Infrared Signatures of Prebiology - or Biology?

1997 ◽  
Vol 161 ◽  
pp. 61-76
Author(s):  
Nalin C. Wickramasinghe ◽  
Fred Hoyle ◽  
Shirwan Al-Mufti ◽  
Daryl H. Wallis

AbstractData on infrared spectra of astronomical sources and on the unidentified infrared bands is reviewed and compared with a range of predictions from organic models of interstellar grains. The best fits to a wide range of data appear to require the widespread occurrence of functional groups distributed in exactly the proportions that characterise biosystems. The question of whether these agreements are consistent with extraterrestrial prebiology, or even cosmic biology is discussed.

2001 ◽  
Vol 55 (10) ◽  
pp. 1394-1403 ◽  
Author(s):  
Kazutoshi Tanabe ◽  
Takatoshi Matsumoto ◽  
Tadao Tamura ◽  
Jiro Hiraishi ◽  
Shinnosuke Saeki ◽  
...  

Structure identification of chemical substances from infrared spectra can be done with various approaches: a theoretical method using quantum chemistry calculations, an inductive method using standard spectral databases of known chemical substances, and an empirical method using rules between spectra and structures. For various reasons, it is difficult to definitively identify structures with these methods. The relationship between structures and infrared spectra is complicated and nonlinear, and for problems with such nonlinear relationships, neural networks are the most powerful tools. In this study, we have evaluated the performance of a neural network system that mimics the methods used by specialists to identify chemical structures from infrared spectra. Neural networks for identifying over 100 functional groups have been trained by using over 10 000 infrared spectral data compiled in the integrated spectral database system (SDBS) constructed in our laboratory. Network structures and training methods have been optimized for a wide range of conditions. It has been demonstrated that with neural networks, various types of functional groups can be identified, but only with an average accuracy of about 80%. The reason that 100% identification accuracy has not been achieved is discussed.


Synthesis ◽  
2021 ◽  
Author(s):  
Alexandre Desaintjean ◽  
Fanny Danton ◽  
Paul Knochel

A wide range of polyfunctionalized di(hetero)aryl- and dialkenyl-magnesium reagents were prepared in toluene within 10 to 120 min between −78 °C and 25 °C via an I/Mg- or Br/Mg-exchange reaction using reagents of the general formula R2Mg (R = sBu, Mes). Highly sensitive functional groups, such as a triazene or a nitro group, were tolerated in these exchange reactions, enabling the synthesis of various functionalized (hetero)arenes and alkenes derivatives after quenching with several electrophiles including allyl bromides, acyl chlorides, aldehydes, ketones, and aryl iodides.


Synlett ◽  
2017 ◽  
Vol 28 (18) ◽  
pp. 2425-2428 ◽  
Author(s):  
Bill Morandi ◽  
Yong Lee

We report that a Lewis acidic silane, Me2SiHCl, can mediate the direct cross-coupling of a wide range of carbonyl compounds with alcohols to form dialkyl ethers. The reaction is operationally simple, tolerates a range of polar functional groups, can be utilized to make sterically hindered ethers, and is extendable to sulfur and nitrogen nucleo­philes.


Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 8
Author(s):  
Hui-Ju Chen ◽  
Chien-Cheng Chiu ◽  
Tsui Wang ◽  
Dong-Sheng Lee ◽  
Ta-Jung Lu

The bis-NHC–Ag/Pd(OAc)2 catalytic system (NHC = N-heterocyclic carbene), a combination of bis-NHC–Ag complex and Pd(OAc)2, was found to be a smart catalyst in the Pd-catalyzed transfer hydrogenation of various functionalized arenes and internal/terminal alkynes. The catalytic system demonstrated high efficiency for the reduction of a wide range of various functional groups such as carbonyls, alkynes, olefins, and nitro groups in good to excellent yields and high chemoselectivity for the reduction of functional groups. In addition, the protocol was successfully exploited to stereoselectivity for the transformation of alkynes to alkenes in aqueous media under air. This methodology successfully provided an alternative useful protocol for reducing various functional groups and a simple operational protocol for transfer hydrogenation.


Materials ◽  
2022 ◽  
Vol 15 (2) ◽  
pp. 466
Author(s):  
Kaixin Chang ◽  
Qianjin Zhu ◽  
Liyan Qi ◽  
Mingwei Guo ◽  
Woming Gao ◽  
...  

Nitrogen-doped carbon quantum dots (N-CQDs) were synthesized in a one-step hydrothermal technique utilizing L-lactic acid as that of the source of carbon and ethylenediamine as that of the source of nitrogen, and were characterized using dynamic light scattering, X-ray photoelectron spectroscopy ultraviolet-visible spectrum, Fourier-transformed infrared spectrum, high-resolution transmission electron microscopy, and fluorescence spectrum. The generated N-CQDs have a spherical structure and overall diameters ranging from 1–4 nm, and their surface comprises specific functional groups such as amino, carboxyl, and hydroxyl, resulting in greater water solubility and fluorescence. The quantum yield of N-CQDs (being 46%) is significantly higher than that of the CQDs synthesized from other biomass in literatures. Its fluorescence intensity is dependent on the excitation wavelength, and N-CQDs release blue light at 365 nm under ultraviolet light. The pH values may impact the protonation of N-CQDs surface functional groups and lead to significant fluorescence quenching of N-CQDs. Therefore, the fluorescence intensity of N-CQDs is the highest at pH 7.0, but it decreases with pH as pH values being either more than or less than pH 7.0. The N-CQDs exhibit high sensitivity to Fe3+ ions, for Fe3+ ions would decrease the fluorescence intensity of N-CQDs by 99.6%, and the influence of Fe3+ ions on N-CQDs fluorescence quenching is slightly affected by other metal ions. Moreover, the fluorescence quenching efficiency of Fe3+ ions displays an obvious linear relationship to Fe3+ concentrations in a wide range of concentrations (up to 200 µM) and with a detection limit of 1.89 µM. Therefore, the generated N-CQDs may be utilized as a robust fluorescence sensor for detecting pH and Fe3+ ions.


2020 ◽  
Author(s):  
Hojoon Park ◽  
jin-quan yu

<div>Cycloaddition reactions provide an expeditious route to construct ring systems in a highly convergent and stereoselective manner. For a typical cycloaddition reaction to occur, however, the installation of multiple reactive functional groups (π-bonds, leaving group, etc.) are required within the substrates, compromising the overall efficiency or scope of the cycloaddition reaction. Here, we report a palladium-catalyzed [3+2] reaction that utilizes C(sp<sup>3</sup>)–H activation to generate the three-carbon unit for formal cycloaddition with maleimides. We implemented a strategy where the initial C(sp<sup>3</sup>)–H activation/olefin insertion would trigger a relayed, second remote C(sp<sup>3</sup>)–H activation to complete a formal [3+2] cycloaddition. The diastereoselectivity profile of this reaction resembles that of a typical pericyclic cycloaddition reaction in that the relationships between multiple stereocenters are exquisitely controlled in a single reaction. The key to success was the use of weakly coordinating amides as the directing group, as undesired Heck or alkylation pathways were preferred with other types of directing groups. The use of the pyridine-3-sulfonic acid ligands is critical to enable C(sp<sup>3</sup>)–H activation directed by this weak coordination. The method is compatible with a wide range of amide substrates, including lactams, which lead to novel spiro-bicyclic products. The [3+2] product is also shown to undergo a reductive desymmetrization process to access chiral cyclopentane bearing multiple stereocenters with excellent enantioselectivity.</div>


Author(s):  
Marta Olivares ◽  
Martin Albrecht

Pyridyl-triazolylidene ligands with variable donor properties were used as tunable ligands at a dihydride iridium(III) center. The straightforward synthesis of this type of ligand allows for an easy incorporation of electron donating substituents in different positions of the pyridine ring or different functional groups such as esters, alkoxy or aliphatic chains on the C4 position of the triazole heterocycle. The stability of these hydride metal systems allowed these complexes to be used as models for studying the influence of the ligand modifications on hydride reactivity. Spectroscopic analysis provided unambiguous structural assignment of the dihydride system. Modulation of the electronic properties of the wingtip substituents did not appreciably alter the reactivity of the hydrides. Reactivity studies using acids with a wide range of pKa values indicated a correlation between hydride reactivity and acidity and showed exclusive reactivity towards the less shielded hydride trans to the carbene carbon rather than the more shielded hydride trans to the pyridine ring, suggesting that the trans effect is more relevant in these reactions than the NMR spectroscopically deduced hydridic character.


1996 ◽  
Vol 169 ◽  
pp. 225-230
Author(s):  
R. D. Blum ◽  
D. L. Depoy ◽  
K. Sellgren

We have obtained R ≈ 570 resolution K band spectra of eight sources in the Galactic Center, including four sources within the IRS 16 cluster, IRS 13, IRS 1W, and the compact He I emission line sources AF (also known as AHH) and AHH NW. We have also obtained R ≈ 570 H and K band spectra of nine galactic and LMC early–type mass–losing stars, including Ofpe/WN9 and WN stars. The spectra of both the Galactic Center sources and the comparison stars show a wide range of behavior in the He I (1.70 μm, 2.06 μm, 2.11 μm) and H I (Brackett series) lines. We find significantly larger He I equivalent widths in the AF source and two galactic early type mass losing stars than in any of the LMC stars. Several of the Galactic Center He I sources are found to have higher He I velocity widths than any of the galactic or LMC early type mass losing stars. At least one source, IRS 13, shows a strong red wing to the He I 2.06 μm emission.


Molecules ◽  
2019 ◽  
Vol 24 (15) ◽  
pp. 2782 ◽  
Author(s):  
Hatem Abushammala ◽  
Jia Mao

Nanocellulose has been subjected to a wide range of chemical modifications towards increasing its potential in certain fields of interest. These modifications either modulated the chemistry of the nanocellulose itself or introduced certain functional groups onto its surface, which varied from simple molecules to polymers. Among many, aliphatic and aromatic mono- and di-isocyanates are a group of chemicals that have been used for a century to modify cellulose. Despite only being used recently with nanocellulose, they have shown great potential as surface modifiers and chemical linkers to graft certain functional chemicals and polymers onto the nanocellulose surface. This review discusses the modification of cellulose and nanocellulose using isocyanates including phenyl isocyanate (PI), octadecyl isocyanate (OI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HMDI), and their derivatives and polymers. It also presents the most commonly used nanocellulose modification strategies including their advantages and disadvantages. It finally discusses the challenges of using isocyanates, in general, for nanocellulose modification.


2020 ◽  
Vol 21 (14) ◽  
pp. 5127
Author(s):  
Olga A. Krasheninina ◽  
Veniamin S. Fishman ◽  
Alexander A. Lomzov ◽  
Alexey V. Ustinov ◽  
Alya G. Venyaminova

We report a universal straightforward strategy for the chemical synthesis of modified oligoribonucleotides containing functional groups of different structures at the 2′ position of ribose. The on-column synthetic concept is based on the incorporation of two types of commercial nucleotide phosphoramidites containing orthogonal 2′-O-protecting groups, namely 2′-O-thiomorpholine-carbothioate (TC, as “permanent”) and 2′-O-tert-butyl(dimethyl)silyl (tBDMS, as “temporary”), to RNA during solid-phase synthesis. Subsequently, the support-bound RNA undergoes selective deprotection and follows postsynthetic 2′ functionalization of the naked hydroxyl group. This convenient method to tailor RNA, utilizing the advantages of solid phase approaches, gives an opportunity to introduce site-specifically a wide range of linkers and functional groups. By this strategy, a series of RNAs containing diverse 2′ functionalities were synthesized and studied with respect to their physicochemical properties.


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