Organocatalytic enantioselective acyl transfer onto racemic as well as meso alcohols, amines, and thiols

Acyl transfer is at the heart of functional-group transfers utilized both in nature and in the chemical laboratory. Acylations are part of the natural assembly machinery for the generation of complex molecules and for energy transport in biological systems. The recognition of covalent acyl-enzyme intermediates led to both mechanistic studies as well as the development of biomimetic approaches. Consequently, chemists first used the tools of nature in the form of enzymes and naturally occurring alkaloids as catalysts, before eventually developing a large variety of synthetic small molecules for selective acyl transfer. In contrast to nature, chemists utilize acylation reactions as a practical way for stereoselection and functional-group protection. Indeed, the number of studies concerning acyl transfer has significantly increased over the last 15 years. This Review examines and highlights these recent developments with the focus as given in the title.     

Ferrocene embedded in an electrode-supported hybrid lipid bilayer membrane: a model system for electrocatalysis in a biomimetic environment

An electrode-supported system in which ferrocene molecules are embedded in a hybrid bilayer membrane (HBM) has been prepared and characterized. The redox properties of the ferrocene molecules were studied by varying the lipid and alkanethiol building blocks of the HBM. The midpoint potential and electron transfer rate of the embedded ferrocene were found to be dependent on the hydrophobic nature of the electrolyte and the distance at which the ferrocene was positioned in the HBM relative to the electrode and the solution. Additionally, the ability of the lipid-embedded ferrocenium ions to oxidize solution phase ascorbic acid was evaluated and found to be dependent on the nature of the counterion.     

Polymerization of Cyclic Imino Ethers. X. Kinetics,Chain Transfer,and Repolymerization

The main conclusions in studies on polymerization catalysts and the nature of chain transfer in the polymerization of cyclic imino ethers were that there is extensive chain transfer in the 2-alkyl oxazolines to produce polymer with a reactive end. Toward the end of polymerization, these chain-transferred molecules repolymerize back on the active center producing a multibranched star polymer. A theory for the data was developed.     

Ultrathin polymer film formation by collision-induced cross-linking of adsorbed organic molecules with hyperthermal protons

A new synthetic approach for the formation of ultrathin polymer films with customizable properties was developed. In this approach, the kinematic nature of proton collisions with simple organic molecules condensed on a substrate is exploited to break C-H bonds preferentially. The subsequent recombination of carbon radicals gives a cross-linked polymer thin film, and the selectivity of C-H cleavage preserves the chemical functionalities of the precursor molecules. The nature and validity of the method are exemplified with theoretical results from ab initio molecular dynamics calculations and experimental evidence from a variety of characterization techniques. Its applicability is demonstrated by the synthesis of ultrathin polymer films with precursor molecules such as dotriacontane, docosanoic acid, poly(acrylic acid) oligomer, and polyisoprene. The approach is fundamentally different from conventional chemical synthesis as it involves an unusual mix of physical and chemical processes including charge exchange, projectile penetration, kinematics, collision-induced dissociation, inelastic energy transfer, chain transfer, and chain cross-linking.     

Semiempirical prediction of the hyperpolarizabilities for cyanovinyl-substituted donor-acceptor molecules

We present here a systematically theoretical study on the nonlinearities and their structure-property relationship of cyanovinyl-substituted donor-acceptor molecules by virtue of semiem-pirical PM3/AM1-FF approach.Good consistency between measured and calculated hyperpolarizabil-ities is obtained.Results show that conformation has a significant effect on hyperpolarizabilities.The torsion angle change between two conjugated parts of the molecular systems can substantially alter the nonlinearities.The total amount of charge transfer difference from donor to acceptor has been introduced to understand the microscopic nature of the nonlinear optical properties for the title molecules.General guidelines may be sought out in the search of molecules with large values of β Some molecules with large molecular hyperpolarizabilities can be predicted by the optimization for the longer π-electron systems with both acceptor and donor groups.     

Evaluation of dialysis as a technique for the removal of lipids prior to the GC determination of ortho- and non-ortho-chlorobiphenyls, using 14C-labelled congeners.

Dialysis was evaluated as a non-destructive clean-up technique to isolate chlorobiphenyls (CBs) from fish-oil prior to further analysis. 14C-CBs were used to study the transfer processes of the CBs across polyethylene membranes. Single step processes using equilibrium dialysis were compared to a dynamic method of refluxing solvent. The dynamic method reduced the duration of the separation to 8 h. The transfer of CBs and the lipids was dependent on temperature and nature of the analyte with smaller molecules being dialysed substantially faster than larger molecules. An optimised dynamic method was used to compare the dialytic clean-up with a traditional method using sulfuric acid-impregnated silica for the determination of CBs in a laboratory reference material. Labelled recovery standards for each individual congener are recommended in combination with dialysis as a method for clean-up.     

Theoretical study of one-, two-, and three-photon absorption properties for a series of Y-shaped molecules

In this paper, the equilibrium geometries, one-, two-, and three-photon absorption properties, and the transition nature of a series of Y-shaped molecules which possess an imidazole-thiazole core have been theoretically studied by using the parametrization model 3 and Zerner's intermediate neglect of differential overlap methods. Our calculated results have confirmed the experimental findings that the investigated molecules are all promising multiphoton absorption materials and both the two-photon absorption and the three-photon absorption cross sections are seriatim increscent along with the increase of the electron-donor strength. The nonlinear optical phenomenon originates from the intramolecular charge transfer within the pi-conjugated system. The calculated results indicate that the heterocyclic core increases the two- and three-photon absorption cross sections due to its pi-excessive nature. So it can provide more free electrons to enlarge the charge transfer within the molecule system. In addition, the design of Y shape and the sulfonyl-based electron-accepting group play a part in the enhancement of multiphoton absorption. It is notable that molecules with heterocyclic core will provide favorable condition for multiphoton absorption applications.     

Ion permeability of SAMs on nanoparticle surfaces

This article reports on the ion permeability of self-assembled monolayers (SAMs) formed on the surface of charged alkanethiol-protected gold nanoparticles, so-called monolayer-protected clusters (MPCs). The capacitance and thus the charging energy required to add/remove an electron from the metal core are extremely sensitive to ions entering the monolayer, and the extent of ion penetration can be tuned by the charge and size of the ions and the permittivity of the solvent. Experimentally, this effect is comparable to ion association with conventional redox molecules, indicating that MPCs despite their large size and the fundamentally differing nature of the electron transfer process can be treated analogously to redox molecules.     

Electronic states of π complexes of <Emphasis Type="Italic">d</Emphasis><Superscript>0</Superscript> early transition metals and energy transfer to unsaturated hydrocarbons

The orbital nature of excited states of organometallic π-complexes of early transition metals of the third-fifth periods with the d ⁰ electronic configuration was surveyed, and their photophysical characteristics were discussed. Examples of long-lived luminescence generated by ligand-to-metal charge transfer in liquid solutions at room temperature were thoroughly considered. Regularities of nonradiative triplet-triplet energy transfer from aromatic molecules and d ⁰ metallocene complexes of Group 4B transition metals to unsaturated hydrocarbons were examined.     

Multilevel and density functional electronic structure calculations of proton affinities and gas-phase basicities involved in biological phosphoryl transfer

Five multilevel model chemistries (CBS-QB3, G3B3, G3MP2B3, MCG3/3, and MC-QCISD/3) and seven hybrid density functional methods (PBE0, B1B95, B3LYP, MPW1KCIS, PBE1KCIS, and MPW1B95) have been applied to the calculation of gas-phase basicity and proton affinity values for a series of 17 molecules relevant to the study of biological phosphoryl transfer. In addition, W1 calculations were performed on a subset of molecules. The accuracy of the methods was assessed and the nature of systematic errors was explored, leading to the introduction of a set of effective bond enthalpy and entropy correction terms. The multicoefficient correlation methods (MCG3/3 and MC-QCISD), with inclusion of specific zero-point scale factors, slightly outperform the other multilevel methods tested (CBS-QB3, G3B3, and G3MP2B3), with significantly less computational cost, and in the case of MC-QCISD, slightly less severe scaling. Four density functional methods, PBE1KCIS, MPW1B95, PBE0, and B1B95 perform nearly as well as the multilevel methods. These results provide an important set of benchmarks relevant to biological phosphoryl transfer reactions.     

DFT study of the monomers and dimers of 2-pyrrolidone: equilibrium structures, vibrational, orbital, topological, and NBO analysis of hydrogen-bonded interactions

A computational study of the monomers and hydrogen-bonded dimers of 2-pyrrolidone was executed at different DFT levels and basis sets. The above dimeric complexes were treated theoretically to elucidate the nature of the intermolecular hydrogen bonds, geometry, thermodynamic parameters, interaction energies, and charge transfer. The processes of dimer formation from monomers and concerted reactions of double proton transfer were considered. The evolution of geometry, vibrational frequencies, charge distribution, and AIM properties in going from monomers to dimers was systematically followed. The solvent effects upon dimer formation were investigated in terms of the self-consistent reaction field (SCRF Onsager model). For the monomers and three dimers, vibrational frequencies were calculated and the changes in frequencies of the vibrations most sensitive to complexation were discussed. The orbital interactions were shown to lengthen the X-H (X = N, O) bond and lower its vibrational frequency (a red shift). To better understand the nature of the corresponding intermolecular interactions, we performed natural bond orbital (NBO) analysis. Topological analysis of electron density at bond critical points (BCP) was executed for complex molecules using the Bader's atoms in molecules (AIM) theory. The interaction energies were calculated, and the basis set superposition errors (BSSE) were estimated systematically. Satisfactory correlations between the structural parameters, interaction energies, and electron density characteristics at BCP were found.     

The role of reaction force and chemical potential in characterizing the mechanism of double proton transfer in the adenine-uracil complex

A theoretical study of the intermolecular double proton transfer in the adenine-uracil base pair has been performed to model the double proton transfer in the adenine-thymine dimer. The mechanism is analyzed in terms of the reaction force profile, which indicates that the activation of the transfer occurs via structural rearrangements to bring the interacting molecules close to each other to let the donor and acceptor atoms in the right position to achieve the transfer. It is found that only when the first proton transfer is partially completed does the second proton get activated, thus illustrating the asynchronous nature of the double proton-transfer process in base pair systems.     

Theoretical Studies on the Dihydrogen Bonding Between Shortchain Hydrocarbon and Magnesium Hydride

The C--H…H dihydrogen-bonded complexes of methane, ethylene, acetylene, and their derivatives with magnesium hydride were systematically investigated at MP2/aug-cc-PVTZ level. The results confirm that the strength of dihydrogen bonding increases in the following order of proton donors： C（sp3）-H〈C（sp2）-H〈C（sp）-H and chlorine substituents enhance the C-H…H interaction. In the majority of the complexes with a cyclic structure, the Mg-H proton-accepting bond is more sensitive to the surroundings than C-H proton-donating bond. The nature of the electrostatic interaction in these C-H…H dihydrogen bonds was also unveiled by means of the atoms in mo- lecules（AIM） analysis. The natural bond orbital（NBO） analysis suggests that the charge transfer in the cyclic com- plexes is characteristic of dual-channel. The direction of the net charge transfer in the cyclic complexes is contrary to that previously found in dihydrogen bonded systems.     

Voltammetry at a liquid–liquid interface supported on a metallic electrode

A liquid–liquid interface supported on a metallic electrode has been used to study ion transfer (IT) and electron transfer (ET) reactions by cyclic voltammetry. The system is composed of an aqueous droplet supported on a platinum disc electrode and immersed into an organic electrolyte solution. Depending on the nature of the dissolved species present in the aqueous solution, and in the organic electrolyte solution, different electrochemical coupled reactions can be observed. This method enables a fast and convenient method to measure standard transfer potentials for example of ionised drug molecules.     

Phase transfer of silver nanoparticles from aqueous to organic solutions using fatty amine molecules

We demonstrate the phase transfer of silver nanoparticles synthesized in an aqueous medium into hexane containing the cationic surfactant octadecylamine (ODA). During vigorous shaking of the biphasic mixture, rapid phase transfer of the silver nanoparticles into the organic phase was observed. The phase transfer of the silver nanoparticles arises due to coupling of the silver nanoparticles with the ODA molecules present in organic phase via either coordination bond formation or weak covalent interaction. This process renders the nanoparticles sufficiently hydrophobic and dispersible in the organic phase. The ODA-stabilized silver nanoparticles could be separated out from the organic phase in the form of a powder and are readily redispersible in different organic solvents. The nature of binding of the ODA molecules to the silver nanoparticle surface was characterized using UV-vis spectroscopy, thermogravimetry, transmission electron microscopy, nuclear magnetic resonance spectroscopy, X-ray photoemission spectroscopy, and Fourier transform infrared spectroscopy.     

Supported liquid membranes (SLM) for recovery of bismuth from aqueous solutions

In this study, the extraction of Bi(III) from synthetic solutions of 2 M H₂SO₄/0.5 M HCl by supported liquid membranes (SLM) using tri-n-octylphosphine oxide (Cyanex 921) as extractant is reported. First, the nature of the Bi(III)/Cyanex 921 solvates extracted to organic phase (in a solvent extraction system) was determined by the slope method. It was found that Bi(III) reacts with 2 molecules of Cyanex 921 to form the solvate BiCl₃·2Cyanex 921. In the recovery of Bi(III) by the SLM system, parameters that influence extraction efficiency were evaluated, including: support, feed solution and stripping solution nature, and extractant concentration in the organic phase which impregnates the support. Results indicate that Cyanex 921 dissolved in kerosene is not able to extract Bi(III) from H₂SO₄ media. Moreover, transfer of H₂SO₄ was observed. HCl addition to the feed solution up to a maximum concentration of 0.5 M increases Bi(III) extraction. Further increase in HCl concentration causes a decrease in Bi(III) transfer. Likewise, the concentration of Cyanex 921 in the SLM organic phase which produced the maximum Bi(III) extraction was found to be 0.3 M. The performance of H₂O and 0.2 M H₂SO₄ as stripping solutions was evaluated, and it was found that only H₂SO₄ enabled Bi(III) transfer.     

Effects of silver nanoparticles doping on morphology and luminescence behaviour of ferroelectric liquid crystals Langmuir–Blodgett films

We report the deposition of Langmuir–Blodgett (LB) thin films of low-weight dispersed composite systems of ferroelectric liquid crystals (FLCs)–functionalised silver (Ag) nanoparticles. Because of their amphiphilic nature the molecules form stable Langmuir monolayers, which were transferred to silicon substrates. We noticed that absorption wave numbers are present for each bond constituting FLC–nanoparticles composite system, ensuring a complete transfer of molecules from water sub-phase. XRD showed intense peaks at 2θ = 3.2° due to the layer structure of FLC molecules. We infer from the morphology of LB films that doping of nanoparticles do not provide any hindrance to SmC* layer structure of FLC molecules. The photoluminescence study indicates blue shift in emission spectra and peak intensity increases with Ag nanoparticles concentration.     

Composition,structure and substrate properties of reconstituted discoidal HDL with apolipoprotein A-I and cholesteryl ester

To investigate the influence of lipid unsaturation and neutral lipid on the maturation of high density lipoproteins, the discoidal complexes of apoA-I, phosphatidylcholine and cholesteryl ester (CE) were prepared. Saturated dipalmitoylphosphatidylcholine (DPPC) and unsaturated palmitoyllinoleoylphosphatidylcholine (PLPC), palmitoyloleoylphosphatidylcholine (POPC), and fluorescent probe cholesteryl 1-pyrenedecanoate (CPD) that forms in a diffusion- and concentration-dependent manner short-lived dimer of unexcited and excited molecules (excimer) were used. The apoA-I/DPPC/CPD complexes were heterogeneous by size, composition and probe location. CPD molecules incorporated more efficiently into larger complexes and accumulated in a central part of the discs. The apoA-I/POPC(PLPC)/CPD were also heterogeneous, however, probe molecules distributed preferentially into smaller complexes and accumulated at disc periphery. The kinetics of CPD transfer by recombinant cholesteryl ester transfer protein (CETP) to human plasma LDL is well described by two-exponential decay, the fast component with a shorter transfer time being more populated in PLPC compared to DPPC complexes. The presence of CE molecules in discoidal HDL results in particle heterogeneity. ApoA-I influences the CETP activity modulating the properties of apolipoprotein–phospholipid interface. This may include CE molecules accumulation in the boundary lipid in unsaturated phosphatidylcholine and cluster formation in the bulk bilayer in saturated phosphatidylcholine.     

2H NMR studies of phase behaviour and molecular motions of doped discotic liquid-crystalline systems

A discotic triphenylene monomer as well as a dimer and a main chain polymer, all substituted with heptyloxy side groups, were doped with an electron acceptor (2,4,7-trinitrofluorenone (TNF)) to give charge transfer complexes. These doped systems were aligned in a magnetic field, thus proving their liquid crystallinity. ²H NMR measurements show that the electron acceptor molecules are incorporated into the columns built of triphenylene cores. In the charge transfer complex with the triphenylene monomer almost all the electron acceptor molecules stack in the columns even close to the clearing temperature T₁, while for the dimer and especially for the polymer a significant fraction of the TNF molecules exhibits isotropic motion, which is attributed to their location in the region between the columns, already way below T₁. This isotropically distributed part increases on approaching T₁. Fast rotation of the discs around their column axes takes place in the monomer and is quenched in the dimer and the polymer, due to the interlinking of the columns by the spacer. The electron acceptor molecules, on the other hand, exhibit free rotation in all samples, even in the charge transfer complexes with the triphenylene dimer and polymer. In the side group labelled triphenylenes increased ²H NMR spectral narrowing is detected in the charge transfer complex samples compared with the corresponding pure triphenylenes. This indicates higher side group mobility in the doped systems, since the incorporation of TNF molecules increases the spacing between the discotic units.     

PVK与新型D-π-A分子掺杂体系的能量转移及发光性质

通过对PVK与4种新型D-π-A分子(分别简写为CKD, TKD, PKD, NKD)掺杂体系的吸收光谱、激发光谱和光致发光光谱的研究, 分析了掺杂体系的光致发光特性和能量转移现象. 制备了结构为ITO/PEDOT/PVK∶D-π-A ω/Alq3/Al的电致发光器件, 研究了掺杂体系的电致发光性能. 研究结果表明, 通过改变D-π-A分子中不同给电子能力的电子给体, 可以调控其带隙, 进而实现对D-π-A分子发光峰位的调节; 给电子基团空间立构效应越高, 其荧光量子效率越高. 在掺杂体系的光致发光和电致发光中, PVK与D-π-A分子之间都发生了有效的能量转移, 通过调节PVK与D-π-A分子的比例, 可以调节掺杂体系的发光性能. 当TKD在PVK中的掺杂质量分数为6％时, 电致发光器件发光亮度为729.1 cd/m2时, 发光效率达到1.75 cd/A.