(-1) is characteristic for intramolecular hydrogen bonding, while the orientation of the ethyl group is reflected by the delocalized modes between 1150 and 1050 cm(-1).

Multi-scale polarisation phenomena.

Multi-scale methods that separate different time or spatial scales are among the most powerful techniques in physics, especially in applications that study nonlinear systems with noise. When the time scales (noise and perturbation) are of the same order, the scales separation becomes impossible. Thus, the multi-scale approach has to be modified to characterise a variety of noise-induced phenomena. Here, based on stochastic modelling and analytical study, we demonstrate in terms of the fluctuation-induced phenomena and Hurst R/S analysis metrics that the matching scales of random birefringence and pump-signal states of polarisation interaction in a fibre Raman amplifier results in a new random birefringence-mediated phenomenon, which is similar to stochastic anti-resonance. The observed phenomenon, apart from the fundamental interest, provides a base for advancing multi-scale methods with application to different coupled nonlinear systems ranging from lasers (multimode, mode-locked, random, etc.) to nanostructures (light-mediated conformation of molecules and chemical reactions, Brownian motors, etc.).

Fast and slowly evolving vector solitons in mode-locked fibre lasers.

We report on a new vector model of an erbium-doped fibre laser mode locked with carbon nanotubes. This model goes beyond the limitations of the previously used models based on either coupled nonlinear Schrödinger or Ginzburg-Landau equations. Unlike the previous models, it accounts for the vector nature of the interaction between an optical field and an erbium-doped active medium, slow relaxation dynamics of erbium ions, linear birefringence in a fibre, linear and circular birefringence of a laser cavity caused by in-cavity polarization controller and light-induced anisotropy caused by elliptically polarized pump field. Interplay of aforementioned factors changes coherent coupling of two polarization modes at a long time scale and so results in a new family of vector solitons (VSs) with fast and slowly evolving states of polarization. The observed VSs can be of interest in secure communications, trapping and manipulation of atoms and nanoparticles, control of magnetization in data storage devices and many other areas.

Polarization attractors in harmonic mode-locked fiber laser.

We report on a polarimetry of harmonic mode-locked erbium-doped fiber laser with carbon nanotubes saturable absorber. We find new types of vector solitons with locked, switching and precessing states of polarization. The underlying physics presents interplay between birefringence of a laser cavity created by polarization controller along with light induced anisotropy caused by polarization hole burning.

Phase noise tolerance study in coherent optical circular QAM transmissions with Viterbi-Viterbi carrier phase estimation.

We present a performance evaluation of a non-conventional approach to implement phase noise tolerant optical systems with multilevel modulation formats. The performance of normalized Viterbi-Viterbi carrier phase estimation (V-V CPE) is investigated in detail for circular m-level quadrature amplitude modulation (C-mQAM) signals. The intrinsic property of C-mQAM constellation points with a uniform phase separation allows a straightforward employment of V-V CPE without the need to adapt constellation. Compared with conventional feed-forward CPE for square QAM signals, the simulated results show an enhanced tolerance of linewidth symbol duration product (ΔνTs) at a low sensitivity penalty by using feed-forward CPE structure with C-mQAM. This scheme can be easily upgraded to higher order modulations without inducing considerable complexity.

Polarisation dynamics of vector soliton molecules in mode locked fibre laser.

Two fundamental laser physics phenomena--dissipative soliton and polarisation of light are recently merged to the concept of vector dissipative soliton (VDS), viz. train of short pulses with specific state of polarisation (SOP) and shape defined by an interplay between anisotropy, gain/loss, dispersion, and nonlinearity. Emergence of VDSs is both of the fundamental scientific interest and is also a promising technique for control of dynamic SOPs important for numerous applications from nano-optics to high capacity fibre optic communications. Using specially designed and developed fast polarimeter, we present here the first experimental results on SOP evolution of vector soliton molecules with periodic polarisation switching between two and three SOPs and superposition of polarisation switching with SOP precessing. The underlying physics presents an interplay between linear and circular birefringence of a laser cavity along with light induced anisotropy caused by polarisation hole burning.