Plasmon-assisted click chemistry at low temperature: an inverse temperature effect on the reaction rate

Plasmon assistance promotes a range of chemical transformations by decreasing their activation energies. In a common case, thermal and plasmon assistance work synergistically: higher temperature results in higher plasmon-enhanced catalysis efficiency. Herein, we report an unexpected tenfold increase in the reaction efficiency of surface plasmon-assisted Huisgen dipolar azide–alkyne cycloaddition (AAC) when the reaction mixture is cooled from room temperature to −35 °C. We attribute the observed increase in the reaction efficiency to complete plasmon-induced annihilation of the reaction barrier, prolongation of plasmon lifetime, and decreased relaxation of plasmon-excited-states under cooling. Furthermore, control quenching experiments supported by theoretical calculations indicate that plasmon-mediated substrate excitation to an electronic triplet state may play the key role in plasmon-assisted chemical transformation. Last but not least, we demonstrated the possible applicability of plasmon assistance to biological systems by AAC coupling of biotin to gold nanoparticles performed at −35 °C.

The decrease of reaction temperature can potentially lead to an increase of plasmon-assisted catalytic efficiency.     

Stereoselectivity reversal of a photochemical reaction in the solid state

The stereoselectivity of Norrish type II cyclobutanol formation resulting from photolysis of α-adamantyl-p-methoxyacetophenone is altered in favor of the more hindered cis isomer as the reaction medium is changed from isotropic liquid phases (benzene or acetonitrile) to the pure crystal. Based on the reactant X-ray crystal structure, it is suggested that the intermediate 1,4-biradical in the solid state is born in, and restricted to, a conformation which is ideal for direct closure to the more hindered product. In the relatively unrestricted solution environment, however, conformational isomerism of the biradical is faster than closure, thus leading to a predominance of the less hindered trans cyclobutanol.     

Novel photochemical reaction of indole with naphthalene and phenanthrene in the solid state

Irradiation of mixed crystals of indole and naphthalene gave an addition product, 1-(1,4-dihydro-1-naphthyl)indole ( ), while irradiation in solution gave another product in addition to . Similar solid-state photoreaction of indole and phenanthrene gave .     

In-situ measurement of photochemical changes of solid samples by fourier transform infrared photoacoustic spectroscopy

Infrared spectral changes of lithographic printing plates were measuredin-situ by PAS and RAS. The advantages of PAS over RAS were discussed for the spectral measurements of organic coatings on roughened metal surface.     

The influence of water on the photochemical reaction cycle of proteorhodopsin at low and high pH

Dried samples were prepared from suspension of proteorhodopsin. With HCl and NaOH the pH of the samples was adjusted below and above the pKa of the proton acceptor Asp-97, which was established earlier to be 7.1. Both types of samples were photoactive, and exhibited a truncated photocycle, compared to that measured in suspension. The photocycle of the low pH sample had a K like red shifted intermediate, decaying through an energized PR' intermediate to the ground state protein. The high pH sample had a more complex photocycle in which beside of the red shifted intermediate an M like intermediate could be identified, having a deprotonated Schiff-base. This blue shifted intermediate decays through an intermediate we designated PR', which is spectrally identical to the unphotolysed ground state. The humidity and temperature dependence of the photocycle in both cases was studied to understand the role of water in the function of the proteorhodopsin. The effects measured on proteorhodopsin were very similar to that measured earlier on bacteriorhodopsin.     

Effect of Lewis acids and low temperature initiators on the allyl transfer reaction involving phthalimido-N-oxyl radical

Previously, we reported allyl transfer reactions of allyl bromide and allyl phthalimido-N-oxyl substrates with hydrocarbons that result in CC bond formation. In both cases, efficient chain transfer processes along with high reaction yields were observed. Since PINO chemistry leads to an environmentally friendly method of hydrocarbon functionalization, additional studies were performed in order to improve the process. To expand the utility of this reaction, we carried out experiments to optimize reaction conditions and tested the effect of Lewis acids and low temperature initiators. Although allyl-PINO substrates reacted slightly slower than the bromides, the reactions were cleaner with little or no side products. The chain lengths for these reactions were compromised at lower temperatures, attributable to the high activation energy required for the hydrogen atom abstraction by PINO. The addition of a Lewis acid catalyst (AlCl₃) improves the product yield and reaction rate, possibly due to the formation of a PINO/AlCl₃ complex which lowers the activation energy for hydrogen abstraction step.     

The low temperature infrared spectrum of solid cyclopropylcyanide

The infrared spectrum of solid cyclopropyl cyanide at −196°C was recorded from 4000 to 400 cm⁻¹. The observed data are not in accord with an assignment of the normal vibrations suggested earlier. A few reassignments are proposed on the basis of the new infrared data and the results of a recent Raman study.     

Effect of reaction temperature and pH on structural and morphological properties of hydroxyapatite from precipitation method

Hydroxyapatite nanoparticle plays a significant role in the field of biomedical industries such as tissue engineering and regenerative medicine, carriers for drug delivery, photocatalyst, biosensors, and membranes for heavy metal removal from polluted water. The present work aims to synthesize the hydroxyapatite from bio-waste materials like cuttlefish bone using a precipitation method by changing reaction temperatures (room temperature, 60 °C, 70 °C, and 80 °C), and pH (9,10,11, and 12). The structure, particle size, and crystallinity of the obtained HAp were evaluated by XRD analysis. The functional groups present in the HAp nanoparticles were analyzed and confirmed by FTIR spectroscopy. The surface morphology of the particles was analyzed by using FESEM and the particle sizes were ranging from 40 to 160 nm for different pH values. The elemental composition was determined by EDAX analysis. The antibacterial activity of the sample was tested against gram-positive and gram-negative bacteria. The zone of inhibition value against gram-negative bacteria was found to be 20 ± 0.32 mm and 16 ± 0.18 mm against gram-positive bacteria for the sample with a pH value of 10. The obtained results confirmed that the optimized temperature, time, and pH are suitable for the preparation of HAp with excellent desired properties, which is employed as a better candidate for biomedical applications.     

Effect of structural stress on the intercalation rate of kaolinite

Particle size in kaolinite intercalation showed an inverse reactivity trend compared with most chemical reactions: finer particles had lower reactivity and some of the fine particles cannot be intercalated. Although this phenomenon was noted in the early 1960s and several hypotheses have been reported, there is no widely accepted theory about the unusual particle size response in the intercalation. We propose that structural stress is a controlling factor in the intercalation and the stress contributes to the higher reactivity of the coarser particles. In this study, we checked the structural deformation spectroscopically and indirectly proved the structural stress hypothesis. A Georgia kaolinite was separated into nine size fractions and their intercalations by hydrazine monohydrate and potassium acetate were investigated with X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) analyses. The apical Si-O band of kaolinite at 1115 cm(-1) shifted to 1124 cm(-1) when the mineral was intercalated to 1.03 nm by hydrazine monohydrate, and its strong pleochroic properties became much weaker. Similar reduction in pleochroism was observed on the surface OH bands of kaolinite after intercalation. Both the bending vibrations of the inner OH group at 914 cm(-1) and of the surface OH group at 937 cm(-1) shifted to 903 cm(-1) after intercalation by hydrazine. A new band for the inner OH group appeared at 3611 cm(-1) during the deintercalation of the 1.03 nm hydrazine kaolinite complex. Pleochroism change in the apical Si-O band suggested the tetrahedra had increased tilt with respect to the (001) plane. The tilt of the Si-O apical bond could occur only if the octahedra had also undergone structural rearrangement during intercalation. These changes in the octahedral and tetrahedral sheets represent some change in the manner of compensation for the structural misfit of the tetrahedral sheet and octahedral sheet. As the lateral dimensions of a kaolinite particle increases, the cumulative degree of misfit increases. Intercalation breaks the hydrogen bonds between layers and allows for the structure to reduce the accumulated stress in some other manner. The reversed size effect on intercalation probably was not caused by crystallinity differences as reported in the literature, because the Hinckley and Lietard crystallinity indices of the four clay fractions were very close to each other. Impurities, such as dickite- or nacrite-like phases are not significant in the studied sample as suggested by the XRD and IR results, they are not the main reasons for the lower reactivity of the finer particles.     

Mössbauer study on the photochemical reactions of pentacarbonyliron with ethene in low temperature nitrogen matrix

The UV-induced photochemical reactions of pentacarbonyliron with ethene in a low temperature nitrogen matrix were studied by means of the Mössbauer technique. Fe/CO/₄/C₂H₄/ was produced by UV-irradiation of penfacarbonyliron in close proximity to ethene molecules in a pure ethene matrix, or a homogeneous cocondensed matrix. The other products were obtained via thermal reactions with ethene of Fe/CO/₄ trapped in stratified matrices.     

Re-examination of the photochemical reaction of octaisopropylcyclotetragermane

The photochemistry of octaisopropylcyclotetragermane was studied by laser flash photolysis and trapping experiments. Upon irradiation of the cyclotetragermane, the main reaction was a ring opening to form octaisopropyltetragermane-1,4-diyl biradical (λ_max = 310 and 550 nm), but generations of diisopropylgermylene and tetraisopropyldigermene are negligible.     

Electron tunneling of photochemical reactions on metal surfaces: nonequilibrium Green's function-density functional theory approach to photon energy dependence of reaction probability

We have developed a theoretical model of photoinduced reactions on metal surfaces initiated by the substrate/indirect excitation mechanism using the nonequilibrium Green's function approach. We focus on electron transfer, which consists of (1) electron-hole pair creation, (2) transport of created hot electrons, and (3) tunneling of hot electrons to form an anion resonance. We assume that steps (1), (2), and (3) are separable. By this assumption, the electron dynamics might be restated as a tunneling problem of an open system. Combining the Keldysh time-independent formalism with the simple transport theory introduced by Berglund and Spicer, we present a practical scheme for first-principle calculation of the reaction probability as a function of incident photon energy. The method is illustrated by application to the photoinduced desorption/dissociation of O2 on a Ag(110) surface by adopting density functional theory.     

Effect of temperature on the rate of corrosion of metals

Russian Chemical Bulletin -     

Effect of high temperature on reduction-controlling reaction rate of agricultural waste chars and coke with steelmaking slag

In the present research, mechanical and thermal properties of high-density polyethylene/wood flour were improved by incorporating nanoclay (Cloisite 30B) and antioxidant (Irganox B225) in the compound. Design of experiments was carried out to optimize composition among nine compounds and to investigate the effect of nanoclay and antioxidant (0–5 phr) and (0–0.4 phr), respectively. The results of mechanical tests showed approximately 24% increase in the tensile strength of compounds containing 2.5 and 5.0 part per hundred (phr) of the nanoclay in the composite compared with the same samples without nanoclay. The tensile modulus of composites increased 7.3% by increasing the level of nanoclay from 0 to 2.5 phr. However, a further increase in the nanoclay content led to a 4.3% decrease in tensile modulus. Evaluation of the thermal oxidation stability of samples confirmed that the thermal oxidation of composites decreased with increasing nanoclay from 0 to 5.0 phr and increased significantly with the addition of the antioxidant.

     

Effect of the reaction temperature on the morphology of nanosized HAp

The main purpose of this study is numerically investigating the flow and heat transfer of nanofluid flow inside a microchannel with L-shaped porous ribs as well as studying the effect of porous media properties on the performance evaluation criterion (PEC) of the fluid. In the present paper, in addition to the pure water fluid, the effect of using water/CuO nanofluid on the PEC of microchannel was investigated. The flow was simulated in four Reynolds numbers and two different volume fractions of nanoparticles in laminar flow regime. The investigated parameters are the thermal conductivity and the porosity rate of porous medium. The results indicate that with the existence of porous ribs, the nanofluid does not have a significant effect on heat transfer increase. By using porous ribs in flow with Reynolds number of 1200, the heat transfer rate increases up to 42% and in flow with Reynolds number of 100, this rate increases by 25%.

     

Cross sections and low temperature rate coefficients for the H + CH+ reaction: a quasiclassical trajectory study

The H + CH(+) reaction is studied by quasiclassical trajectory (QCT) calculations, along with phase space theory (PST) and quantum rigid rotor calculations, employing a global single-valued potential energy surface recently derived by our group. We report QCT total cross sections for each of the three channels, for low collision energies and different reactant rotational quantum numbers. At the lowest collision energies, all cross sections exhibit a capture-like behaviour, as expected from a barrierless reaction. At higher energies, there are important dynamical effects coming from the opening of new channels in the inelastic and reactive exchange collisions. The inelastic cross sections turn out to largely increase, while the reactive abstraction cross sections are declining faster than predicted by the capture theory. A large value of the reactant rotational quantum number tends to suppress these dynamical effects. The QCT rate coefficients are reported for a temperature range from 1-700 K. Below 20 K, the abstraction and exchange QCT rate coefficients are almost constant, as predicted by the capture theory. Above this temperature, the abstraction rate coefficient declines, while the exchange and inelastic rate coefficients are increasing, due to the opening of new channels. A good agreement is observed between the experimental abstraction rate coefficient and the QCT and PST ones. The QCT inelastic results are also compared with those obtained from rigid rotor close coupling (CCRR) calculations in order to check the ability of this approach to provide a reliable estimate of the inelastic rate coefficients for a reactive system without a barrier. The laws of variation as a function of temperature are found to be very similar and the curves are parallel above 20 K. However, reaction is not allowed in the rigid rotor approximation, therefore the CCRR results are about twice as large as their QCT counterparts.     

An infrared study of the formation and photochemical decomposition of tetrachlorocyclopentadienone O-oxide in low temperature matrices

Photolysis of tetrachlorodiazocyclopentadiene at 12 K in Ar or N₂ matrices containing O₂ yields tetrachlorocyclopentadienone and tetrachloro-2-pyrone. Matrix i.r. spectra are reported for each of these products. The reaction proceeds by the addition of O₂ to the previously identified carbene, tetrachlorocyclopentadienylidene, giving initially the highly labile carbonyl oxide, tetrachlorocyclopentadienone O-oxide. The identification of the carbonyl oxide was assisted by experiments using isotopically labelled O₂, and this reactive intermediate has now been characterized in low temperature matrices by both u.v.-visible and i.r. spectroscopy.     

Preparation of poly(vinyl chloride) at low temperature by a photochemical method

A convenient method has been developed for the polymerization of vinyl chloride at low temperatures (to at least ?75°C) by using a tungsten–iodine rather than an ultraviolet lamp, and uranyl nitrate as sensitizer. The use of predominantly visible light minimizes degradation reactions sometimes encountered with ultraviolet light. Measurements of the fraction of racemic (or syndiotactic) diads and per cent crystallinity confirm that the products resemble polymers prepared by other techniques, such as polymerization initiated by a boron alkyl. It is concluded, therefore, that the method can provide a useful alternate to the more common, organometallic system. Measurements of torsional modulus as a function of temperature were also made. As the temperature of polymerization is lowered, the fraction of racemic diads and the per cent crystallinity are increased. The higher the per cent crystallinity, the higher the glass temperature, the broader the glass transition, and the higher the modulus in the rubbery state. Thus, the increased stereoregularity permits the development of a higher level of crystallinity which, in turn, restricts the mobility of the polymer chains.     

Preparation of functionalized ketones via low temperature grignard reaction

δ-Chloroketones and 5-oxo-9-decenoic acid methyl ester were prepared from 5-chlorovaleryl chloride and methyl 4-(chloroformyl)-butyrate via Grignard reaction in tetrahydrofuran at ?70°.     

The mechanism of the low temperature polymerization reaction in diacetylene crystals

The mechanism of the low temperature polymerization reaction in TSHD diacetylene crystals has been investigated by the transient ESR of the paramagnetic triplet (S = 1) and quintet (S ≈ 2) reaction intermediates. The reaction schemes of the thermal and optical addition and transformation reactions after UV photoinitiation are obtained. The activation energies of the chain propagation reaction and the singlet—triplet and singlet—quintet energy separations of the different dicarbene and diradical intermediates are deduced from the experiments.