The chemistry involved in the steam treatment of lignocellulosic materials

Pretreatment of lignocellulosic materials is essential for bioconversion because of the various physical and chemical barriers that greatly inhibit their susceptibility to bioprocesses such as hydrolysis and fermentation. The aim of this article is to review some of the most important pretreatment methods developed to date to enhance the conversion of lignocellulosics. Steam explosion, which precludes the treatment of biomass with high-pressure steam under optimal conditions, is presented as the pretreatment method of choice and its mode of action on lignocellulosics is discussed. The optimal pretreatment conditions for a given plant biomass are defined as those in which the best substrate for hydrolysis is obtained with the least amount of soluble sugars lost to side reactions such as dehydration. Therefore, pretreatment optimization results from a compromise between two opposite trends because hemicellulose recovery in acid hydrolysates can only be maximized at lower pretreatment severities, whereas the development of substrate accessibility requires more drastic pretreatment conditions in which sugar losses are inevitable. To account for this heterogeneity, the importance of several process-oriented parameters is discussed in detail, such as the pretreatment temperature, residence time into the steam reactor, use of an acid catalyst, susceptibility of the pretreated biomass to bioconversion, and process design.

Quantum-to-classical crossover in full counting statistics

The reduction of quantum scattering leads to the suppression of shot noise. In this Letter, we analyze the crossover from the quantum transport regime with universal shot noise to the classical regime where noise vanishes. By making use of the stochastic path integral approach, we find the statistics of transport and the transmission properties of a chaotic cavity as a function of a system parameter controlling the crossover. We identify three different scenarios of the crossover.

Quantum suppression of shot noise in field emitters

We have analyzed the shot noise of electron emission under strong applied electric fields within the Landauer-Bttiker scheme. In contrast to the previous studies of vacuum-tube emitters, we show that in new generation electron emitters, scaled down to the nanometer dimensions, shot noise much smaller than the Schottky noise is observable. Carbon nanotube field emitters are among possible candidates to observe the effect of shot-noise suppression caused by quantum partitioning.

The saccharinate anion: a versatile and fascinating ligand in coordination chemistry

The saccharinate anion, obtained by deprotonation of the N-H moiety of saccharin (o-sulfobenzimide) is a very versatile and polyfunctional ligand in coordination chemistry. In this review the different forms of metal-to-ligand interactions involving this anion and some other coordination peculiarities are briefly discussed on the basis of some selected examples.

Do general chemistry textbooks facilitate conceptual understanding?

Research in chemistry education has recognized the need for facilitating students' understanding of different concepts. In contrast, most general chemistry curricula and textbooks not only ignore the context in which science progresses but also emphasize rote learning and algorithmic strategies. A historical reconstruction of scientific progress shows that it inevitably leads to controversy and debate, which can arouse students' interest and thus facilitate understanding. The objective of this article is to review research related to the evaluation of general chemistry textbooks (based on history and philosophy of science, HPS) and suggest alternatives that can facilitate conceptual understanding.

Probing quantum gravity using photons from a flare of the active galactic nucleus Markarian 501 observed by the MAGIC telescope

We analyze the timing of photons observed by the MAGIC telescope during a flare of the active galactic nucleus Mkn 501 for a possible correlation with energy, as suggested by some models of quantum gravity (QG), which predict a vacuum refractive index similar or equal to 1 + (E/M-QGn)(n), n = 1, 2. Parametrizing the delay between gamma-rays of different energies as Delta t = +/-tau E-1 or Delta t = +/-tau E-q(2), we find tau(1) = (0.030 +/- 0.012) s/GeV at the 2.5-sigma level, and tau(q) = (3.71 +/- 2.57) x 10(-6) s/GeV2, respectively. We use these results to establish lower limits M-QG1 > 0.21 X 10(18) GeV and M-QG2 > 0.26 x 10(11) GeV at the 95% C.L. Monte Carlo studies confirm the MAGIC sensitivity to propagation effects at these levels. Thermal plasma effects in the source are negligible, but we cannot exclude the importance of some other source effect.

Quantum magnetic deflagration in Mn12 acetate

We report controlled ignition of magnetization reversal avalanches by surface acoustic waves in a single crystal of Mn12 acetate. Our data show that the speed of the avalanche exhibits maxima on the magnetic field at the tunneling resonances of Mn12. Combined with the evidence of magnetic deflagration in Mn12 acetate [Y. Suzuki et al., Phys. Rev. Lett. 95, 147201 (2005)], this suggests a novel physical phenomenon: deflagration assisted by quantum tunneling.

Uma introdução à espectroscopia atômica: II - o espectro do sódio

The present article is devoted to Chemistry or Physics undergraduate students, given their difficulty to understand fundamental concepts and technical language used in atomic spectroscopy and quantum mechanics. An easy approach is shown in the treatment of the emission spectrum of the sodium atom without any involved calculations. In a previous article, the hydrogen spectrum was considered and the energy degeneracy of the angular momentum quantum number was observed. For the sodium spectrum, due to the valence electron penetration into internal shells, a breakdown of this degeneracy occurs and a dependence of this penetration on the angular momentum quantum number is observed. The eigenvalues are determined introducing the quantum defect correction (Rydberg correction) in the denominator of the Balmer equation, and the energy diagram is obtained. The intensity ratio for the observed doublets is explained by introducing new wave functions, containing the magnetic quantum number of the total angular momentum.

Propriedades químico-quânticas empregadas em estudos das relações estrutura-atividade

In this work we show that structure-activity relationship studies are of great importance in modern chemistry and biochemistry. In order to obtain a significant correlation, it is crucial that appropriate descriptors be employed. Thus, quantum chemical calculations are an attractive source of new molecular descriptors which can, in principle, express all the electronic and geometric properties of molecules and their interactions with the biological receptor.

Quantum dynamics of the parabolic model

Kvanttimekaniikan teoriassa suljettuja, ympäristöstään eristettyjä systeemejä koskevat tulokset ovat hyvin tunnettuja. Eräs tärkeä erityispiirre tällaisille systeemeille on, että niiden aikakehitys on unitaarista. Oletus siitä, että systeemi on suljettu, on osaltaan tietysti vain yksinkertaistus. Käytännössä kaikki kvanttimekaaniset systeemit vuorovaikuttavat ympäristönsä kanssa ja tästä johtuen niiden dynamiikka monimutkaistuu oleellisesti. Kuitenkin tietyissä tapauksissa systeemin aikakehitys voidaan ratkaista, ainakin approksimatiivisesti. Tärkeimpinä esimerkkeinä on ympäristön joko nopea tai erittäin hidas muutos kvanttisysteemin ominaiseen aikaskaalaan verrattuna. Näistä erityisesti jälkimmäinen on käyttökelpoinen oletus monissa fysikaalisissa tilanteissa. Tällöin voidaan suorittaa niin sanottu adiabaattinen approksimaatio. Sen mukaan systeemi, joka on aikakehityksen generoivan Hamiltonin operaattorin ominaistilassa, pysyy vastaavassa ominaistilassa ympäristön muuttuessa äärettömän hitaasti, mikäli systeemin eri energiatasot eivät leikkaa toisiaan. Todellisissa tilanteissa muutos ei tietenkään voi olla äärettömän hidasta ja myös energiatasojen leikkaukset ovat mahdollisia, jolloin tapahtuu transitio eri ominaistilojen välillä. Energiatasojen leikkauksilla on oleellisia vaikutuksia erittäin monissa fysikaalisissa prosesseissa ja niitä kuvaamaan on luotu monia malleja kvanttimekaniikan alkuajoista lähtien aina tähän päivään saakka. Nykyinen teknologinen kehitys on avannut uudenlaisen mahdollisuuden ilmiön kokeelliseen varmentamiseen ja hyödyntämiseen. Tämän vuoksi kyseisten mallien dynamiikan ja erityisesti energiatasojen useiden peräkkäisten leikkausten aiheuttamien koherenssi-ilmiöiden selvittäminen on tärkeää. Tässä työssä käsitellään kvanttimekaanisia kaksitasosysteemejä, joissa esiintyy energiatasojen leikkauksia sekä niiden pitkän aikavälin dynamiikkaa. Tutkielmassa perehdytään tarkemmin kahteen tiettyyn malliin. Näistä ensimmäinen, Landau-Zener -malli, on tunnetuin ja sovelluksissa käytetyin malli. Kuitenkin erityisen mielenkiinnon kohteena on niin kutsuttu parabolinen malli, jolle johdetaan eri approksimaatioita käyttäen asymptoottiset transitiotodennäköisyydet eri tilojen välille. Näitä verrataan numeerisiin tuloksiin.

The contributions of Henri Victor Regnault in the context of organic chemistry of the first half of the nineteenth century

A very little known aspect of the scientific career of Regnault is his contribution to the emerging organic chemistry in the first half of the nineteenth century. The purpose of this article is not only to describe two of his most important researches in this field, as were the discovery of two series of halogenated derivates of certain organic compounds and the precise identification of some of the then recently discovered alkaloids, but also the main features that identified his research method. With the involvement in these subjects, Regnault unintentionally positioned himself in the midst of some of the polemics about the classification of organic compounds that characterized this age of science.

A brief introduction to molecular orbital theory of simple polyatomic molecules for undergraduate chemistry students

A simple, four-step method for better introducing undergraduate students to the fundamentals of molecular orbital (MO) theory of the polyatomic molecules H2O, NH3, BH3 and SiH4 using group theory is reported. These molecules serve to illustrate the concept of ligand group orbitals (LGOs) and subsequent construction of MO energy diagrams on the basis of molecular symmetry requirements.

Theoretical investigation of electronic excitation transfer between chlorophylls in light-harvesting antenna of photosystem ii using quantum computers

The excitation energy transfer between chlorophylls in major and minor antenna complexes of photosystem II (PSII) was investigated using quantum Fourier transforms. These transforms have an important role in the efficiency of quantum algorithms of quantum computers. The equation 2n=N was used to make the connection between excitation energy transfers using quantum Fourier transform, where n is the number of qubits required for simulation of transfers and N is the number of chlorophylls in the antenna complexes.

Tropical biodiversity: has it been a potential source of secondary metabolites useful for medicinal chemistry?

The use of natural products has definitely been the most successful strategy in the discovery of novel medicines. Secondary metabolites from terrestrial and marine organisms have found considerable use in the treatment of numerous diseases and have been considered lead molecules both in their natural form and as templates for medicinal chemistry. This paper seeks to show the great value of secondary metabolites and emphasize the rich chemical diversity of Brazilian biodiversity. This natural chemical library remains understudied, but can be a useful source of new secondary metabolites with potential application as templates for drug discovery.

Probing the (empirical) quantum structure embedded in the periodic table with an effective Bohr model

The atomic shell structure can be observed by inspecting the experimental periodic properties of the Periodic Table. The (quantum) shell structure emerges from these properties and in this way quantum mechanics can be explicitly shown considering the (semi-)quantitative periodic properties. These periodic properties can be obtained with a simple effective Bohr model. An effective Bohr model with an effective quantum defect (u) was considered as a probe in order to show the quantum structure embedded in the Periodic Table. u(Z) shows a quasi-smoothed dependence of Z, i.e., u(Z) ≈ Z2/5 - 1.