Theoretical studies on the reaction mechanism of palladium(0)-catalyzed addition of thiocyanates to alkynes

The reaction mechanism of the Pd(0)-catalyzed alkyne cyanothiolation reaction is investigated by MP2, CCSD(T) and the density functional method B3LYP. The overall reaction mechanism is examined. The B3LYP results are consistent with the results of CCSD(T) and MP2 methods for the isomerization, acetylene insertion and reductive elimination steps, but not for the oxidative addition step. For the oxidative addition, the bisphosphine and monophosphine pathways are competitive in B3LYP, while the bisphosphine one is preferred for CCSD(T) and MP2 methods. The electronic mechanisms for the oxidative addition of thiocyanate HS-CN to Pd(PH(3))(2) and Pd(PH(3)) and for the acetylene insertion into Pd-S and Pd-CN are discussed in terms of the electron-donation and back-donation. The chemo-selectivity that acetylene inserts into the Pd-S bond rather than into the Pd-CN bond is due to the involvement of the S p orbital. It is the doubly occupied S p unhybridized orbital that donates an electron to the alkylene pi* anti-bonding orbital, which makes insertion into Pd-S bond more favorable than into the Pd-CN bond. During the insertion into the Pd-S bond, the S sp(2) hybrid orbital and unhybridized p orbital transform into each other, while the C sp hybrid orbital shifts its direction for insertion into Pd-CN bond. By using the monosubstituted acetylenes (CN, Me and NH(2)), the influence of substituents at acetylene on the chemo- and regio-selectivities is analyzed.     

Application of thermal analysis to the study of lipidic prodrug incorporation into nanocarriers

Anti HIV molecules as numerous drugs cannot efficiently penetrate into the brain. Prodrug synthesis and encapsulation into pegylated nanocarriers have been proposed as an approach for brain delivery. Pegylated polymeric nanoparticles and liposomes were chosen to incorporate glycerolipidic prodrugs of didanosine. Differential scanning calorimetry experiments were performed on mixtures of prodrugs and lipids or polymer in order to study their interaction. The optimal incorporation ratios were determined for each prodrug and compared for both types of nanocarriers. All these results would be used to prepare optimised formulations of didanosine prodrugs loaded into pegylated nanocarriers for brain drug delivery.     

Role of acidity on the electrochemistry of Prussian Blue at plain and Nation filmcoated electrodes

Prussian Blue (PB) coated on plain platinum (Pt) shows a redox wave at 0.44V vs SCE in addition to the two usual redox waves at 0.82 and 0.12 V vs SCE when the electrodes were dipped in acidic KC1 solution. PB incorporated into Nation film-coated on Pt electrode exhibited the same behaviour even in the presence of neutral KG solution. In acidic KC1, the additional redox wave observed for PB incorporated into Nation film shifted positively to 0.39V vs SCE and the peak separation was reduced to 30mV. The observed additional redox wave for PB coated on plain Pt electrode and incorporated into Nafion film-coated Pt electrodes was assigned to the partial reduction of PB occurring due to the insertion of protons into the film. The effect of various cations on the electrochemistry of PB incorporated into Nafion film-coated electrode was also studied.     

Application of computer simulation free-energy methods to compute the free energy of micellization as a function of micelle composition. 2. Implementation

In this paper, the implementation of the CS-FE/MT model introduced in article 1 is discussed, and computer simulations are performed to evaluate the feasibility of the new theoretical approach. As discussed in article 1, making predictions of surfactant/solubilizate aqueous solution behavior using the CS-FE/MT model requires evaluation of DeltaDeltaG for multiple surfactant-to-solubilizate or surfactant-to-cosurfactant transformations. The central goal of this article is to evaluate the quantitative accuracy of the alchemical computer simulation method used in the CS-FE/MT modeling approach to predict DeltaDeltaG for a single surfactant-to-solubilizate or for a single surfactant-to-cosurfactant transformation. A hybrid single/dual topology approach was used to morph the ionic surfactant sodium dodecyl sulfate (SDS) into the ionic solubilizate ibuprofen (IBU), and a dual topology approach was used to morph the nonionic surfactant octyl glucoside (OG) into the nonionic solubilizate p-aminobenzoate (PAB). In addition, a single topology approach was used to morph the nonionic surfactant n-decyl dimethylphosphine oxide (C10PO) into the nonionic cosurfactant n-decyl methyl sulfoxide (C10SO), the nonionic surfactant octylsulfinyl ethanol (C8SE) into the nonionic cosurfactant decylsulfinyl ethanol (C10SE), and the nonionic surfactant n-decyl methyl sulfoxide (C10SO) into the nonionic cosurfactant n-octyl methyl sulfoxide (C8SO). Each DeltaDeltaG value was computed by using thermodynamic integration to determine the difference in free energy associated with (i) transforming a surfactant molecule of type A into a cosurfactant/solubilizate molecule of type B in a micellar environment (referred to as DeltaG2) and (ii) transforming a surfactant molecule of type A into a cosurfactant/solubilizate molecule of type B in aqueous solution (referred to as DeltaG1). CS-FE/MT model predictions of DeltaDeltaG for each alchemical transformation were made at a number of simulation conditions, including (i) different equilibration times at each value of the coupling parameter lambda, (ii) different data-gathering times at each lambda value, and (iii) simulation at a different number of lambda values. For the three surfactant-to-cosurfactant transformations considered here, the DeltaDeltaG values predicted by the CS-FE/MT model were compared with DeltaDeltaG values predicted by an accurate molecular thermodynamic (MT) model developed by fitting to experimental CMC data. Even after performing lengthy equilibration and data gathering at each lambda value, physically unrealistic values of DeltaDeltaG were predicted by the CS-FE/MT model for the transformations of SDS into IBU and of OG into PAB. However, more physically realistic DeltaDeltaG values were predicted for the transformation of C10PO into C10SO, and reasonable free-energy predictions were obtained for the transformations of C8SE into C10SE and C10SO into C8SO. Each of the surfactant-to-cosurfactant transformations considered here involved less extensive structural changes than the surfactant-to-solubilizate transformations. As computer power increases and as improvements are made to alchemical free-energy methods, it may become possible to apply the CS-FE/MT model to make accurate predictions of the free-energy changes associated with forming multicomponent surfactant and solubilizate micelles in aqueous solution where the chemical structures of the surfactants, cosurfactants, and solubilizates differ significantly.     

Separation of the molecular species of diacyl and alkenylacyl subclasses of the methyl ester of dinitrophenylethanolamine glycerophospholipid by high-performance liquid chromatography

A high-performance liquid chromatographic (HPLC) procedure for the separation of the molecular species of alkenylacyl and diacyl subclasses after the derivatization of ethanolamine glycero-phospholipids (EGP) to the methyl ester of the dinitrophenylated lipids is described. Methyl esters of dinitrophenylethanolamine glycerophospholipids were first separated into alkenylacyl, alkylacyl and diacyl subclasses by thin-layer chromatography, then each subclass was separated into individual molecular species by reversed-phase HPLC. By converting the EGP into UV-absorbing derivatives, it proved possible to utilize the specificity of spectrophotometric detection for the determination of the individual molecular species. Alkenylacyl and diacyl derivatives were resolved into fifteen to twenty different species in a single HPLC run. The method should facilitate studies on the metabolism of the polar head group of both molecular species of alkenylacyl and diacyl glycerophosphoethanolamine in a variety of tissues using radioactive precursors.     

Efficiency of layered double hydroxide nanoparticle-mediated delivery of siRNA is determined by nucleotide sequence

In this paper, we report the novel finding that the cellular delivery efficiency of siRNAs or their mimic double-stranded (ds)DNA using layered double hydroxide (LDH) nanoparticles is dependent upon the nucleotide sequence. Efficacy of LDH-mediated delivery of four different siRNAs into cortical neurons and NIH 3T3 cells was found to vary widely (from 6 to 80%, and 2-11%, respectively). Our investigation into the formation of dsDNA-LDH complexes through monitoring the dsDNA:LDH mass ratio at the point of zero charge (PZC) indicated that the degree of intercalation of the individual dsDNA sequences into the LDH nanoparticles varied significantly. The dsDNA:LDH mass ratio at the PZC was found to be dependent on the nucleotide sequence. We further observed that PZC for each sequence was positively related to the extent of LDH-mediated internalization of the equivalent siRNA into neurons and fibroblasts. This novel finding therefore suggests that the mass ratio at the PZC is a useful predictive tool with which to assess the intercalation efficiency of selected siRNA sequences into the LDH interlayer and subsequent internalization into the cell cytoplasm. This finding will allow a more controlled approach to the design of suitable siRNA sequences for LDH-mediated siRNA delivery.     

The use of formamidine protection for the derivatization of aminobenzoic acids

N,N-Dimethylformamidine and novel N,N-diisopropylformamidine protecting groups were used to carry out a one-pot conversion of aminobenzoic acids into the corresponding amides. General conditions for an in situ transformation of aminobenzoic acids and their heterocyclic analogues into the corresponding formamidine-protected acid chlorides were developed. These chlorides were used in reactions with amines, including poorly reactive anilines. The protected amides were then smoothly deprotected by heating with ethylenediamine derivatives, resulting in a general procedure for the one-pot transformation of aminobenzoic acids into their amides. Our one-pot procedure was successfully applied to the preparation of several compounds of pharmaceutical interest.     

Thermoplasticization of wood. I. Benzylation of wood

A study of converting wood into thermoplastic materials was undertaken to develop a new technique in effective utilization of wood wastes. Thermoplasticizatoin of wood carried out by means benzylation. Various reaction parameters, such as alkalinity of reaction media, reaction temperature, and time were taken into account to produce benzylated wood with different degrees of substitution (based on weight gain) FTIR, DSC, DMTA, SEM and x-ray crystallography were used to characterize the chemical and mechanical properties of benzylated wood. Experimental data showed that preswelling and reaction temperature had critical effects on benzylation reaction. Lignin in wood appeared to inhibit benzylation but extractives had little effect. Different species showed some variation in reaction rates. The thermoplasticized wood exhibited good melting properties and were readily molded into bulk materials or extruded into films and sheets. A wide range of glass transition temperatures from 66 to 280°C for the benezylatedwoods was achieved, and they were larely dependent on the weight gain. The molded and extruded products exhibited acceptable mechanical strength for structural engineering applications. The property and structure relationship for the thermoplasticized wood were discussed     

Room-temperature cold-welding of gold nanoparticles for enhancing the electrooxidation of carbon monoxide

A cold-welding strategy is proposed to rapidly join together Au nanoparticles (AuNPs) into two-dimensional continuous structures for enhancing the electrooxidation of carbon monoxide by injecting a mixture of ethanol and tolulene into the bottom of a AuNP solution.     

Method for Measuring the Combustion Heat of Natural Gas with Isothermal Calorimeter

Factors that are to be taken into account in developing a calorimetric technique are considered. The possible deviations of temperatures at the inlet and outlet of gases in the calorimeter from the nominal values are evaluated and an example of such estimate is given for the case of methane burning in batch and continuous operation modes. The necessity for taking into account the humidity of gases fed into the calorimeter burner is demonstrated. The proposed method was used to perform absolute measurements of the combustion heat of methane.     

Cryolite precipitation by the Reaction of aluminium salt with sodium fluoride in aqueous solution

When aqueous solution of aluminium salt involving nitrate, chloride or sulfate was added into sodium fluoride solution, an immediate reaction occured to form cryolite-like precipitate. Examination into the resultant solution and analysis for the precipitate were carried out, leading to the fact that fluorine ion can substitute for bound water molecules around central Al⁺⁺⁺ ion, but hardly for bound hydroxide and sulfate ion which should go or be “frozen”, as it is, into cryolite-like precipitate. These ligand substitution reaction seems to contribute to identification of ion species of aluminium in aqueous solution.     

Modification of films of heat-resistant polyimides by adding hydrosilicate and carbon nanoparticles of various geometries

The possibility of modifying the properties of poly(4,4′-oxydiphenylene)pyromellitimide films by introducing into prepolymer solutions nanoparticles of various compositions and structures [hydrosilicate nanoparticles in the form of layered structures (montmorillonite) and nanotubes; carbon nanofibers] was examined. New intercalating agents, tetranuclear aromatic diamines, were suggested for pretreatment of montmorillonite prior to introduction into heat-resistant polymers. The mechanical characteristics of the nanocomposites with hydrosilicate nanotubes can be optimized by chemical pretreatment of the nanotubes prior to introduction into the polymer matrix. Introduction of the above-named nanoparticles into the polymer matrix appreciably increases the elastic modulus of the material. The largest increase in the elastic modulus is observed with hydrosilicate nanotubes of the chrysotile structure, coated with an aromatic modifier.     

Theory of laser-induced two-step electron-ion recombination

A theoretical framework for the quantitative interpretation of laser-induced electron-ion recombination is presented in terms of the density matrix taking into account stochastic bandwidth and pulse duration of the laser. The theory deals with recombination induced from the continuum into one group of states by one laser and further stabilized into a lower group of states by a second laser. Rate equations are then derived from the complete density matrix, and the conditions for their validity are discussed. Both density matrix and rate equations are applied to the interpretation of a recent experiment with equally good agreement.     

Hydrodynamic control of droplet division in bifurcating microchannel and its application to particle synthesis

We describe herein a microfluidic system for active and precise control of droplet division at a bifurcation point in a microchannel. Water-in-oil or oil-in-water droplets, which were initially formed at a T-junction, were introduced into the bifurcation point, and then divided into two daughter droplets. By continuously introducing 'tuning flow' into the downstream of one of the branch channels, and by controlling the flow rates distributed into the two branch channels, the sizes of the daughter droplets could be precisely tuned. The ratio of the volumetric flow rates into the branch channels was estimated by regarding the microchannel network as a resistive circuit. In addition, we performed synthesis of monodispersed polymer particles with controlled sizes utilizing the presented system. The ability to hydrodynamically control the droplet sizes will open new possibilities not only for producing useful emulsions, but also for conducting controlled chemical and biochemical reactions in a confined space.     

Continuous introduction of powdered samples in emission spectroscopy The use of a tube-electrode

A device for the continuous introduction of powdered samples into spark and arc sources is described. The sample is pushed by a motor-driven spindle into the electrode gap through a tubular electrode. The method was found to be simple and versatile.     

Investigation of the functionality of different burner types used for the Wickbold decomposition method

The functionality of different burner types used for the Wickbold decomposition method was investigated to understand the low recovery rate problem. The elements chlorine and sulphur were the subject of recovery experiments. The influence of the amount of sample transported into the oxyhydrogen flame on the efficiency of combustion is presented. The difference between the manner of transportation into the flame, direct nebulisation of liquids or previous evaporation are investigated. A new nebuliser for introducing liquids into the oxyhydrogen flame with an evaporation step was developed to reduce decomposition problems. Received: 6 November 1996 / Revised: 16 December 1996 / Accepted: 3 January 1997     

Characterization of solvation properties of lipid bilayer membranes in liposome electrokinetic chromatography

The nature of solute interactions with biomembrane-like liposomes, made of naturally occurring phospholipids and cholesterol, was characterized using electrokinetic chromatography (EKC). Liposomes were used as a pseudo-stationary phase in EKC that provided sites of interactions for uncharged solutes. The retention factors of uncharged solutes in liposome EKC are directly proportional to their liposome-water partition coefficients. Linear solvation energy relationship (LSER) models were developed to unravel the contributions from various types of interactions for solute partitioning into liposomes. Size and hydrogen bond acceptor strength of solutes are the main factors that determine partitioning into lipid bilayers. This falls within the general behavior of solute partitioning from an aqueous into organic phases such as octanol and micelles. However, there exist subtle differences in the solvation properties of liposomes as compared to those of octanol and various micellar pseudo-phases such as aggregates of sodium dodecyl sulfate (SDS), sodium cholate (SC), and tetradecylammonium bromide (TTAB). Among these phases, the SDS micelles are the least similar to the liposomes, while octanol, SC, and TTAB micelles exhibit closer solvation properties. Subsequently, higher correlations are observed between partitioning into liposomes and the latter three phases than that into SDS.     

Development of a simple HPLC method for determination of paeoniflorin-metabolizing activity of intestinal bacteria in rat feces

A simple and reproducible HPLC method for the determination of paeoniflorin (PF)-metabolizing activity of intestinal bacteria in rat feces was developed and validated. Orally administered PF, a major active constituent of Paeoniae Radix, is metabolized into a bioactive compound, paeonimetabolin I (PM-I) by intestinal bacteria. Direct determination of the PF-metabolizing rate into PM-I is hard to achieve by HPLC due to the lack of intense chromophore in PM-I. However, when PF was incubated with Lactobacillus brevis, an intestinal bacterium, in the presence of phenylmercaptan, the metabolizing rate of PF into 8-phenylthio-paeonimetabolin I (PT-PM-I) was found to be equivalent to that of PF into PM-I. Thus, the PF-metabolizing activity of intestinal bacteria in rat feces was determined by measuring the rate of biotransformation of PF into PT-PM-I, which was detected by HPLC at 255 nm. This method can be utilized in the biopharmaceutical study of traditional Chinese formulations containing Paeoniae Radix.     

Biomimetic fabrication of 3D structures by spontaneous folding of tapes

This paper describes a biomimetic strategy for the fabrication of 3D structures-including an electrically functional light detector-modeled on the folding of biological macromolecules into globular shapes. The process started by fabricating precursors to 3D, millimeter-sized structures using flexible polymer tapes. These tapes were patterned with metal features supporting liquid solder, crimped into strings of 3D corrugations, and attached to flat polymer tapes to generate linear 3D structures. Capillary interactions between droplets of molten solder on adjacent faces of the crimped tapes resulted in folding of the precursors into quasi-3D and truly 3D structures.     

Dramatic thermal stability of virus-polymer conjugates in hydrophobic solvents

We have developed a method for integrating the self-assembling tobacco mosaic virus capsid into hydrophobic solvents and hydrophobic polymers. The capsid was modified at tyrosine residues to display an array of linear poly(ethylene glycol) chains, allowing it to be transferred into chloroform. In a subsequent step, the capsids could be transferred to a variety of hydrophobic solvents, including benzyl alcohol, o-dichlorobenzene, and diglyme. The thermal stability of the material against denaturation increased from 70 °C in water to at least 160 °C in hydrophobic solvents. With a view toward material fabrication, the polymer-coated TMV rods were also incorporated into solid polystyrene and thermally cast at 110 °C. Overall, this process significantly expands the range of processing conditions for TMV-based materials, with the goal of incorporating these templated nanoscale systems into conductive polymer matrices.