Interaction between Sulfated Zirconia and Alkanes: Prerequisites for Active Sites – Formation and Stability of Reaction Intermediates

Two sulfated zirconia catalysts were prepared via sulfation and calcination at 873 K of zirconium hydroxide aged at room temperature for 1 h (SZ-1) or aged at 373 K for 24 h (SZ-2). SZ-1 was active for n-butane isomerisation at 373 K; SZ-2 reached similar performance only at 473 K. Both materials contained about 9 wt% sulfate and were tetragonal. Due to a BET lower surface area (105 m2/g vs. 148 m2/g) SZ-1 featured a higher sulfate density, and XRD and EXAFS analysis showed larger (ca. 10 nm) and more well ordered crystals than for SZ-2. n-Butane TPD on SZ-1 showed a butene desorption peak at low temperature, whereas, no obvious butene desorption was observed with SZ-2, suggesting that SZ-1 has a higher oxidizing power at low temperature than SZ-2. The number of sites capable of dehydrogenation are less than 5 µmol/g, because the differential heats of n-butane adsorption as measured by microcalorimetry were 45–60 kJ/mol for higher coverages, indicating weak and reversible interaction. TAP experiments describe the adsorption and desorption behavior of n-butane at different activity states and are the basis for a simple adsorption model. Reactant pulses and purge experiments show that the active species, presumably formed in an oxidative dehydrogenation step, are stable at the surface under reaction conditions

Solid-state NMR of nanomachines involved in photosynthetic energy conversion

Solid state NMR/Biophysical Organic Chemistr

Метод итерации решения некорректных уравнений с приближенным оператором в случае априорного выбора параметра регуляризации

In the introduction, the object of investigation is indicated – incorrect problems described by first-kind operator equations. The subject of the study is an explicit iterative method for solving first-kind equations. The aim of the paper is to prove the convergence of the proposed method of simple iterations with an alternating step alternately and to obtain error estimates in the original norm of a Hilbert space for the cases of self-conjugated and non self-conjugated problems. The a priori choice of the regularization parameter is studied for a source-like representable solution under the assumption that the operator and the right-hand side of the equation are given approximately. In the main part of the work, the achievement of the stated goal is expressed in four reduced and proved theorems. In Section 1, the first-kind equation is written down and a new explicit method of simple iteration with alternating steps is proposed to solve it. In Section 2, we consider the case of the selfconjugated problem and prove Theorem 1 on the convergence of the method and Theorem 2, in which an error estimate is obtained. To obtain an error estimate, an additional condition is required – the requirement of the source representability of the exact solution. In Section 3, the non-self-conjugated problem is solved, the convergence of the proposed method is proved, which in this case is written differently, and its error estimate is obtained in the case of an a priori choice of the regularization parameter. In sections 2 and 3, the error estimates obtained are optimized, that is, a value is found – the step number of the iteration, in which the error estimate is minimal. Since incorrect problems constantly arise in numerous applications of mathematics, the problem of studying them and constructing methods for their solution is topical. The obtained results can be used in theoretical studies of solution of first-kind operator equations, as well as applied ill-posed problems encountered in dynamics and kinetics, mathematical economics, geophysics, spectroscopy, systems for complete automatic processing and interpretation of experiments, plasma diagnostics, seismic and medicine.Аннотация. Указан объект исследования – некорректные задачи, описываемые операторными уравнениями I рода. Предмет исследования – явный итерационный метод решения уравнений I рода. Цель работы заключается в доказательстве сходимости предложенного метода простых итераций с попеременно чередующимся шагом и получении оценок погрешности в исходной норме гильбертова пространства для случаев самосопряженной и несамосопряженной задач. Априорный выбор параметра регуляризации изучается для истокообразно представимого решения в предположении, что оператор и правая часть уравнения заданы приближенно. Достижение поставленной цели выражено в четырех приведенных и доказанных теоремах: записано уравнение I рода и предлагается новый явный метод простой итерации с попеременно чередующимся шагом для его решения; рассматривается случай самосопряженной задачи; доказана теорема 1 о сходимости метода и теорема 2, в которой получена оценка погрешности (для получения оценки погрешности потребовалось дополнительное условие – требование истокопредставимости точного решения); решается несамосопряженная задача, доказана сходимость предложенного метода, который в этом случае запишется по-другому, и получена его оценка погрешности в случае априорного выбора параметра регуляризации. Полученные оценки погрешности оптимизированы, т. е. найдено значение nопт – номер шага итерации, при котором оценка погрешности минимальна. Поскольку некорректные задачи постоянно возникают в многочисленных приложениях математики, то проблема их изучения и построения методов их решения является актуальной. Полученные результаты могут быть использованы в теоретических исследованиях при решении операторных уравнений I рода, а также прикладных некорректных задач, встречающихся в динамике и кинетике, математической экономике, геофизике, спектроскопии, системах полной автоматической обработки и интерпретации экспериментов, диагностике плазмы, сейсмике и медицине

Bacteriopheophytin a in the active branch of the reaction center of Rhodobacter sphaeroides is not disturbed by the protein matrix as shown by C-13 photo-CIDNP MAS NMR

Solid state NMR/Biophysical Organic Chemistr

Field-cycling NMR with high-resolution detection under magic-angle spinning: determination of field-window for nuclear hyperpolarization in a photosynthetic reaction center

Several parameters in NMR depend on the magnetic field strength. Field-cycling NMR is an elegant way to explore the field dependence of these properties. The technique is well developed for solution state and in relaxometry. Here, a shuttle system with magic-angle spinning (MAS) detection is presented to allow for field-dependent studies on solids. The function of this system is demonstrated by exploring the magnetic field dependence of the solid-state photochemically induced nuclear polarization (photo-CIDNP) effect. The effect allows for strong nuclear spin-hyperpolarization in light-induced spin-correlated radical pairs (SCRPs) under solid-state conditions. To this end, (13)C MAS NMR is applied to a photosynthetic reaction center (RC) of the purple bacterium Rhodobacter (R.) sphaeroides wildtype (WT). For induction of the effect in the stray field of the magnet and its subsequent observation at 9.4 T under MAS NMR conditions, the sample is shuttled by the use of an aerodynamically driven sample transfer technique. In the RC, we observe the effect down to 0.25 T allowing to determine the window for the occurrence of the effect to be between about 0.2 and 20 T.Solid state NMR/Biophysical Organic Chemistr

Comparison of photoacoustic spectroscopy and cavity ring-down spectroscopy for ambient methane monitoring at Hohenpeißenberg

With an atmospheric concentration of approximately 2000 parts per billion (ppbV, 10−9), methane (CH4) is the second most abundant greenhouse gas (GHG) in the atmosphere after carbon dioxide (CO2). The task of long-term and spatially resolved GHG monitoring to verify whether climate policy actions are effective is becoming more crucial as climate change progresses. In this paper we report the CH4 concentration readings of our photoacoustic (PA) sensor over a 5 d period at Hohenpeißenberg, Germany. As a reference device, a calibrated cavity ring-down spectrometer, Picarro G2301, from the meteorological observatory of the German Weather Service (DWD) was employed. Trace gas measurements with photoacoustic instruments promise to provide low detection limits at comparably low costs. However, PA devices are often susceptible to cross-sensitivities related to fluctuating environmental conditions, e.g. ambient humidity. The obtained results show that for PA sensor systems non-radiative relaxation effects induced by varying humidity are a non-negligible factor. Applying algorithm compensation techniques, which are capable of calculating the influence of non-radiative relaxation effects on the photoacoustic signal, increase the accuracy of the photoacoustic sensor significantly. With an average relative deviation of 1.11 % from the G2301, the photoacoustic sensor shows good agreement with the reference instrument.</p

The solid-state photo-CIDNP effect

The solid-state photo-CIDNP effect is the occurrence of a non-Boltzmann nuclear spin polarization in rigid samples upon illumination. For solid-state NMR, which can detect this enhanced nuclear polarization as a strong modification of signal intensity, the effect allows for new classes of experiments. Currently, the photo- and spin-chemical machinery of various RCs is studied by photo-CIDNP MAS NMR in detail. Until now, the effect has only been observed at high magnetic fields with 13C and 15N MAS NMR and in natural photosynthetic RC preparations in which blocking of the acceptor leads to cyclic electron transfer. In terms of irreversible thermodynamics, the high-order spin structure of the initial radical pair can be considered as a transient order phenomenon emerging under non-equilibrium conditions and as a first manifestation of order in the photosynthetic process. The solid-state photo-CIDNP effect appears to be an intrinsic property of natural RCs. The conditions of its occurrence seem to be conserved in evolution. The effect may be based on the same fundamental principles as the highly optimized electron transfer. Hence, the effect may allow for guiding artificial photosynthesis

Exploring Chromophore-Binding Pocket: High-Resolution Solid-State 1H–13C Interfacial Correlation NMR Spectra with Windowed PMLG Scheme

High-resolution two-dimensional (2D) 1H–13C heteronuclear correlation spectra are recorded for selective observation of interfacial 3–5.5 Å contacts of the uniformly 13C-labeled phycocyanobilin (PCB) chromophore with its unlabeled binding pocket. The experiment is based on a medium- and long-distance heteronuclear correlation (MELODI–HETCOR) method. For improving 1H spectral resolution, a windowed phase-modulated Lee–Goldburg (wPMLG) decoupling scheme is applied during the t1 evolution period. Our approach allows for identification of chromophore–protein interactions, in particular for elucidation of the hydrogen-bonding networks and charge distributions within the chromophore-binding pocket. The resulting pulse sequence is tested on the cyanobacterial (Cph1) phytochrome sensory module (residues 1–514, Cph1Δ2) containing uniformly 13C- and 15N-labeled PCB chromophore (u-[13C,15N]-PCB-Cph1Δ2) at 17.6 T

Solid-state NMR applied to photosynthetic light-harvesting complexes

This short review describes how solid-state NMR has provided a mechanistic and electronic picture of pigment–protein and pigment–pigment interactions in photosynthetic antenna complexes. NMR results on purple bacterial antenna complexes show how the packing of the protein and the pigments inside the light-harvesting oligomers induces mutual conformational stress. The protein scaffold produces deformation and electrostatic polarization of the BChl macrocycles and leads to a partial electronic charge transfer between the BChls and their coordinating histidines, which can tune the light-harvesting function. In chlorosome antennae assemblies, the NMR template structure reveals how the chromophores can direct their self-assembly into higher macrostructures which, in turn, tune the light-harvesting properties of the individual molecules by controlling their disorder, structural deformation, and electronic polarization without the need for a protein scaffold. These results pave the way for addressing the next challenge, which is to resolve the functional conformational dynamics of the lhc antennae of oxygenic species that allows them to switch between light-emitting and light-energy dissipating states