Latest Trends in Lipase-Catalyzed Synthesis of Ester Carbohydrate Surfactants: From Key Parameters to Opportunities and Future Development.

Carbohydrate-based surfactants are amphiphilic compounds containing hydrophilic moieties linked to hydrophobic aglycones. More specifically, carbohydrate esters are biosourced and biocompatible surfactants derived from inexpensive renewable raw materials (sugars and fatty acids). Their unique properties allow them to be used in various areas, such as the cosmetic, food, and medicine industries. These multi-applications have created a worldwide market for biobased surfactants and consequently expectations for their production. Biobased surfactants can be obtained from various processes, such as chemical synthesis or microorganism culture and surfactant purification. In accordance with the need for more sustainable and greener processes, the synthesis of these molecules by enzymatic pathways is an opportunity. This work presents a state-of-the-art lipase action mode, with a focus on the active sites of these proteins, and then on four essential parameters for optimizing the reaction: type of lipase, reaction medium, temperature, and ratio of substrates. Finally, this review discusses the latest trends and recent developments, showing the unlimited potential for optimization of such enzymatic syntheses.

Microtubule-binding domains in Katanin p80 subunit are essential for severing activity in C. elegans.

Microtubule-severing enzymes (MSEs), such as Katanin, Spastin, and Fidgetin play essential roles in cell division and neurogenesis. They damage the microtubule (MT) lattice, which can either destroy or amplify the MT cytoskeleton, depending on the cellular context. However, little is known about how they interact with their substrates. We have identified the microtubule-binding domains (MTBD) required for Katanin function in C. elegans. Katanin is a heterohexamer of dimers containing a catalytic subunit p60 and a regulatory subunit p80, both of which are essential for female meiotic spindle assembly. Here, we report that p80-like(MEI-2) dictates Katanin binding to MTs via two MTBDs composed of basic patches. Substituting these patches reduces Katanin binding to MTs, compromising its function in female meiotic-spindle assembly. Structural alignments of p80-like(MEI-2) with p80s from different species revealed that the MTBDs are evolutionarily conserved, even if the specific amino acids involved vary. Our findings highlight the critical importance of the regulatory subunit (p80) in providing MT binding to the Katanin complex.

Optimization of Alkali Treatment for Production of Fermentable Sugars and Phenolic Compounds from Potato Peel Waste Using Topographical Characterization and FTIR Spectroscopy.

Potato peel waste (PPW) was utilized as a bio-template for the production of valuable compounds such as reducing sugars (RS), total sugar (TS) and total phenolic compounds (TPC). Two methods of alkali treatments, i.e., chemical (NaOH) and thermochemical (NaOH assisted with autoclaving) processes, were employed for the deconstruction of PPW. Response surface methodology (RSM) was used to study the effects of alkali concentration (0.6-1.0 w/v), substrate concentration (5-15 g) and time (4-8 h) on the extraction of RS, TS and TP from PPW. The application of alkali plus steam treatment in Box-Behnken design (BBD) with three levels yielded the optimum releases of RS, TS and TP as 7.163, 28.971 and 4.064 mg/mL, respectively, corresponding to 10% substrate loading, in 0.6% NaOH for 8 h. However, the alkali treatment reported optimum extractions of RS, TS and TP as 4.061, 17.432 and 2.993 mg/mL, respectively. The thermochemical pretreatment was proven a beneficial process as it led to higher productions of TP. FTIR and SEM were used to analyze the deterioration levels of the substrate. The present work was used to explore the sustainable management of PPW, which is a highly neglected substrate bioresource but is excessively dumped in open environment, raising environmental concerns. The cost-effective methods for the breakdown of PPW starch into fermentable sugars might be utilized to extract valuable compounds.

Blue-Light Induced Iron-Catalyzed Synthesis of γ,δ-Unsaturated Ketones.

A visible-light-induced iron-catalyzed α-alkylation of ketones with allylic and propargylic alcohols as pro-electrophiles is reported. The diaminocyclopentadienone iron tricarbonyl complex plays a dual role by harvesting light and facilitating dehydrogenation and reduction steps without the help of any exogenous photosensitizer. γ,δ-Unsaturated ketones can now be accessed through this borrowing hydrogen methodology at room temperature. Mechanistic investigations revealed that the steric hindrance on the δ-position of either the dienone or ene-ynone intermediate is the key feature to prevent or decrease the competitive 1,6-reduction (and consequently the formation of the saturated ketone) and to favor the synthesis of a set of non-conjugated enones and ynones.

Low-noise supercontinuum generation in chiral all-normal dispersion photonic crystal fibers.

We present the advantages of supercontinuum generation in chiral, therefore circularly birefringent, all-normal dispersion fibers. Due to the absence of nonlinear power transfer between the polarization eigenstates of the fiber, chiral all-normal dispersion fibers do not exhibit any polarization instabilities and thus are an ideal platform for a low-noise supercontinuum generation. By pumping a chiral all-normal dispersion fiber at 802 nm, we obtained an octave-spanning, robustly circularly polarized supercontinuum with a low noise.

Unpacking the lifelong secrets of little penguins: individual quality, energy allocation, and stochasticity in defining fitness.

While the heterogeneity among individuals of a population is more and more documented, questions on the paths through which it arises, particularly whether it is linked to fixed heterogeneity or chance alone, are still widely debated. Here, we tested how individual quality, energy allocation trade-offs, and environmental stochasticity define individual fitness. To do so, we simultaneously investigated the contribution of 18 life-history traits to the fitness of breeding little penguins (Eudyptula minor), using a structural equation model. Fitness was highly variable amongst the 162 birds monitored over their entire lifespan. It increased with the individual penguin's ability to increase (a) the number of breeding events (i.e., living longer, breeding younger, breeding more often, and producing more second clutches) and (b) the breeding success per event through increased foraging performances (i.e., mass gained at sea). While all three processes (stochasticity, individual quality, and allocation trade-offs) affected fitness, interindividual variability in fitness was mainly driven by individual quality, birds consistently breeding earlier in the season and displaying higher foraging efficiency exhibiting higher fitness. Why some birds consistently can perform better at sea and breed earlier remains a question to investigate to understand how selection applies to these traits.

Tunable fiber source of entangled UV-C and infrared photons.

Pairs of entangled photons-biphotons-are indispensable in quantum applications. However, some important spectral ranges, like the ultraviolet, have been inaccessible to them so far. Here, we use four-wave mixing in a xenon-filled single-ring photonic crystal fiber to generate biphotons with one of the photons in the ultraviolet and its entangled partner in the infrared spectral range. We tune the biphotons in frequency by varying the gas pressure inside the fiber and thus tailoring the fiber dispersion landscape. The ultraviolet photons are tunable from 271 nm to 231 nm and their entangled partners, from 764 nm to 1500 nm, respectively. Tunability up to 192 THz is achieved by adjusting the gas pressure by only 0.68 bar. At 1.43 bar, the photons of a pair are separated by more than 2 octaves. The access to ultraviolet wavelengths opens the possibility for spectroscopy and sensing with undetected photons in this spectral range.

Single-pulse terahertz spectroscopy monitoring sub-millisecond time dynamics at a rate of 50 kHz.

Slow motion movies allow us to see intricate details of the mechanical dynamics of complex phenomena. If the images in each frame are replaced by terahertz (THz) waves, such movies can monitor low-energy resonances and reveal fast structural or chemical transitions. Here, we combine THz spectroscopy as a non-invasive optical probe with a real-time monitoring technique to demonstrate the ability to resolve non-reproducible phenomena at 50k frames per second, extracting each of the generated THz waveforms every 20 µs. The concept, based on a photonic time-stretch technique to achieve unprecedented data acquisition speeds, is demonstrated by monitoring sub-millisecond dynamics of hot carriers injected in silicon by successive resonant pulses as a saturation density is established. Our experimental configuration will play a crucial role in revealing fast irreversible physical and chemical processes at THz frequencies with microsecond resolution to enable new applications in fundamental research as well as in industry.

Measurement of Minute Liquid Volumes of Chiral Molecules Using In-Fiber Polarimetry.

We report an optofluidic method that enables to efficiently measure the enantiomeric excess of chiral molecules at low concentrations. The approach is to monitor the optical activity induced by a Kagome-lattice hollow-core photonic crystal fiber filled with a sub-µL volume of chiral compounds. The technique also allows monitoring the enzymatic racemization of R-mandelic acid.

Towards the Hydrophobization of Thermoplastic Starch Using Fatty Acid Starch Ester as Additive.

To bring surface hydrophobicity to thermoplastic starch (TPS) materials for food packaging, fatty acid starch esters (FASE), specifically starch tri-laurate, were incorporated into TPS formulations. A total of three different ratios of FASE (2%, 5% and 10%) were added to the TPS formulation to evaluate the influence of FASE onto physico-chemical properties of TPS/FASE blends, i.e., surface hydrophobicity, dynamic vapor sorption (DVS), and tensile behaviors. Blending TPS with FASE leads to more hydrophobic materials, whatever the FASE ratio, with initially measured contact angles ranging from 90° for the 2%-FASE blend to 99° for the 10%-blend. FT-IR study of the material surface and inner core shows that FASE is mainly located at the material surface, justifying the increase of material surface hydrophobicity. Despite this surface hydrophobicity, blending TPS with FASE seems not to affect blend vapor sorption behavior. From a mechanical behavior perspective, the variability of tensile properties of starch-based materials with humidity rate is slightly reduced with increasing FASE ratio (a decrease of maximal stress of 10-30% was observed for FASE ratio 2% and 10%), leading to more ductile materials.

Flower-like Highly Open-Structured Binder-Free Zn-Co-Oxide Nanosheet for High-Performance Supercapacitor Electrodes.

Scientific research is being compelled to develop highly efficient and cost-effective energy-storing devices such as supercapacitors (SCs). The practical use of SC devices is hindered by their low energy density and poor rate capability due to the binding agents in fabricating electrodes. Herein, we proposed flower-like highly open-structured binder-free ZnCo2O4 micro-flowers composed of nanosheets supported in nickel foam (ZnCoO@NF) with improved rate capability up to 91.8% when current varied from 2 to 20 A·g-1. The ZnCoO@NF electrode exhibited a superior specific capacitance of 1132 F·g-1 at 2 A·g-1 and revealed 99% cycling stability after 7000 cycles at a high current density of 20 A·g-1. The improved performance of the ZnCoO@NF electrode is attributed to the highly stable structure of the micro/nano-multiscale architecture, which provides both the high conduction of electrons and fast ionic transportation paths simultaneously.

Blue-Light-Induced Iron-Catalyzed α-Alkylation of Ketones.

We report a visible-light-induced iron-catalyzed α-alkylation of ketones. The photocatalytic system is based on the single diaminocyclopentadienone iron tricarbonyl complex. Two catalytic intermediates of this complex are able to harvest light, allowing the synthesis of substituted aromatic and aliphatic ketones at room temperature using the borrowing hydrogen strategy in the presence of various substituted primary alcohols as alkylating reagents. Preliminary mechanistic studies unveil the role of light for both the dehydrogenation and reduction step.

Cortical microtubule pulling forces contribute to the union of the parental genomes in the Caenorhabditis elegans zygote.

Previously, we reported that the Polo-like kinase PLK-1 phosphorylates the single Caenorhabditis elegans lamin (LMN-1) to trigger lamina depolymerization during mitosis. We showed that this event is required to form a pronuclear envelope scission event that removes membranes on the juxtaposed oocyte and sperm pronuclear envelopes in the zygote, allowing the parental chromosomes to merge in a single nucleus after segregation (Velez-Aguilera et al., 2020). Here, we show that cortical microtubule pulling forces contribute to pronuclear envelopes scission by promoting mitotic spindle elongation, and conversely, nuclear envelopes remodeling facilitates spindle elongation. We also demonstrate that weakening the pronuclear envelopes via PLK-1-mediated lamina depolymerization, is a prerequisite for the astral microtubule pulling forces to trigger pronuclear membranes scission. Finally, we provide evidence that PLK-1 mainly acts via lamina depolymerization in this process. These observations thus indicate that temporal coordination between lamina depolymerization and mitotic spindle elongation facilitates pronuclear envelopes scission and parental genomes unification.

Effects of Geomaterial-Originated Fillers on Microstructure and Mechanical/Physical Properties of α- and ß-Chitosan-Based Films.

Edible films and coatings with good mechanical/physical properties are highly required for carrying medical substances and food packaging. So, solvent-cast films of α- or ß-chitosan filled with palygorskite, montmorillonite or geopolymer-containing material (GCM), were prepared, and the effects of their clay contents (up to 50 wt.%) on the mechanical/physical properties were assessed. The microstructure of the films was investigated using FT-IR spectroscopy, SEM and thermal analysis. The results showed that, except for the films composed of GCM and ß-chitosan, the mechanical properties of the films with limited (up to 5 wt.%) to moderate (5-25 wt.%) amounts of fillers increased as a result of the attractive electrostatic forces formed between the fillers and chitosan functional groups (-NH3+, CH2OH and NHCOCH3). However, due to the occurrence of coarse aggregates, the strength of filler-rich films declined. The addition of fillers led to an increase in porosity and water absorption of the films, but it had irregular effects on their wettability and water vapor transmission rate. These observations as well as the thermal stability of the films were discussed in relation to the characterization results.

Doppler optical frequency domain reflectometry for remote fiber sensing: erratum.

This erratum corrects a typographical error in Eq. (10) of our paper [Opt. Express29, 14615 (2021)10.1364/OE.421842].

Deep-UV-enhanced supercontinuum generated in a tapered gas-filled photonic crystal fiber.

We present the use of a linearly down-tapered gas-filled hollow-core photonic crystal fiber in a single stage, pumped with pulses from a compact infrared (IR) laser source, to generate a supercontinuum (SC) carrying significant spectral power in the deep ultraviolet (UV) [200-300 nm]. The generated SC extends from the near IR down to ∼213nm with 0.58 mW/nm and down to ∼220nm with 0.83 mW/nm in the deep UV.

Fiber-based biphoton source with ultrabroad frequency tunability.

Tunable biphotons are highly important for a wide range of quantum applications. For some applications, especially interesting are cases where two photons of a pair are far apart in frequency. Here, we report a tunable biphoton source based on a xenon-filled hollow-core photonic crystal fiber. Tunability is achieved by adjusting the pressure of the gas inside the fiber. This allows us to tailor the dispersion landscape of the fiber, overcoming the principal limitations of solid-core fiber-based biphoton sources. We report a maximum tunability of 120 THz for a pressure range of 4 bar with a continuous shift of 30 THz/bar. At 21 bar, the photons of a pair are separated by more than one octave. Despite the large separation, both photons have large bandwidths. At 17 bar, they form a very broad (110 THz) band around the frequency of the pump.

Tumbling and anomalous alignment of optically levitated anisotropic microparticles in chiral hollow-core photonic crystal fiber.

The complex tumbling motion of spinning nonspherical objects is a topic of enduring interest, both in popular culture and in advanced scientific research. Here, we report all-optical control of the spin, precession, and nutation of vaterite microparticles levitated by counterpropagating circularly polarized laser beams guided in chiral hollow-core fiber. The circularly polarized light causes the anisotropic particles to spin about the fiber axis, while, regulated by minimization of free energy, dipole forces tend to align the extraordinary optical axis of positive uniaxial particles into the plane of rotating electric field. The end result is that, accompanied by oscillatory nutation, the optical axis reaches a stable tilt angle with respect to the plane of the electric field. The results reveal new possibilities for manipulating optical alignment through rotational degrees of freedom, with applications in the control of micromotors and microgyroscopes, laser alignment of polyatomic molecules, and study of rotational cell mechanics.

Enzymatic synthesis of amphiphilic carbohydrate esters: Influence of physicochemical and biochemical parameters.

Glycolipids, carbohydrate fatty esters or sugar esters are amphiphilic molecules containing hydrophilic groups bonded to hydrophobic parent structures. Recently, glycolipids have shown their antimicrobial and antitumor capacities. Their surface activity properties have applications in the food, pharmaceutical and cosmetic industries. Sugar esters' building blocks can be obtained from natural resources and/or be transformed by biochemical pathways for uses as surfactants. Biosurfactants are non-ionic, nontoxic, biodegradable, tasteless, and odourless. The biocatalysis of these molecules involves sustainable, green, and safer methods. The advantages of producing biosurfactants from enzymatic catalysis are the energy economy, high selectivity, production of natural products, reduction of the use of fossil-based solvents and chloride compounds. This review presents the most recent studies concerning the evaluation of the impact of the main parameters and their levels influencing the enzymatic synthesis of glycolipids. Various enzyme catalysed synthetic methods were described. The parameters studied were temperature, reaction time, solvent system, type of biocatalyst, substrates molar ratio proportion and the nature of substrates. This review discusses the influence of different biocatalysts in the conversions of glycolipids; The reactivity from mono to polysaccharides and their interaction with fatty acids of different carbon chain lengths in the presence of specific enzymes; The effect of the solvent polarity, the use of multiple solvents, ionic liquids, supercritical CO2, and solvent-free media in sugar ester conversions; And the optimization of temperature and reaction time in different enzymatic systems.

Polyacrylamide Grafted Xanthan: Microwave-Assisted Synthesis and Rheological Behavior for Polymer Flooding.

Application of polymer-flooding systems in secondary and tertiary oil recovery represents a real challenge for oil industry. In this work, our main objective is to explore possibilities of making use of xanthan-g-polyacrylamide for polymer flooding in a particular Devonian oilfield of medium salinity. The graft polymer was synthesized by using microwave-assisted graft copolymerization reaction of acrylamide on xanthan. The synthesized copolymer with optimized grafting parameters has been characterized by Infrared Spectroscopy and Thermal Analysis (DSC). Rheological analysis by steady shear and oscillatory flow experiments have been subsequently performed for xanthan and grafted xanthan under reservoir conditions. In steady shear, as expected the grafted polymer solutions flow as shear-thinning materials and apparent viscosity showed good fits with Cross's model. The viscosity losses due to salinity or temperature are more controlled for the grafted xanthan compared to pristine xanthan. When the grafted polymer concentration is increased to 2000 ppm the losses were halved. In oscillatory shear, the copolymer solutions followed a global behavior of semi-dilute entangled systems; furthermore, all dynamic properties were influenced by the brine salinity. Compared to xanthan, the elastic properties of xanthan-g-polyacrylamide solutions have been significantly improved in saline media and the losses in elasticity of grafted polymer solutions are lower.