Measuring, Understanding, and Controlling Heteroatom Distributions in Layered and Zeolite Boro- and Alumino-silicate Frameworks

Site-specific heteroatom incorporation imparts catalytic and adsorption properties to silicate-based catalysts (e.g., zeolites and clays), leading to diverse technologically important industrial processes. In such applications, reactions are typically catalyzed at Brønsted acid sites associated with H+ cations that balance the anionic charges near framework heteroatom species (generally aluminum) in heteroatom-containing silicate frameworks. Despite the fact that the catalytic and adsorption properties of these catalysts have been observed to be greatly influenced by several factors, such as heteroatom type, contents, and distributions, the associated fundamental understanding of heteroatom site distributions is still very limited and has been elusive. This is partially due to lack of experimental methods that can probe the complicated order and disorder around heteroatom sites even in well-ordered crystalline silicate frameworks. Among various characterization methods, solid-state nuclear magnetic resonance (NMR) spectroscopy can be considered as a promising technique because of its high sensitivity to electronic environments of NMR-active nuclei, which allows their molecular proximities and connectivities to be established.Herein, newly modified two-dimensional (2D) NMR techniques were applied to probe specific covalent site connectivities between framework boron or aluminum heteroatoms and their nearby silicate sites in zeolite and layered boro- and alumino-silicate materials. The established site connectivities, in conjunction with crystallography, enable the determination of boron or aluminum heteroatom site distributions. We applied the new 2D NMR methods to boron- or aluminum-containing surfactant-directed silicates and zeolite SSZ-70, aiming for understanding similarities and differences between boron and aluminum incorporation. Interestingly, boron atoms are shown to be preferentially incorporated into specific silicate sites in most cases, whereas aluminum atoms appear to be non-selectively distributed among different silicate sites in all cases. Such observations may suggest that boron and aluminum species participate differently in the formation of boro- and aluminosilicates, respectively.Based on the molecular understanding of boron and aluminum siting learned from these materials, a synthesis protocol to control heteroatom siting in zeolite catalysts is proposed using borosilicate zeolite SSZ-70 (B-SSZ-70) as an example. The protocol begins with the preparation of B-SSZ-70 that was delaminated to increase its external surface area for reactions involving bulky molecules, during which boron siting was monitored ex-situ at different synthesis stages. The results show that boron site distributions were retained during the course of post-synthetic treatments. Subsequently, the framework boron species in the delaminated B-SSZ-70 were post-synthetically exchanged with aluminum atoms. Notably, as expected, the reinserted aluminum species are concluded to be located at certain silicate sites on external surface sites. This is very different from the aluminum siting in Al-SSZ-70 (i.e., Al is everywhere ). Overall, these analyses, methods, and synthesis protocols are expected to provide insights into the local environments of heteroatoms and their distributions in zeolite catalysts, which would enable rational zeolite synthesis with engineered heteroatom site distributions

Characterizing First Arrival Position Channels: Noise Distribution and Capacity Analysis

This paper addresses two fundamental problems in diffusive molecular communication: characterizing the first arrival position (FAP) density and bounding the information transmission capacity of FAP channels. Previous studies on FAP channel models, mostly captured by the density function of noise, have been limited to specific spatial dimensions, drift directions, and receiver geometries. In response, we propose a unified solution for identifying the FAP density in molecular communication systems with fully-absorbing receivers. Leveraging stochastic analysis tools, we derive a concise expression with universal applicability, covering any spatial dimension, drift direction, and receiver shape. We demonstrate that several existing FAP density formulas are special cases of this innovative expression. Concurrently, we establish explicit upper and lower bounds on the capacity of three-dimensional, vertically-drifted FAP channels, drawing inspiration from vector Gaussian interference channels. In the course of deriving these bounds, we unravel an explicit analytical expression for the characteristic function of vertically-drifted FAP noise distributions, providing a more compact characterization compared to the density function. Notably, this expression sheds light on a previously undiscovered weak stability property intrinsic to vertically-drifted FAP noise distributions.Comment: 30 pages; 3 figures, 1 table; this paper is submitted to IEEE Transactions on Communication

Fractional phenomena of the spontaneous emission of a two-level atom in photonic crystals

We suggest a better mathematical method, fractional calculus, for studying the behavior of the atom-field interaction in photonic crystals. By studying the spontaneous emission of an atom in a photonic crystal with one-band isotropic model, we found that the long-time inducing memory of the spontaneous emission is a fractional phenomenon. This behavior could be well described by the fractional calculus. And the results show no steady photon-atom bound state for the atomic resonant transition frequency lying in the proximity of allowed band edge which is encountered in the previous study [J. Opt. B: Quantum Semiclass. Opt. {\bf 5}, R43 (2003)]. The correctness of this result is validated by the ``cut-off smoothing'' density of photon states (DOS) with fractional calculus. By obtaining a rigorous solution without the multiple-valued problem for the system, we show the method of fractional calculus has logically concise property.Comment: 12 Pages, 3 figure

Studies of Aluminum Reinsertion into Borosilicate Zeolites with Intersecting Channels of 10- and 12-Ring Channel Systems

The work here describes the kinetic analyses of aluminum replacement for boron in a suite of borosilicate molecular sieves. While the method has been described before as a means of converting synthesized borosilicates (with weak inherent acidity) to aluminosilicates (with much stronger acid strength) when there are large pores in the structure, here we carry out the transformation under less than optimal replacement concentrations, in order to better follow the kinetics. We examined several zeolite structures with boundary conditions of boron MEL where there are only 10-ring (or intermediate) pore structures and no Al is taken up, to multidimensional large pore zeolites, like boron beta, where Al substitution can occur everywhere. We also studied materials with both intermediate and large pores, SSZ-56, 57, 70, and 82. In the case of 57 up to 90% of the structure is made up of boron MEL. We observe that the pH drop is proportional to the Al reinsertion and is the same for all zeolites we studied. In one case, we compared a zeolite (SSZ-24) with boron and then no boron sites and found that Al does not go into defect sites. It was again confirmed (shown in earlier work) that Al will go into nest sites created by boron hydrolysis out of the substrate before Al treatment. Along those lines we also made two new observations: (1) the profile for Al uptake, as followed by pH drop, is the same kinetically, whether the boron is there or not; and (2) NMR showed that the boron is leaving the structure faster than Al can go back in (SSZ-33 study), even when we treat a material with boron in the lattice

Studies of Aluminum Reinsertion into Borosilicate Zeolites with Intersecting Channels of 10- and 12-Ring Channel Systems

The work here describes the kinetic analyses of aluminum replacement for boron in a suite of borosilicate molecular sieves. While the method has been described before as a means of converting synthesized borosilicates (with weak inherent acidity) to aluminosilicates (with much stronger acid strength) when there are large pores in the structure, here we carry out the transformation under less than optimal replacement concentrations, in order to better follow the kinetics. We examined several zeolite structures with boundary conditions of boron MEL where there are only 10-ring (or intermediate) pore structures and no Al is taken up, to multidimensional large pore zeolites, like boron beta, where Al substitution can occur everywhere. We also studied materials with both intermediate and large pores, SSZ-56, 57, 70, and 82. In the case of 57 up to 90% of the structure is made up of boron MEL. We observe that the pH drop is proportional to the Al reinsertion and is the same for all zeolites we studied. In one case, we compared a zeolite (SSZ-24) with boron and then no boron sites and found that Al does not go into defect sites. It was again confirmed (shown in earlier work) that Al will go into nest sites created by boron hydrolysis out of the substrate before Al treatment. Along those lines we also made two new observations: (1) the profile for Al uptake, as followed by pH drop, is the same kinetically, whether the boron is there or not; and (2) NMR showed that the boron is leaving the structure faster than Al can go back in (SSZ-33 study), even when we treat a material with boron in the lattice

Regulation of MMP-3 expression and secretion by the chemokine eotaxin-1 in human chondrocytes

<p>Abstract</p> <p>Background</p> <p>Osteoarthritis (OA) is characterized by the degradation of articular cartilage, marked by the breakdown of matrix proteins. Studies demonstrated the involvement of chemokines in this process, and some may potentially serve as diagnostic markers and therapeutic targets; however, the underlying signal transductions are not well understood.</p> <p>Methods</p> <p>We investigated the effects of the CC chemokine eotaxin-1 (CCL11) on the matrix metalloproteinase (MMP) expression and secretion in the human chondrocyte cell line SW1353 and primary chondrocytes.</p> <p>Results</p> <p>Eotaxin-1 significantly induced MMP-3 mRNA expression in a dose-dependent manner. Inhibitors of extracellular signal-regulated kinase (ERK) and p38 kinase were able to repress eotaxin-1-induced MMP-3 expression. On the contrary, Rp-adenosine-3',5'-cyclic monophosphorothioate (Rp-cAMPs), a competitive cAMP antagonist for cAMP receptors, and H-89, a protein kinase A (PKA) inhibitor, markedly enhanced eotaxin-1-induced MMP-3 expression. These results suggest that MMP-3 expression is specifically mediated by the G protein-coupled eotaxin-1 receptor activities. Interestingly, little amount of MMP-3 protein was detected in the cell lysates of eotaxin-1-treated SW1353 cells, and most of MMP-3 protein was in the culture media. Furthermore we found that the eotaxin-1-dependent MMP-3 protein secretion was regulated by phospholipase C (PLC)-protein kinase C (PKC) cascade and c-Jun N-terminal kinase (JNK)/mitogen-activated protein (MAP) kinase pathways. These data indicate a specific regulation of MMP-3 secretion also by eotaxin-1 receptor activities.</p> <p>Conclusions</p> <p>Eotaxin-1 not only induces MMP-3 gene expression but also promotes MMP-3 protein secretion through G protein-coupled eotaxin-1 receptor activities. Chemokines, such as eotaxin-1, could be a potential candidate in the diagnosis and treatment of arthritis.</p

Antimicrobial susceptibility and clinical outcomes of Candida parapsilosis bloodstream infections in a tertiary teaching hospital in Northern Taiwan

BackgroundCandida parapsilosis is an emerging non-albicans Candida that is associated with central line-associated infection. C. parapsilosis has higher minimal inhibitory concentration to echinocandin than Candida albicans, and the effects of echinocandin on C. parapsilosis are ambiguous. Therefore, in this study, we aimed to investigate the susceptibility and the correlation between incidence and drug consumption.MethodsThis retrospective study was conducted in a tertiary teaching hospital in northern Taiwan between 2008 and 2012. The Candida species distribution, the correlation between the use of antifungal agents and the incidence of C. parapsilosis bloodstream infection, demographic information, clinical characteristics, mortality rate, and in vitro susceptibility of C. parapsilosis were analyzed.ResultsA total of 77 episodes from 77 patients were included for analysis. The overall 90-day mortality rate was 41.6%. The incidence of C. parapsilosis bloodstream infection showed a moderate positive correlation with the increased defined daily dose of echinocandin. The risk factors associated with mortality included malignancy or a metastatic tumor. Multivariate logistical regression analysis showed that patients with malignancy had higher odds ratios in terms of mortality. The rate of C. parapsilosis resistance to fluconazole was 3%, whereas the susceptibility rate was 95.5%.ConclusionUnderlying comorbidity and malignancy were factors leading to death in patients with C. parapsilosis bloodstream infection. Catheter removal did not influence the mortality rate. The survival rate of patients receiving echinocandin was lower than the group receiving fluconazole. Fluconazole remains the drug of choice to treat C. parapsilosis bloodstream infections

Quantum state tomography via non-convex Riemannian gradient descent

The recovery of an unknown density matrix of large size requires huge computational resources. The recent Factored Gradient Descent (FGD) algorithm and its variants achieved state-of-the-art performance since they could mitigate the dimensionality barrier by utilizing some of the underlying structures of the density matrix. Despite their theoretical guarantee of a linear convergence rate, the convergence in practical scenarios is still slow because the contracting factor of the FGD algorithms depends on the condition number $\kappa$ of the ground truth state. Consequently, the total number of iterations can be as large as $O(\sqrt{\kappa}\ln(\frac{1}{\varepsilon}))$ to achieve the estimation error $\varepsilon$. In this work, we derive a quantum state tomography scheme that improves the dependence on $\kappa$ to the logarithmic scale; namely, our algorithm could achieve the approximation error $\varepsilon$ in $O(\ln(\frac{1}{\kappa\varepsilon}))$ steps. The improvement comes from the application of the non-convex Riemannian gradient descent (RGD). The contracting factor in our approach is thus a universal constant that is independent of the given state. Our theoretical results of extremely fast convergence and nearly optimal error bounds are corroborated by numerical results.Comment: Comments are welcome

Increased renal ANP synthesis, but decreased or unchanged cardiac ANP synthesis in water-deprived and salt-restricted rats

Increased renal ANP synthesis, but decreased or unchanged cardiac ANP synthesis in water-deprived and salt-restricted rats.BackgroundExperiments were performed to examine the effect of water deprivation and salt restriction on ANP synthesis in the kidneys and hearts of normal rats.MethodsA 4-day water deprivation (WD) and 7-day salt restriction (SR; 0.01% NaCl) were performed in 12 and 14 rats, respectively. Atrial natriuretic peptide (ANP) mRNA expression in the kidney was assessed with reverse transcription-polymerase chain reaction coupled with Southern blot hybridization, while the ANP mRNA in the hearts was measured by Northern blot hybridization. ANP and angiotensin II concentrations in the extracted plasma were measured by radioimmunoassay. The molecular form of renal ANP-like protein was characterized by reverse phase—high-performance liquid chromatography (RP-HPLC).ResultsRenal outer and inner medullary ANP mRNA showed a respective 11-fold and ninefold increase in WD rats, and an eightfold and fivefold increase in SR rats as compared to corresponding control groups. Inversely, cardiac atrial ANP mRNA and plasma ANP were decreased in WD rats, whereas they did not change in the SR group. Plasma angiotensin II concentration increased in conjunction with the decrease of urine sodium excretion in both groups. RP-HPLC analysis revealed a 45% extraction of ANP in the WD rat kidneys, whereas only 3% ANP in the control kidneys migrated in a molecular form similar to cardiac atrial proANP.ConclusionsOur results demonstrate that water deprivation and salt restriction markedly enhance renal ANP mRNA, whereas water deprivation suppresses cardiac atrial ANP mRNA and plasma ANP concentrations. The current study indicates that renal ANP and cardiac atrial ANP appear to be two distinct systems regulated by different mechanisms and possibly exhibiting different intra-renal paracrine and systemic endocrine functions