Showing papers on "Molecule published in 2015"

Chitin and Chitosan Preparation from Marine Sources. Structure, Properties and Applications

Abstract: This review describes the most common methods for recovery of chitin from marine organisms. In depth, both enzymatic and chemical treatments for the step of deproteinization are compared, as well as different conditions for demineralization. The conditions of chitosan preparation are also discussed, since they significantly impact the synthesis of chitosan with varying degree of acetylation (DA) and molecular weight (MW). In addition, the main characterization techniques applied for chitin and chitosan are recalled, pointing out the role of their solubility in relation with the chemical structure (mainly the acetyl group distribution along the backbone). Biological activities are also presented, such as: antibacterial, antifungal, antitumor and antioxidant. Interestingly, the relationship between chemical structure and biological activity is demonstrated for chitosan molecules with different DA and MW and homogeneous distribution of acetyl groups for the first time. In the end, several selected pharmaceutical and biomedical applications are presented, in which chitin and chitosan are recognized as new biomaterials taking advantage of their biocompatibility and biodegradability.

Bidentate, monoanionic auxiliary-directed functionalization of carbon-hydrogen bonds.

Abstract: ConspectusIn recent years, carbon–hydrogen bond functionalization has evolved from an organometallic curiosity to a tool used in mainstream applications in the synthesis of complex natural products and drugs. The use of C–H bonds as a transformable functional group is advantageous because these bonds are the most abundant functionality in organic molecules. One-step conversion of these bonds to the desired functionality shortens synthetic pathways, saving reagents, solvents, and labor. Less chemical waste is generated as well, showing that this chemistry is environmentally beneficial. This Account describes the development and use of bidentate, monoanionic auxiliaries for transition-metal-catalyzed C–H bond functionalization reactions. The chemistry was initially developed to overcome the limitations with palladium-catalyzed C–H bond functionalization assisted by monodentate directing groups. By the use of electron-rich bidentate directing groups, functionalization of unactivated sp3 C–H bonds under palla...

Charge-transfer-based gas sensing using atomic-layer MoS2.

Abstract: Two-dimensional (2D) molybdenum disulphide (MoS2) atomic layers have a strong potential to be used as 2D electronic sensor components. However, intrinsic synthesis challenges have made this task difficult. In addition, the detection mechanisms for gas molecules are not fully understood. Here, we report a high-performance gas sensor constructed using atomic-layered MoS2 synthesised by chemical vapour deposition (CVD). A highly sensitive and selective gas sensor based on the CVD-synthesised MoS2 was developed. In situ photoluminescence characterisation revealed the charge transfer mechanism between the gas molecules and MoS2, which was validated by theoretical calculations. First-principles density functional theory calculations indicated that NO2 and NH3 molecules have negative adsorption energies (i.e., the adsorption processes are exothermic). Thus, NO2 and NH3 molecules are likely to adsorb onto the surface of the MoS2. The in situ PL characterisation of the changes in the peaks corresponding to charged trions and neutral excitons via gas adsorption processes was used to elucidate the mechanisms of charge transfer between the MoS2 and the gas molecules.

Additive covalent radii for single-, double-, and triple-bonded molecules and tetrahedrally bonded crystals: a summary.

Abstract: The recent fits of additive covalent radii RAB = rA + rB for the title systems are reviewed and compared with alternative systems of radii by other authors or with further experimental data. The agreement of the predicted R with experiment is good, provided that the A–B bond is not too ionic, or the coordination numbers of the two atoms too different from the original input data, used in the fit. Bonds between transition metals and halides are not included in the single-bond set, because of their partial multiple-bond character.

A Facile One‐Pot Synthesis of a Two‐Dimensional MoS2/Bi2S3 Composite Theranostic Nanosystem for Multi‐Modality Tumor Imaging and Therapy

Abstract: 2D PEG-ylated MoS2/Bi2 S3 composite nanosheets are successfully constructed by introducing bismuth ions to react with the two extra S atoms in a (NH4)2 MoS4 molecule precursor for solvothermal synthesis of MoS2. The MBP nanosheets can serve as a promising platform for computed tomography and photoacoustic-imaging-guided tumor diagnosis, as well as combined tumor photothermal therapy and sensitized radiotherapy.

Increasing Mechanical Strength of Gelatin Hydrogels by Divalent Metal Ion Removal

Abstract: The usage of gelatin hydrogel is limited due to its instability and poor mechanical properties, especially under physiological conditions Divalent metal ions present in gelatin such as Ca2+ and Fe2+ play important roles in the gelatin molecule interactions The objective of this study was to determine the impact of divalent ion removal on the stability and mechanical properties of gelatin gels with and without chemical crosslinking The gelatin solution was purified by Chelex resin to replace divalent metal ions with sodium ions The gel was then chemically crosslinked by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) Results showed that the removal of divalent metal ions significantly impacted the formation of the gelatin network The purified gelatin hydrogels had less interactions between gelatin molecules and form larger-pore network which enabled EDC to penetrate and crosslink the gel more efficiently The crosslinked purified gels showed small swelling ratio, higher crosslinking density and dramatically increased storage and loss moduli The removal of divalent ions is a simple yet effective method that can significantly improve the stability and strength of gelatin hydrogels The in vitro cell culture demonstrated that the purified gelatin maintained its ability to support cell attachment and spreading

Energetics, Charge Transfer, and Magnetism of Small Molecules Physisorbed on Phosphorene

Abstract: First-principles calculations are performed to investigate the interaction of physisorbed small molecules, including CO, H2, H2O, NH3, NO, NO2, and O2, with phosphorene, and their energetics, charge transfer, and magnetic moment are evaluated on the basis of dispersion-corrected density functional theory. Our calculations reveal that CO, H2, H2O, and NH3 molecules act as a weak donor, whereas O2 and NO2 act as a strong acceptor. While the NO molecule donates electrons to graphene, it receives electrons from phosphorene. Among all the investigated molecules, NO2 has the strongest interaction through hybridizing its frontier orbitals with the 3p orbital of phosphorene. The nontrivial and distinct charge transfer occurring between phosphorene and these physisorbed molecules not only renders phosphorene promising for application as a gas sensor but also provides an effective route for modulating the polarity and density of carriers in phosphorene. In addition, the intermediate binding energy of hydrogen molec...

Density functional theory and molecular dynamics simulation study on corrosion inhibition performance of mild steel by mercapto-quinoline Schiff base corrosion inhibitor

Abstract: Corrosion inhibition mechanism of two mercapto-quinoline Schiff bases, eg., 3-((phenylimino)methyl)quinoline-2-thiol (PMQ) and 3-((5-methylthiazol-2-ylimino)methyl) quinoline-2-thiol (MMQT) on mild steel surface is investigated by quantum chemical calculation and molecular dynamics simulation. Quantum chemical parameters such as EHOMO, ELUMO, energy gap (ΔE), dipolemoment (µ), electronegativity (χ), global hardness (η) and fraction of electron transfers from the inhibitor molecule to the metallic atom surface (ΔN) have been studied to investigate their relative corrosion inhibition performance. Parameters like local reactive sites of the present molecule have been analyzed through Fukui indices. Moreover, adsorption behavior of the inhibitor molecules on Fe (1 1 0) surface have been analyzed using molecular dynamics simulation. The binding strength of the concerned inhibitor molecules on mild steel surface follows the order MMQT>PMQ, which is in good agreement with the experimentally determined inhibition efficiencies. In view of the above, our approach will be helpful for quick prediction of a potential inhibitor from a lot of similar inhibitors and subsequently in their rational designed synthesis for corrosion inhibition application following a wet chemical synthetic route.

Energetic salts with π-stacking and hydrogen-bonding interactions lead the way to future energetic materials.

Abstract: Among energetic materials, there are two significant challenges facing researchers: 1) to develop ionic CHNO explosives with higher densities than their parent nonionic molecules and (2) to achieve a fine balance between high detonation performance and low sensitivity. We report a surprising energetic salt, hydroxylammonium 3-dinitromethanide-1,2,4-triazolone, that exhibits exceptional properties, viz., higher density, superior detonation performance, and improved thermal, impact, and friction stabilities, then those of its precursor, 3-dinitromethyl-1,2,4-triazolone. The solid-state structure features of the new energetic salt were investigated with X-ray diffraction which showed π-stacking and hydrogen-bonding interactions that contribute to closer packing and higher density. According to the experimental results and theoretical analysis, the newly designed energetic salt also gives rise to a workable compromise in high detonation properties and desirable stabilities. These findings will enhance the future prospects for rational energetic materials design and commence a new chapter in this field.

Computational design of molecules for an all-quinone redox flow battery

Abstract: Inspired by the electron transfer properties of quinones in biological systems, we recently showed that quinones are also very promising electroactive materials for stationary energy storage applications. Due to the practically infinite chemical space of organic molecules, the discovery of additional quinones or other redox-active organic molecules for energy storage applications is an open field of inquiry. Here, we introduce a high-throughput computational screening approach that we applied to an accelerated study of a total of 1710 quinone (Q) and hydroquinone (QH2) (i.e., two-electron two-proton) redox couples. We identified the promising candidates for both the negative and positive sides of organic-based aqueous flow batteries, thus enabling an all-quinone battery. To further aid the development of additional interesting electroactive small molecules we also provide emerging quantitative structure-property relationships.

Metal-catalysed azidation of tertiary C–H bonds suitable for late-stage functionalization

Abstract: Many enzymes oxidize unactivated aliphatic C-H bonds selectively to form alcohols; however, biological systems do not possess enzymes that catalyse the analogous aminations of C-H bonds. The absence of such enzymes limits the discovery of potential medicinal candidates because nitrogen-containing groups are crucial to the biological activity of therapeutic agents and clinically useful natural products. In one prominent example illustrating the importance of incorporating nitrogen-based functionality, the conversion of the ketone of erythromycin to the -N(Me)CH2- group in azithromycin leads to a compound that can be dosed once daily with a shorter treatment time. For such reasons, synthetic chemists have sought catalysts that directly convert C-H bonds to C-N bonds. Most currently used catalysts for C-H bond amination are ill suited to the intermolecular functionalization of complex molecules because they require excess substrate or directing groups, harsh reaction conditions, weak or acidic C-H bonds, or reagents containing specialized groups on the nitrogen atom. Among C-H bond amination reactions, those forming a C-N bond at a tertiary alkyl group would be particularly valuable, because this linkage is difficult to form from ketones or alcohols that might be created in a biosynthetic pathway by oxidation. Here we report a mild, selective, iron-catalysed azidation of tertiary C-H bonds that occurs without excess of the valuable substrate. The reaction tolerates aqueous environments and is suitable for the functionalization of complex structures in the late stages of a multistep synthesis. Moreover, this azidation makes it possible to install a range of nitrogen-based functional groups, including those from Huisgen 'click' cycloadditions and the Staudinger ligation. We anticipate that these reactions will create opportunities to modify natural products, their precursors and their derivatives to produce analogues that contain different polarity and charge as a result of nitrogen-containing groups. It could also be used to help identify targets of biologically active molecules by creating a point of attachment--for example, to fluorescent tags or 'handles' for affinity chromatography--directly on complex molecular structures.

BN heterosuperbenzenes: synthesis and properties.

Abstract: Replacement of CC unit with its isoelectronic BN unit in aromatics provides a new class of molecules with appealing properties, which have attracted great attention recently. In this Concept, we focus on BN-substituted polycyclic aromatics with fused structures, and review their synthesis, photophysical, and redox properties, as well as their applications in organic electronics. We also present challenging synthetic targets, large BN- substituted polycyclic aromatics, such as regioregular BN heterosuperbenzenes, which can be viewed as BN-doped nanographenes. Finally, we propose an atomically precise bottom-up synthesis of structurally well-defined BN-doped graphenes.

Multistep continuous-flow synthesis of ( R )- and ( S )-rolipram using heterogeneous catalysts

Abstract: Chemical manufacturing is conducted using either batch systems or continuous-flow systems. Flow systems have several advantages over batch systems, particularly in terms of productivity, heat and mixing efficiency, safety, and reproducibility. However, for over half a century, pharmaceutical manufacturing has used batch systems because the synthesis of complex molecules such as drugs has been difficult to achieve with continuous-flow systems. Here we describe the continuous-flow synthesis of drugs using only columns packed with heterogeneous catalysts. Commercially available starting materials were successively passed through four columns containing achiral and chiral heterogeneous catalysts to produce (R)-rolipram, an anti-inflammatory drug and one of the family of γ-aminobutyric acid (GABA) derivatives. In addition, simply by replacing a column packed with a chiral heterogeneous catalyst with another column packed with the opposing enantiomer, we obtained antipole (S)-rolipram. Similarly, we also synthesized (R)-phenibut, another drug belonging to the GABA family. These flow systems are simple and stable with no leaching of metal catalysts. Our results demonstrate that multistep (eight steps in this case) chemical transformations for drug synthesis can proceed smoothly under flow conditions using only heterogeneous catalysts, without the isolation of any intermediates and without the separation of any catalysts, co-products, by-products, and excess reagents. We anticipate that such syntheses will be useful in pharmaceutical manufacturing.

Towards single molecule switches

Abstract: The concept of using single molecules as key building blocks for logic gates, diodes and transistors to perform basic functions of digital electronic devices at the molecular scale has been explored over the past decades. However, in addition to mimicking the basic functions of current silicon devices, molecules often possess unique properties that have no parallel in conventional materials and promise new hybrid devices with novel functions that cannot be achieved with equivalent solid-state devices. The most appealing example is the molecular switch. Over the past decade, molecular switches on surfaces have been intensely investigated. A variety of external stimuli such as light, electric field, temperature, tunneling electrons and even chemical stimulus have been used to activate these molecular switches between bistable or even multiple states by manipulating molecular conformations, dipole orientations, spin states, charge states and even chemical bond formation. The switching event can occur either on surfaces or in break junctions. The aim of this review is to highlight recent advances in molecular switches triggered by various external stimuli, as investigated by low-temperature scanning tunneling microscopy (LT-STM) and the break junction technique. We begin by presenting the molecular switches triggered by various external stimuli that do not provide single molecule selectivity, referred to as non-selective switching. Special focus is then given to selective single molecule switching realized using the LT-STM tip on surfaces. Single molecule switches operated by different mechanisms are reviewed and discussed. Finally, molecular switches embedded in self-assembled monolayers (SAMs) and single molecule junctions are addressed.

A Novel Mechanochromic and Photochromic Polymer Film: When Rhodamine Joins Polyurethane.

Abstract: A rhodamine-based molecule, Rh-OH, is synthesized. Rh-OH exhibits a reversible mechanochromic luminescent character but a passivating response to UV light. An elastomeric polymer film based on polyurethane with embedded Rh-OH is prepared via a polycondensation reaction. The film shows mechanochromic and photochromic properties with reversible color change, which originates from the isomerization of the Rh-OH molecule from a twisted spirolactam in the ring-closed form to a planarized zwitterionic structure in the ring-open state.

Combined covalent-electrostatic model of hydrogen bonding improves structure prediction with Rosetta

Abstract: Interactions between polar atoms are challenging to model because at very short ranges they form hydrogen bonds (H-bonds) that are partially covalent in character and exhibit strong orientation preferences; at longer ranges the orientation preferences are lost, but significant electrostatic interactions between charged and partially charged atoms remain. To simultaneously model these two types of behavior, we refined an orientation dependent model of hydrogen bonds [Kortemme et al. J. Mol. Biol. 2003, 326, 1239] used by the molecular modeling program Rosetta and then combined it with a distance-dependent Coulomb model of electrostatics. The functional form of the H-bond potential is physically motivated and parameters are fit so that H-bond geometries that Rosetta generates closely resemble H-bond geometries in high-resolution crystal structures. The combined potentials improve performance in a variety of scientific benchmarks including decoy discrimination, side chain prediction, and native sequence reco...

Electrochemical (De)Lithiation of 1D Sulfur Chains in Li–S Batteries: A Model System Study

Abstract: In contrast to the extensive studies of the electrochemical behavior of conventional cyclic S8 molecules in Li–S batteries, there has been hardly any investigation of the electrochemistry of S chains. Here we use S chains encapsulated in single- and double-walled carbon nanotubes as a model system and report the electrochemical behavior of 1D S chains in Li–S batteries. An electrochemical test shows that S chains have high electrochemical activity during lithiation and extinctive electrochemistry compared with conventional S8. The confined steric effect provides Li+ solid-phase diffusion access to insert/egress reactions with S chains. During lithiation, the long S chains spontaneously become short chains, which show higher discharge plateaus and better kinetics. The unique electrochemistry of S chains supplements the existing knowledge of the S cathode mechanism and provides avenues for rational design of S cathode materials in Li–S batteries.

Fine-Tuning of Crystal Packing and Charge Transport Properties of BDOPV Derivatives through Fluorine Substitution

Abstract: Molecular packing in organic single crystals greatly influences their charge transport properties but can hardly be predicted and designed because of the complex intermolecular interactions. In this work, we have realized systematic fine-tuning of the single-crystal molecular packing of five benzodifurandione-based oligo(p-phenylenevinylene) (BDOPV)-based small molecules through incorporation of electronegative fluorine atoms on the BDOPV backbone. While these molecules all exhibit similar column stacking configurations in their single crystals, the intermolecular displacements and distances can be substantially modified by tuning of the amounts and/or the positions of the substituent fluorine atoms. Density functional theory calculations showed that the subtle differences in charge distribution or electrostatic potential induced by different fluorine substitutions play an important role in regulating the molecular packing of the BDOPV compounds. Consequently, the electronic couplings for electron transfe...

On the existence of and mechanism for microwave-specific reaction rate enhancement

Abstract: The use of microwave radiation to drive chemical reactions has become ubiquitous in almost all fields of chemistry. In all of these areas it is principally due to rapid and convenient heating resulting in significantly higher rates of reaction, with other advantages including enhanced product selectivity and control of materials properties. Although microwave heating continues to grow as an enabling technology, fundamental research into the nature of microwave heating has not grown at the same rate. In the case of chemical reactions run in homogeneous solution, particularly synthetic organic reactions, there is considerable controversy over the origins of rate enhancement, with a fundamental question being whether there exist microwave-specific effects, distinct from what can be attained under conventional convective heating, that can accelerate a reaction rate. In this Perspective, we discuss unique aspects of microwave heating of molecules in solution and discuss the origin and nature of microwave-specific effects arising from the process of “selective heating” of reactants in solution. Integral to this discussion is work from the field of dielectric relaxation spectroscopy, which provides a model for selective heating by Debye relaxation processes. The Perspective also includes a critical discussion of hypotheses of non-thermal effects (alternatively classified here as resonant processes) and an outline of specific reaction parameters for chemical systems in which microwave-specific Debye relaxation processes can result in observable reaction rate enhancement.

New excited state proton transfer mechanisms for 1,8-dihydroxydibenzo[a,h]phenazine

Abstract: The excited state intramolecular proton transfer (ESIPT) mechanisms of 1,8-dihydroxydibenzo[a,h]phenazine (DHBP) in toluene solvent have been investigated based on time-dependent density functional theory (TD-DFT). The results suggest that both a single and double proton transfer mechanisms are relevant, in constrast to the prediction of a single one proposed previously (Piechowska et al. J. Phys. Chem. A 2014, 118, 144–151). The calculated results show that the intramolecular hydrogen bonds were formed in the S0 state, and upon excitation, the intramolecular hydrogen bonds between −OH group and pyridine-type nitrogen atom would be strengthened in the S1 state, which can facilitate the proton transfer process effectively. The calculated vertical excitation energies in the S0 and S1 states reproduce the experimental UV–vis absorption and fluorescence spectra well. The constructed potential energy surfaces of the S0 and S1 states have been used to explain the proton transfer process. Four minima have been f...

Harnessing Excited-State Intramolecular Proton-Transfer Reaction via a Series of Amino-Type Hydrogen-Bonding Molecules

Abstract: A series of new amino (NH)-type hydrogen-bonding (H-bonding) compounds comprising 2-(2′-aminophenyl)benzothiazole and its extensive derivatives were designed and synthesized. Unlike in the hydroxyl (OH)-type H-bonding systems, one of the amino hydrogens can be replaced with electron-donating/withdrawing groups. This, together with a versatile capability for modifying the parent moiety, makes feasible the comprehensive spectroscopy and dynamics studies of amino-type excited-state intramolecular proton transfer (ESIPT), which was previously inaccessible in the hydroxyl-type ESIPT systems. Empirical correlations were observed among the hydrogen-bonding strength (the N–H bond distances and proton acidity), ESIPT kinetics, and thermodynamics, demonstrating a trend that the stronger N–H···N hydrogen bond leads to a faster ESIPT, as experimentally observed, and a more exergonic reaction thermodynamics. Accordingly, ESIPT reaction can be harnessed for the first time from a highly endergonic type (i.e., prohibitio...

Molecular and ionic diffusion in aqueous – deep eutectic solvent mixtures: probing inter-molecular interactions using PFG NMR

Abstract: Pulsed field gradient (PFG) NMR has been used to probe self-diffusion of molecular and ionic species in aqueous mixtures of choline chloride (ChCl) based deep eutectic solvents (DESs), in order to elucidate the effect of water on motion and inter-molecular interactions between the different species in the mixtures, namely the Ch+ cation and hydrogen bond donor (HBD). The results reveal an interesting and complex behaviour of such mixtures at a molecular level. In general, it is observed that the hydroxyl protons (1H) of Ch+ and the hydrogen bond donor have diffusion coefficients significantly different from those measured for their parent molecules when water is added. This indicates a clear and significant change in inter-molecular interactions. In aqueous Ethaline, the hydroxyl species of Ch+ and HBD show a stronger interaction with water as water is added to the system. In the case of Glyceline, water has little effect on both hydroxyl proton diffusion of Ch+ and HBD. In Reline, it is likely that water allows the formation of small amounts of ammonium hydroxide. The most surprising observation is from the self-diffusion of water, which is considerably higher that expected from a homogeneous liquid. This leads to the conclusion that Reline and Glyceline form mixtures that are inhomogeneous at a microscopic level despite the hydrophilicity of the salt and HBD. This work shows that PFG NMR is a powerful tool to elucidate both molecular dynamics and inter-molecular interactions in complex liquid mixtures, such as the aqueous DES mixtures.

Tunable molecular orientation and elevated thermal stability of vapor-deposited organic semiconductors.

Abstract: Physical vapor deposition is commonly used to prepare organic glasses that serve as the active layers in light-emitting diodes, photovoltaics, and other devices. Recent work has shown that orienting the molecules in such organic semiconductors can significantly enhance device performance. We apply a high-throughput characterization scheme to investigate the effect of the substrate temperature (Tsubstrate) on glasses of three organic molecules used as semiconductors. The optical and material properties are evaluated with spectroscopic ellipsometry. We find that molecular orientation in these glasses is continuously tunable and controlled by Tsubstrate/Tg, where Tg is the glass transition temperature. All three molecules can produce highly anisotropic glasses; the dependence of molecular orientation upon substrate temperature is remarkably similar and nearly independent of molecular length. All three compounds form “stable glasses” with high density and thermal stability, and have properties similar to stable glasses prepared from model glass formers. Simulations reproduce the experimental trends and explain molecular orientation in the deposited glasses in terms of the surface properties of the equilibrium liquid. By showing that organic semiconductors form stable glasses, these results provide an avenue for systematic performance optimization of active layers in organic electronics.