Abdul-Hamid Emwas

MOF Crystal Chemistry Paving the Way to Gas Storage Needs: Aluminum-Based soc-MOF for CH4, O2, and CO2 Storage

The molecular building block approach was employed effectively to construct a series of novel isoreticular, highly porous and stable, aluminum-based metal-organic frameworks with soc topology. From this platform, three compounds were experimentally isolated and fully characterized: namely, the parent Al-soc-MOF-1 and its naphthalene and anthracene analogues. Al-soc-MOF-1 exhibits outstanding gravimetric methane uptake (total and working capacity). It is shown experimentally, for the first time, that the Al-soc-MOF platform can address the challenging Department of Energy dual target of 0.5 g/g (gravimetric) and 264 cm(3) (STP)/cm(3) (volumetric) methane storage. Furthermore, Al-soc-MOF exhibited the highest total gravimetric and volumetric uptake for carbon dioxide and the utmost total and deliverable uptake for oxygen at relatively high pressures among all microporous MOFs. In order to correlate the MOF pore structure and functionality to the gas storage properties, to better understand the structure-property relationship, we performed a molecular simulation study and evaluated the methane storage performance of the Al-soc-MOF platform using diverse organic linkers. It was found that shortening the parent Al-soc-MOF-1 linker resulted in a noticeable enhancement in the working volumetric capacity at specific temperatures and pressures with amply conserved gravimetric uptake/working capacity. In contrast, further expansion of the organic linker (branches and/or core) led to isostructural Al-soc-MOFs with enhanced gravimetric uptake but noticeably lower volumetric capacity. The collective experimental and simulation studies indicated that the parent Al-soc-MOF-1 exhibits the best compromise between the volumetric and gravimetric total and working uptakes under a wide range of pressure and temperature conditions.

NMR-based metabolomics in human disease diagnosis: applications, limitations, and recommendations

Metabolomics is a dynamic and emerging research field, similar to proteomics, transcriptomics and genomics in affording global understanding of biological systems. It is particularly useful in functional genomic studies in which metabolism is thought to be perturbed. Metabolomics provides a snapshot of the metabolic dynamics that reflect the response of living systems to both pathophysiological stimuli and/or genetic modification. Because this approach makes possible the examination of interactions between an organism and its diet or environment, it is particularly useful for identifying biomarkers of disease processes that involve the environment. For example, the interaction of a high fat diet with cardiovascular disease can be studied via such a metabolomics approach by modeling the interaction between genes and diet. The high reproducibility of NMR-based techniques gives this method a number of advantages over other analytical techniques in large-scale and long-term metabolomic studies, such as epidemiological studies. This approach has been used to study a wide range of diseases, through the examination of biofluids, including blood plasma/serum, urine, blister fluid, saliva and semen, as well as tissue extracts and intact tissue biopsies. However, complicating the use of NMR spectroscopy in biomarker discovery is the fact that numerous variables can effect metabolic composition including, fasting, stress, drug administration, diet, gender, age, physical activity, life style and the subject’s health condition. To minimize the influence of these variations in the datasets, all experimental conditions including sample collection, storage, preparation as well as NMR spectroscopic parameters and data analysis should be optimized carefully and conducted in an identical manner as described by the local standard operating protocol . This review highlights the potential applications of NMR-based metabolomics studies and gives some recommendations to improve sample collection, sample preparation and data analysis in using this approach.

Standardizing the experimental conditions for using urine in NMR-based metabolomic studies with a particular focus on diagnostic studies: a review

AbstractThe metabolic composition of human biofluids can provide important diagnostic and prognostic information. Among the biofluids most commonly analyzed in metabolomic studies, urine appears to be particularly useful. It is abundant, readily available, easily stored and can be collected by simple, noninvasive techniques. Moreover, given its chemical complexity, urine is particularly rich in potential disease biomarkers. This makes it an ideal biofluid for detecting or monitoring disease processes. Among the metabolomic tools available for urine analysis, NMR spectroscopy has proven to be particularly well-suited, because the technique is highly reproducible and requires minimal sample handling. As it permits the identification and quantification of a wide range of compounds, independent of their chemical properties, NMR spectroscopy has been frequently used to detect or discover disease fingerprints and biomarkers in urine. Although protocols for NMR data acquisition and processing have been standardized, no consensus on protocols for urine sample selection, collection, storage and preparation in NMR-based metabolomic studies have been developed. This lack of consensus may be leading to spurious biomarkers being reported and may account for a general lack of reproducibility between laboratories. Here, we review a large number of published studies on NMR-based urine metabolic profiling with the aim of identifying key variables that may affect the results of metabolomics studies. From this survey, we identify a number of issues that require either standardization or careful accounting in experimental design and provide some recommendations for urine collection, sample preparation and data acquisition.

The Strengths and Weaknesses of NMR Spectroscopy and Mass Spectrometry with Particular Focus on Metabolomics Research

Mass spectrometry (MS) and nuclear magnetic resonance (NMR) have evolved as the most common techniques in metabolomics studies, and each brings its own advantages and limitations. Unlike MS spectrometry, NMR spectroscopy is quantitative and does not require extra steps for sample preparation, such as separation or derivatization. Although the sensitivity of NMR spectroscopy has increased enormously and improvements continue to emerge steadily, this remains a weak point for NMR compared with MS. MS-based metabolomics provides an excellent approach that can offer a combined sensitivity and selectivity platform for metabolomics research. Moreover, different MS approaches such as different ionization techniques and mass analyzer technology can be used in order to increase the number of metabolites that can be detected. In this chapter, the advantages, limitations, strengths, and weaknesses of NMR and MS as tools applicable to metabolomics research are highlighted.

Gold Doping of Silver Nanoclusters: A 26‐Fold Enhancement in the Luminescence Quantum Yield

A high quantum yield (QY) of photoluminescence (PL) in nanomaterials is necessary for a wide range of applications. Unfortunately, the weak PL and moderate stability of atomically precise silver nanoclusters (NCs) suppress their utility. Herein, we accomplished a ≥26-fold PL QY enhancement of the Ag29 (BDT)12 (TPP)4 cluster (BDT: 1,3-benzenedithiol; TPP: triphenylphosphine) by doping with a discrete number of Au atoms, producing Ag29-x Aux (BDT)12 (TPP)4 , x=1-5. The Au-doped clusters exhibit an enhanced stability and an intense red emission around 660 nm. Single-crystal XRD, mass spectrometry, optical, and NMR spectroscopy shed light on the PL enhancement mechanism and the probable locations of the Au dopants within the cluster.

Silicon oxynitrides of KCC-1, SBA-15 and MCM-41 for CO2 capture with excellent stability and regenerability

We report the use of silicon oxynitrides as novel adsorbents for CO2 capture. Three series of functionalized materials based on KCC-1, SBA-15 and MCM-41 with Si–NH2 groups were prepared using a simple one-step process via thermal ammonolysis using ammonia gas, and they demonstrated excellent CO2 capture capabilities. These materials overcome several limitations of conventional amine-grafted mesoporous silica. They offer good CO2 capture capacity, faster adsorption–desorption kinetics, efficient regeneration and reuse, more crucially excellent thermal and mechanical stability even in oxidative environments, and a clean and green synthesis route, which allows the overall CO2 capture process to be practical and sustainable.

How different is the composition of the fouling layer of wastewater reuse and seawater desalination RO membranes

To study the effect of water quality and operating parameters on membrane fouling, a comparative analysis of wastewater (WW) and seawater (SW) fouled reverse osmosis (RO) membranes was conducted. Membranes were harvested from SWRO and WWRO pilot plants located in Vilaseca (East Spain), both using ultrafiltration as pretreatment. The SWRO unit was fed with Mediterranean seawater and the WWRO unit was operated using secondary effluent collected from the municipal wastewater treatment plant. Lead and terminal SWRO and WWRO modules were autopsied after five months and three months of operation, respectively. Ultrastructural, chemical, and microbiological analyses of the fouling layers were performed. Results showed that the WWRO train had mainly bio/organic fouling at the lead position element and inorganic fouling at terminal position element, whereas SWRO train had bio/organic fouling at both end position elements. In the case of WWRO membranes, Betaproteobacteria was the major colonizing species; while Ca, S, and P were the major present inorganic elements. The microbial population of SWRO membranes was mainly represented by Alpha and Gammaproteobacteria. Ca, Fe, and S were the main identified inorganic elements of the fouling layer of SWRO membranes. These results confirmed that the RO fouling layer composition is strongly impacted by the source water quality.

Unlocking the secrets of Al-tobermorite in Roman seawater concrete

Abstract Ancient Roman syntheses of Al-tobermorite in a 2000-year-old concrete block submerged in the Bay of Pozzuoli (Baianus Sinus), near Naples, have unique aluminum-rich and silica-poor compositions relative to hydrothermal geological occurrences. In relict lime clasts, the crystals have calcium contents that are similar to ideal tobermorite, 33 to 35 wt%, but the low-silica contents, 39 to 40 wt%, reflect Al3+ substitution for Si4+ in Q2(1Al), Q3(1Al), and Q3(2 Al) tetrahedral chain and branching sites. The Al-tobermorite has a double silicate chain structure with long chain lengths in the b [020] crystallographic direction, and wide interlayer spacing, 11.49 Å. Na+ and K+ partially balance Al3+ substitution for Si4+. Poorly crystalline calcium-aluminum-silicate-hydrate (C-A-S-H) cementitious binder in the dissolved perimeter of relict lime clasts has Ca/(Si+Al) = 0.79, nearly identical to the Al-tobermorite, but nanoscale heterogeneities with aluminum in both tetrahedral and octahedral coordination. The concrete is about 45 vol% glassy zeolitic tuff and 55 vol% hydrated lime-volcanic ash mortar; lime formed <10 wt% of the mix. Trace element studies confirm that the pyroclastic rock comes from Flegrean Fields volcanic district, as described in ancient Roman texts. An adiabatic thermal model of the 10 m2 by 5.7 m thick Baianus Sinus breakwater from heat evolved through hydration of lime and formation of C-A-S-H suggests maximum temperatures of 85 to 97 °C. Cooling to seawater temperatures occurred in two years. These elevated temperatures and the mineralizing effects of seawater and alkali- and alumina-rich volcanic ash appear to be critical to Al-tobermorite crystallization. The long-term stability of the Al-tobermorite provides a valuable context to improve future syntheses in innovative concretes with advanced properties using volcanic pozzolans.

Recommendations and Standardization of Biomarker Quantification Using NMR-Based Metabolomics with Particular Focus on Urinary Analysis

NMR-based metabolomics has shown considerable promise in disease diagnosis and biomarker discovery because it allows one to nondestructively identify and quantify large numbers of novel metabolite biomarkers in both biofluids and tissues. Precise metabolite quantification is a prerequisite to move any chemical biomarker or biomarker panel from the lab to the clinic. Among the biofluids commonly used for disease diagnosis and prognosis, urine has several advantages. It is abundant, sterile, and easily obtained, needs little sample preparation, and does not require invasive medical procedures for collection. Furthermore, urine captures and concentrates many “unwanted” or “undesirable” compounds throughout the body, providing a rich source of potentially useful disease biomarkers; however, incredible variation in urine chemical concentrations makes analysis of urine and identification of useful urinary biomarkers by NMR challenging. We discuss a number of the most significant issues regarding NMR-based urinary metabolomics with specific emphasis on metabolite quantification for disease biomarker applications and propose data collection and instrumental recommendations regarding NMR pulse sequences, acceptable acquisition parameter ranges, relaxation effects on quantitation, proper handling of instrumental differences, sample preparation, and biomarker assessment.

High energy lithium–oxygen batteries – transport barriers and thermodynamics

We show that it is possible to achieve higher energy density lithium–oxygen batteries by simultaneously lowering the discharge overpotential and increasing the discharge capacity via thermodynamic variables alone. By assessing the relative effects of temperature and pressure on the cell discharge profiles, we characterize and diagnose the critical roles played by multiple dynamic processes that have hindered implementation of the lithium–oxygen battery.