A high-swelling reagent scaffold suitable for use in aqueous and organic solvents

A polymeric scaffold with excellent swelling properties in organic and aqueous environments is highly desirable for the medicinal chemist. Here, we demonstrate that a cross-linked polyacrylamide hydrogel that displays large swelling properties in both organic solvent and water can serve as a scaffold for the photosensitizer hematoporphyrin. Upon exposure to light, the resulting resin efficiently generates singlet oxygen which can then react with appropriate substrates.     

The biochemiresistor: an ultrasensitive biosensor for small organic molecules

New sensation: A resistance-based biosensor uses gold-coated magnetic nanoparticles (Au@MNPs) functionalized with the antibiotic enrofloxin (see picture; purple), which bind to anti-enrofloxin as analyte (blue). The Au@MNPs can be magnetically assembled between electrodes, and the measured resistance R is a function of analyte concentration.     

Modulation of protein-protein interactions with small organic molecules

Many proteins exert their biological roles as components of complexes, and the functions of proteins are often determined by their specific interactions with other proteins. Because of the central importance of protein-protein interactions for cellular processes, the ability to interfere with specific protein-protein interactions provides a powerful means of influencing the function of selected proteins within the cell. Cell-permeable small organic modulators of protein-protein interactions are thus highly desirable tools both for the study of physiological cellular processes and for the treatment of numerous diseased states. Herein a number of protein-protein interactions that are considered to be pharmaceutical targets are presented, which will familiarize the reader with the strategies that have been employed for the successful identification of small molecule modulators of these protein-protein interactions. These encouraging examples suggest that combined research efforts in the areas of functional proteomics, assay development, and organic synthesis will open up novel possibilities for the treatment of human diseases in the future.     

Colloidal crystallization of colloidal silica modified with ferrocenyl group-contained polymers in organic solvents

Surface modification of colloidal silica with ferrocenyl-grafted polymer and colloidal crystallization of the particles in organic solvent were studied. Poly(methyl methacrylate-co-vinylferrocene)-grafted silica never formed colloidal crystals in polar solvent, such as acetone, acetonitrile, ethanol and N,N-dimethylformamide (DMF), while poly(methyl methacrylate-co-ferrocenyl acrylate)-grafted silica gave colloidal crystallization in DMF. The particles prepared by grafting of poly(N,N-dimethylacrylamide-co-vinylferrocene), with vinylferrocene (Vfc) mole fraction of 1/13 and 1/23, were observed to give the crystallization in ethanol and DMF over particle volume fraction of 0.058. Further, silica modified with copolymer of Vfc and N-vinyl-2-pyrrolidone, N-vinylcarbazole or N-isopropylacrylamide formed colloidal crystals in ethanol and DMF. Especially, poly(N-isopropylacrylamide-co-Vfc)-grafted silica, which was composed of the highest mole fraction of vinylferrocene, 1/3, afforded colloidal crystallization in ethanol over particle volume fraction of 0.053. Relatively high polar vinylferrocene copolymer grafting of silica resulted in colloidal polymerization in organic solvents.     

Solubility of drug-like molecules in pure organic solvents with the CPA EoS

Solubility data in different solvents are an important issue for separation processes involving complex molecules such as natural products and pharmaceutical drugs. Nonetheless, solubility data are in general scarce and difficult to obtain, and so models are important tools to generate the necessary estimates.Different correlative, statistical and thermodynamic models have been proposed to evaluate solubilities. From these, the more theoretically sound thermodynamic models allow to generate estimates at broader temperature, pressure and composition conditions while using a smaller amount of experimental information. Among these, the cubic-plus-association equation of state that combines the simplicity and robustness of a cubic equation of state with the Wertheim's association contribution has been under attention. In this work, this EoS is for the first time proposed to model organic phase solubilities of drug-like molecules in a wide range of temperatures.Solubilities of acetanilide, acetylsalicylic acid, adipic acid, ascorbic acid, hydroquinone, ibuprofen, paracetamol and stearic acid were estimated in alcohols, ketones, alkanes, esters, acids, aromatics, chlorinated solvents, as well as in other common solvents. The hydrogen bonding behaviour was explicitly accounted for with each associating group being treated individually, as well as multiple group substitutions.Accurate correlations were obtained using a single binary interaction parameter (global AAD of 24.2%), while considering the complexity of the studied systems predictions were generally also satisfactory.     

The static electric permittivity of solutions of organic molecules in dipolar solvents

The permittivity of solutions of pyrazine and of 1,4-diazabicyclo-[2,2,2]-octane (TED) in various dipolar solvents has been measured at 10 MHz by means of a sensitive bridge method. The solvents used were water, methanol, formamide, N-methylformamide, N,N-dimethylformamide, and dimethylsulfoxide. The results of the measurements are compared with those of theoretical mixture formulas. It is shown that — depending on structural properties — the permittivity attributed to the solvation shells around the organic solute molecules is changed with respect to the pure solvent value.     

Enantioselective organocatalytic aldol reaction using small organic molecules

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Enantioselective reactions catalyzed by small organic molecules (asymmetric organocatalysis) are a comparatively new and popular segment in the area of contemporary research in asymmetric synthesis. The great synthetic utility of the aldol reaction for the formation of C–C bonds has geared up for a hard battle for research in this area resulting in a rapid evolution of tremendous highly enantioselective chiral catalysts. This review emphasizes asymmetric direct aldol reactions catalyzed by small enantioenriched organic molecules, particularly those involving enamine catalysis through primary and secondary amines. We have made significant efforts to include several important contributions from different groups in this area.     

Novel small organic molecules for a highly enantioselective direct aldol reaction

Novel organic molecules containing an l-proline amide moiety and a terminal hydroxyl for catalyzing direct asymmetric aldol reactions of aldehydes in neat acetone are designed and prepared. Catalyst 3d, prepared from l-proline and (1S,2S)-diphenyl-2-aminoethanol, exhibits high enantioselectivities of up to 93% ee for aromatic aldehydes and up to >99% ee for aliphatic aldehydes. A theoretical study of transition structures demonstrates the important role of the terminal hydroxyl group in the catalyst in the stereodiscrimination. Our results suggest a new strategy in the design of new organic catalysts for direct asymmetric aldol reactions and related transformations because plentiful chiral resources containing multi-hydrogen bond donors, for example, peptides, might be adopted in the design.     

Chiral coordination polymer as a luminescence sensor for small organic molecules

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Spectrophotometric determination of traces of water in organic solvents (oxygen-free molecules)

Spectrophotometry and potentiometry have been used to determine the self-ionization product of formic acid and the acidity constants of hydrobromic, hydrochloric, methanesulfonic, p-toluenesulfonic, sulfuric, trifluoroacetic, pieric and benzoic acids in formic acid.     

Prediction of infinite dilution activity coefficients of sulfur dioxide in organic solvents

Infinite dilution activity coefficients of sulfur dioxide in various organic solvents were correlated with two basicity scales: the solvent Gutmann donor number and Arnett heat of hydrogen bonding. Linear correlations were observed for both basicity scales, and the accuracy of activity coefficient prediction is estimated to be ±20 to 25%. Infinite dilution activity coefficients of sulfur dioxide in over 80 organic solvents were estimated from the correlations.     

Packed capillary HPLC: An attractive separation technique for small organic molecules

The feasibility of using packed capillary HPLC for the analysis of small organic molecules has been demonstrated by three examples: the separation of glucose and sucrose telomers, the separation of the different components of a solvent extraction reagent, and the separation of mono-, di-, and trioleins, all of which have been achieved with packed capillary columns of 0.32 mm inner diameter and eluent flow rates of 3 microliters per minute. Application to the analysis of the solvent extraction reagents has shown that this technique can be used as a quantitative tool in just the same way as any conventional HPLC method. The feasibility of a direct packed capillary HPLC – mass spectrometry interface has been demonstrated for the glucose telomer separation; direct coupling is only possible because of the microliter flow rates employed by the technique.     

Efficient overlay of small organic molecules using 3D pharmacophores

Aligning and overlaying two or more bio-active molecules is one of the key tasks in computational drug discovery and bio-activity prediction. Especially chemical-functional molecule characteristics from the view point of a macromolecular target represented as a 3D pharmacophore are the most interesting similarity measure when describing and analyzing macromolecule-ligand interaction. In this study, a novel approach for aligning rigid three-dimensional molecules according to their chemical-functional pharmacophoric features is presented and compared to the overlay of experimentally determined poses in a comparable macromolecule coordinate frame. The presented approach identifies optimal chemical feature pairs using distance and density characteristics obtained by correlating pharmacophoric geometries and thus proves to be faster than existing combinatorial alignment methods and creates more reasonable alignments than pure atom-based methods. Examples will be provided to demonstrate the feasibility, speed and intuitiveness of this method.     

Unusual assembly of small organic building molecules in common solvent

During the process of self-association, reaching a thermodynamic equilibrium state in dilute solution is usually very fast, taking at most seconds for small organic (such as surfactants) solutions and hours for polymer solutions. It is very rare that days are necessary for soluble small organic molecules to reach thermodynamic stability in dilute solutions. This work reports such an unusually slow association of two polymerizable organic molecules, HOOC(CH2)3CCCC(CH2)3COOH and (EtO)3Si(CH2)3NH2, in their common solvent. The self-organization process of above complexes spanned several minutes to several days, depending on their concentrations. The morphologies of resultant aggregates, ranging from vesicles to solid spheres and to hollow spheres, were also tunable by varying the molar ratios of two precursors. Enriched functional COOH/NH2 groups on the aggregate surface can attach various antibodies, which endow the nanaoparticles with great potential applications as targeted drug-delivery vehicles. In addition, as-synthesized hybrid aggregates could be further stabilized by either addition reaction of diacetylenic acid or hydrolysis and condensation reactions of 3-aminopropyltriethoxysilane. In particular, the derived polydiacetylenic aggregates demonstrate a thermochromatic property and may be applied as sensing materials. Those novel phenomena, along with the simplicity in the preparation of aggregates, make the system promising in addressing related theoretical problems and practical applications.     

一维有机微纳米光功能材料研究进展

近年来,一维有机小分子微纳材料因为其新颖的光学性能和在未来小型化器件中的广泛应用,受到了人们越来越多的关注.相比于传统无机半导体材料,有机小分子材料具有结构多样性、功能可设计性、易大量制备、易机械加工等显著优势.本文将从一维有机小分子纳米材料的制备方法、形貌调控、光学性能(如光波导、受激发射、电致发光等),及其在光学器件上的应用出发,对近十年来的相关研究进展及成果进行总结和介绍.     

Transport and separation of small organic molecules through nanotubules.

An electroless plating method was applied to deposit Au onto the surfaces and the walls of pores of polycarbonate membranes to prepare gold nanotubules. The nanotubules were modified with cysteine (Cys) or with carbamidine thiocyante (Gua). The effects of modifiers and of the fine structure of organic molecules on the transport properties of those molecules through the gold nanotubules were investigated. Studies show that the hydrophilicity of modifiers and the planar structure of permeating molecules clearly affect the transport of small organic molecules in gold nanotubules. Tryptophan (Try) and vitamin B(2) (VB(2)) was cleanly separated at pH 6.8.     

DFT and TD-DFT calculation of new thienopyrazine-based small molecules for organic solar cells

Background

Novel six organic donor-π-acceptor molecules (D-π-A) used for Bulk Heterojunction organic solar cells (BHJ), based on thienopyrazine were studied by density functional theory (DFT) and time-dependent DFT (TD-DFT) approaches, to shed light on how the π-conjugation order influence the performance of the solar cells. The electron acceptor group was 2-cyanoacrylic for all compounds, whereas the electron donor unit was varied and the influence was investigated.

Methods

The TD-DFT method, combined with a hybrid exchange-correlation functional using the Coulomb-attenuating method (CAM-B3LYP) in conjunction with a polarizable continuum model of salvation (PCM) together with a 6-31G(d,p) basis set, was used to predict the excitation energies, the absorption and the emission spectra of all molecules.

Results

The trend of the calculated HOMO–LUMO gaps nicely compares with the spectral data. In addition, the estimated values of the open-circuit photovoltage (V_oc) for these compounds were presented in two cases/PC₆₀BM and/PC₇₁BM.

Conclusion

The study of structural, electronics and optical properties for these compounds could help to design more efficient functional photovoltaic organic materials.

     

Effect of electron-withdrawing units on triphenylamine-based small molecules for solution-processed organic solar cells

Organic small molecules(TPA-BT3T,TPA-PT3T,and TPA-DFBT3T)using triphenylamine as a donor unit,terthiophene as a bridge,and benzo-2,1,3-thiadiazole(BT),[1,2,5]thiadiazolo[3,4-c]pyridine(PT)or 5,6-difluorobenzo[c][1,2,5]thiadiazole(DFBT)as an acceptor unit were designed and synthesized through Suzuki coupling reactions.These molecules exhibited good thermal stability with decomposition temperatures over 380°C and broad absorption from 300 to 700 nm.Photovoltaic devices were fabricated with these small molecules as donors and PC71BM as an acceptor.The TPA-BT3T based devices exhibited a power conversion efficiency of 2.89%,higher than those of the TPA-PT3T-and TPA-DFBT3T-based devices(1.34%and1.54%respectively).The effects of electron-withdrawing units on absorption,energy level,charge transport,morphology,and photovoltaic properties also were investigated.