Interstellar formation of lactaldehyde, a key intermediate in the methylglyoxal pathway.

Aldehydes are ubiquitous in star-forming regions and carbonaceous chondrites, serving as essential intermediates in metabolic pathways and molecular mass growth processes to vital biomolecules necessary for the origins of life. However, their interstellar formation mechanisms have remained largely elusive. Here, we unveil the formation of lactaldehyde (CHCH(OH)CHO) by barrierless recombination of formyl (HĊO) and 1-hydroxyethyl (CHĊHOH) radicals in interstellar ice analogs composed of carbon monoxide (CO) and ethanol (CHCHOH).

Quantized current steps due to the synchronization of microwaves with Bloch oscillations in small Josephson junctions.

Synchronization of Bloch oscillations in small Josephson junctions (JJs) under microwave radiation, which leads to current quantization, has been proposed as an effect that is dual to the appearance of Shapiro steps. This current quantization was recently demonstrated in superconducting nanowires in a compact high-impedance environment. Direct observation of current quantization in JJs would confirm the synchronization of Bloch oscillations with microwaves and help with the realisation of the metrological current standard.

Formation of methylglyoxal (CHC(O)CHO) in interstellar analog ices - a key intermediate in cellular metabolism.

Ketoaldehydes are key intermediates in biochemical processes including carbohydrate, lipid, and amino acid metabolism. Despite their crucial role in the interstellar synthesis of essential biomolecules necessary for the Origins of Life, their formation mechanisms have largely remained elusive. Here, we report the first bottom-up formation of methylglyoxal (CHC(O)CHO)-the simplest ketoaldehyde-through the barrierless recombination of the formyl (HĊO) radical with the acetyl (CHĊO) radical in low-temperature interstellar ice analogs upon exposure to energetic irradiation as proxies of galactic cosmic rays.

Hypergolic ionic liquids: to be or not to be?

Hypergolic ionic liquids (HIL) - ionic liquids which ignite spontaneously upon contact with an oxidizer - emerged as green space propellants. Exploiting the previously marked hypergolic [EMIM][CBH] - WFNA (1-ethyl-3-methylimidazolium cyanoborohydride - white fuming nitric acid) system as a benchmark, through the utilization of a novel chirped-pulse droplet-merging technique in an ultrasonic levitation environment and electronic structure calculations, this work deeply questions the hypergolicity of the [EMIM][CBH]-WFNA system. Molecular oxygen is critically required for the [EMIM][CBH]-WFNA system to ignite spontaneously.

rare codon UUA: from features associated with 2 related locations to candidate phage regulatory translational bypassing.

In species, the cell cycle involves a switch from an early and vegetative state to a later phase where secondary products including antibiotics are synthesized, aerial hyphae form and sporulation occurs. AdpA, which has two domains, activates the expression of numerous genes involved in the switch from the vegetative growth phase. The mRNA of many species has a UUA codon in a linker region between 5' sequence encoding one domain and 3' sequence encoding its other and C-terminal domain.

Enhancing reactivity of SiO ions by controlled excitation to extreme rotational states.

Optical pumping of molecules provides unique opportunities for control of chemical reactions at a wide range of rotational energies. This work reports a chemical reaction with extreme rotational excitation of a reactant and its kinetic characterization. We investigate the chemical reactivity for the hydrogen abstraction reaction SiO + H → SiOH + H in an ion trap.

Processing of methane and acetylene ices by galactic cosmic rays and implications to the color diversity of Kuiper Belt objects.

Kuiper Belt objects exhibit a wider color range than any other solar system population. The origin of this color diversity is unknown, but likely the result of the prolonged irradiation of organic materials by galactic cosmic rays (GCRs). Here, we combine ultrahigh-vacuum irradiation experiments with comprehensive spectroscopic analyses to examine the color evolution during GCR processing methane and acetylene under Kuiper Belt conditions.

Exotic Inverse Kinetic Isotopic Effect in the Thermal Decomposition of Levitated Aluminum Iodate Hexahydrate Particles.

Aluminum iodate hexahydrate ([Al(HO)](IO)(HIO); AIH) represents a novel, oxidizing material for energetic applications. Recently, AIH was synthesized to replace the aluminum oxide passivation layer of aluminum nanoenergetic materials (ALNEM). The design of reactive coatings for ALNEM-doped hydrocarbon fuels in propulsion systems requires fundamental insights of the elementary steps of the decomposition of AIH.

Unraveling the initial steps of the ignition chemistry of the hypergolic ionic liquid 1-ethyl-3-methylimidazolium cyanoborohydride ([EMIM][CBH]) with nitric acid (HNO) exploiting chirped pulse triggered droplet merging.

The composition of the products and the mechanistic routes for the reaction of the hypergolic ionic liquid (HIL) 1-ethyl-3-methylimidazolium cyanoborohydride ([EMIM][CBH]) and nitric acid (HNO) at various concentrations from 10% to 70% were explored using a contactless single droplet merging within an ultrasonic levitation setup in an inert atmosphere of argon to reveal the initial steps that cause hypergolicity. The reactions were initiated through controlled droplet-merging manipulation triggered by a frequency chirp pulse amplitude modulation. Utilizing the high-speed optical and infrared cameras surrounding the levitation process chamber, intriguing visual images were unveiled: (i) extensive gas release and (ii) temperature rises of up to 435 K in the merged droplets.

Discovery of Discrete Stages in the Oxidation of -Tetrahydrodicyclopentadiene (CH) Droplets Doped with Titanium-Aluminum-Boron Reactive Mixed-Metal Nanopowder.

Titanium (Ti), aluminum (Al), and boron (B) reactive mixed-metal nanopowders (Ti-Al-B RMNPs) represent attractive additives to hydrocarbon fuels such as -tetrahydrodicyclopentadiene (CH; JP-10) enhancing the limited volumetric energy densities of traditional hydrocarbons, but fundamental mechanisms and combustion stages in the oxidation have been obscure. This understanding is of vital significance in the development of next-generation propulsion systems and energy-generation technologies. Here, we expose distinct oxidation stages of single droplets of JP-10 doped with Ti-Al-B-RMNP exploiting innovative ultrasonic levitator technology coupled with time-resolved spectroscopic (UV-vis) and imaging diagnostics (optical and infrared).

Quantized current steps due to the a.c. coherent quantum phase-slip effect.

The a.c. Josephson effect predicted in 1962 and observed experimentally in 1963 as quantized 'voltage steps' (the Shapiro steps) from photon-assisted tunnelling of Cooper pairs is among the most fundamental phenomena of quantum mechanics and is vital for metrological quantum voltage standards.

Translational Frameshifting in the Gene Gives a Clue to the Coevolution of the Chlorophyll and Cobalamin Biosyntheses.

Today, hundreds of prokaryotic species are able to synthesize chlorophyll and cobalamin (vitamin B12). An important step in the biosynthesis of these coenzymes is the insertion of a metal ion into a porphyrin ring. Namely, Mg-chelatase ChlIDH and aerobic Co-chelatase CobNST are utilized in the chlorophyll and vitamin B12 pathways, respectively.

Application of Barophoresis in Chronic Generalized Periodontitis: a Mathematical Substantiation.

Unlabelled: was to evaluate the use of barophoresis for the delivery of liquid-air drug substances to the gums using a mathematical model of the interaction of the drug mixture with periodontal tissues.

Materials And Methods: The solution to the problem was preceded by generation of a geometric CAD model of the device and nozzle for barophoresis, including the nozzle and injector geometry. The Ansys SpaceClaim software package was used to generate the CAD geometry.

Dramatic Conformer-Dependent Reactivity of the Acetaldehyde Oxide Criegee Intermediate with Dimethylamine a 1,2-Insertion Mechanism.

The reactivity of carbonyl oxides has previously been shown to exhibit strong conformer and substituent dependencies. Through a combination of synchrotron-multiplexed photoionization mass spectrometry experiments (298 K and 4 Torr) and high-level theory [CCSD(T)-F12/cc-pVTZ-F12//B2PLYP-D3/cc-pVTZ with an added CCSDT(Q) correction], we explore the conformer dependence of the reaction of acetaldehyde oxide (CHCHOO) with dimethylamine (DMA). The experimental data support the theoretically predicted 1,2-insertion mechanism and the formation of an amine-functionalized hydroperoxide reaction product.

Precisely spun super rotors.

Improved optical control of molecular quantum states promises new applications including chemistry in the quantum regime, precision tests of fundamental physics, and quantum information processing. While much work has sought to prepare ground state molecules, excited states are also of interest. Here, we demonstrate a broadband optical approach to pump trapped SiO molecules into pure super rotor ensembles maintained for many minutes.

Direct Interactions with Nascent Transcripts Is Potentially a Common Targeting Mechanism of Long Non-Coding RNAs.

Although thousands of mammalian long non-coding RNAs (lncRNAs) have been reported in the last decade, their functional annotation remains limited. A wet-lab approach to detect functions of a novel lncRNA usually includes its knockdown followed by RNA sequencing and identification of the deferentially expressed genes. However, identification of the molecular mechanism(s) used by the lncRNA to regulate its targets frequently becomes a challenge.

Cooling of a Zero-Nuclear-Spin Molecular Ion to a Selected Rotational State.

We demonstrate rotational cooling of the silicon monoxide cation via optical pumping by a spectrally filtered broadband laser. Compared with diatomic hydrides, SiO^{+} is more challenging to cool because of its smaller rotational interval. However, the rotational level spacing and the large dipole moment of SiO^{+} allows for direct manipulation by microwaves, and the absence of hyperfine structure in its dominant isotopologue greatly reduces demands for pure quantum state preparation.

Geometrically nonlinear dynamic model for a hexagonal lattice.

It is shown that angular stiffness in the hexagonal lattice model plays a significant role in the geometrical nonlinear terms in the equations of the continuum limit. A geometrically nonlinear discrete model is formulated for the hexagonal lattice by considering the interaction of two sublattices. An asymptotic procedure is developed in order to obtain the nonlinear coupled equations of motion in the continuum limit of the discrete model.

Two Cobalt Chelatase Subunits Can Be Generated from a Single chlD Gene via Programed Frameshifting.

Magnesium chelatase chlIDH and cobalt chelatase cobNST enzymes are required for biosynthesis of (bacterio)chlorophyll and cobalamin (vitamin B12), respectively. Each enzyme consists of large, medium, and small subunits. Structural and primary sequence similarities indicate common evolutionary origin of the corresponding subunits.

Practical Guidance in Genome-Wide RNA:DNA Triple Helix Prediction.

Long noncoding RNAs (lncRNAs) play a key role in many cellular processes including chromatin regulation. To modify chromatin, lncRNAs often interact with DNA in a sequence-specific manner forming RNA:DNA triple helices. Computational tools for triple helix search do not always provide genome-wide predictions of sufficient quality.

Sensitive Mass Spectrometer for Time-Resolved Gas-Phase Chemistry Studies at High Pressures.

We report a new experimental apparatus for direct time-resolved probing of high-pressure gas-phase chemical reactions by photoionization mass spectrometry. The apparatus uses a laser photolysis flow reactor, capable of operating at = 0.3-100 bar and = 300-1000 K.

To Boldly Look Where No One Has Looked Before: Identifying the Primary Photoproducts of Acetylacetone.

We investigate the gas-phase photochemistry of the enolone tautomer of acetylacetone (pentane-2,4-dione) following S(ππ*) ← S excitation at λ = 266 and 248 nm, using three complementary time-resolved spectroscopic methods. Contrary to earlier reports, which claimed to study one-photon excitation of acetylacetone and found OH and CH as the only important gas-phase products, we detect 15 unique primary photoproducts and demonstrate that five of them, including OH and CH, arise solely by multiphoton excitation. We assign the one-photon products to six photochemical channels and show that the most significant pathway is phototautomerization to the diketone form, which is likely an intermediate in several of the other product channels.

Influence of the Ether Functional Group on Ketohydroperoxide Formation in Cyclic Hydrocarbons: Tetrahydropyran and Cyclohexane.

Photolytically initiated oxidation experiments were conducted on cyclohexane and tetrahydropyran using multiplexed photoionization mass spectrometry to assess the impact of the ether functional group in the latter species on reaction mechanisms relevant to autoignition. Pseudo-first-order conditions, with [O]:[R] > 2000, were used to ensure that R + O → products were the dominant reactions. Quasi-continuous, tunable vacuum ultraviolet light from a synchrotron was employed over the range 8.

Experimental and computational studies of Criegee intermediate reactions with NH and CHNH.

Ammonia and amines are emitted into the troposphere by various natural and anthropogenic sources, where they have a significant role in aerosol formation. Here, we explore the significance of their removal by reaction with Criegee intermediates, which are produced in the troposphere by ozonolysis of alkenes. Rate coefficients for the reactions of two representative Criegee intermediates, formaldehyde oxide (CH2OO) and acetone oxide ((CH3)2COO) with NH3 and CH3NH2 were measured using cavity ring-down spectroscopy.