Natural Abundance Research Articles

Evaluation of Hepatic Glucose and Palmitic Acid Metabolism in Rodents on High‐Fat Diet Using Deuterium Metabolic Imaging

BackgroundOne of the main features of several metabolic disorders is dysregulation of hepatic glucose and lipid metabolism. Deuterium metabolic imaging (DMI) allows for assessing the uptake and breakdown of 2H‐labeled substrates, giving specific insight into nutrient processing in healthy and diseased organs. Thus, DMI could be a useful approach for analyzing the differences in liver metabolism of healthy and diseased subjects to gain a deeper understanding of the alterations related to metabolic disorders.PurposeEvaluating the feasibility of DMI as a tool for the assessment of metabolic differences in rodents with healthy and fatty livers (FLs).Study TypeAnimal Model.Population18 male Sprague Dawley rats on standard (SD, n = 9, healthy) and high‐fat diet (HFD, n = 9, FL disease).Field Strength/SequencePhase‐encoded 1D pulse‐acquire sequence and anatomy co‐registered phase‐encoded 3D pulse‐acquire chemical shift imaging for 2H at 9.4T.AssessmentLocalized and nonlocalized liver spectroscopy was applied at eight time points over 104 minutes post injection. The obtained spectra were preprocessed and quantified using jMRUI (v7.0) and the resulting amplitudes translated to absolute concentration (mM) according to the 2H natural abundance water peak.Statistical TestsTwo‐way repeated measures ANOVA were employed to assess between‐group differences, with statistical significance at P < 0.05.ResultsDMI measurements demonstrated no significant difference (P = 0.98) in the uptake of [6,6′‐2H2]glucose between healthy and impaired animals (AUCSD = 1966.0 ± 151.5 mM ‐ minutes vs. AUCHFD = 2027.0 ± 167.6 mM·minutes). In the diseased group, the intrahepatic uptake of palmitic acid d‐31 was higher (AUCHFD = 57.4 ± 17.0 mM·minutes, AUCSD = 33.3 ± 10.5 mM·minutes), but without statistical significance owing to substantial in‐group variation (P = 0.73).Data ConclusionDMI revealed higher concentrations of palmitic acid in rats with FL disease and no difference in hepatic glucose concentration between healthy and impaired animals. Thus, DMI appears to be a useful tool for evaluating metabolism in rodents with FL disease.Level of Evidence2Technical EfficacyStage 3.

Nondestructive determination of isotopic abundance using multi-energy nuclear resonance fluorescence driven by laser Compton scattering source

We report on the quantitative nondestructive analysis of the natural isotopic abundances of hafnium and tungsten elements using nuclear resonance fluorescence. Metallic samples of hafnium and tungsten were irradiated to six quasi-monochromatic γ-ray beams generated by laser Compton scattering in the energy range of 2.4–3.2 MeV. Multiple nuclei were simultaneously excited at each of the six γ-ray beam energies. A high-purity germanium detector array detected deexcitations of the nuclei. In total, 51 transitions were unprecedentedly employed to estimate the isotopic abundances of heavy elements nondestructively. The estimated abundances of three hafnium isotopes and three tungsten isotopes are consistent with standard known natural abundances within the experimental uncertainties. The deviation from the standard values ranges from 0.18% to 1.36%.

Root mucilage nitrogen for rhizosphere microorganisms under drought

Nitrogen (N) is a crucial nutrient for the growth and activity of rhizosphere microorganisms, particularly during drought conditions. Plant root-secreted mucilage contains N that could potentially nourish rhizosphere microbial communities. However, there remains a significant gap in understanding mucilage N content, its source, and its utilization by microorganisms under drought stress. In this study, we investigated the impact of four maize varieties (DH02 and DH04 from Kenya, and Kentos and Keops from Germany) on the secretion rates of mucilage from aerial roots and explored the origin of mucilage N supporting microbial life in the rhizosphere. We found that DH02 exhibited a 96% higher mucilage secretion rate compared to Kentos, while Keops showed 114% and 89% higher secretion rates compared to Kentos and DH04, respectively. On average, the four maize varieties released 4 μg N per root tip per day, representing 2% of total mucilage secretion. Notably, the natural abundance of 15N isotopes increased (higher δ15N signature) with mucilage N release. This indicates a potential dilution of the isotopic signal from biological fixation of atmospheric N by mucilage-inhabiting bacteria as mucilage secretion rates increase. We proposed a model linking mucilage secretion to a mixture of isotopic signatures and estimated that biological N fixation may contribute to 45 - 75% of mucilage N per root tip. The N content of mucilage from a single maize root tip can support a bacterial population ranging from 107 to 1010 cells per day. In conclusion, mucilage serves as a significant N-rich resource for microbial communities in the rhizosphere during drought conditions.

Natural low corrosive phytic acid electrolytes enable green, ultrafast, stable and high-voltage aqueous proton battery

Proton is a promising charge carrier for aqueous rechargeable batteries due to its small ionic radius, fast diffusion kinetics and great abundance in nature. However, commonly-used proton battery electrolytes are strong acids, such as sulfuric acid, phosphoric acid, etc., which always leads to the notorious rapid corrosion of electrode and metal components, and thus the poor cyclability, the limited materials option and high maintenance cost. Here, we reported a new-type high-concentration phytic acid (PA) electrolytes, which exhibits marvellous superiorities including environmental friendliness, low corrosiveness, high ionic conductivity (133.3 mS cm−1) and wide working potential window (∼2.9 V) in contrast to conventional acid electrolytes. The experimental and calculation results indicated that the scarcity of free water in high-concentration PA electrolytes and the desolvation effect of the preferentially absorbed PA interfacial layer on the electrode surface work in synergy to inhibit the water activity and thus prevent electrode dissolution and side reactions. Benefiting from this, the assembled K0.2VO0.6[Fe(CN)6]0.8•6H2O (VHCF)//MoO3 button-type proton battery shows an average discharge voltage of 0.7 V with a pair of well-defined redox peak at about 1.4 V, great rate performance, excellent cycling stability (87.9% capacity retention after 1000 cycles at 5 A g−1) and superb coulombic efficiency at various current densities (1 A g−1–50 A g−1). Attributed to good anti-freezing properties of the electrolytes, the proton battery can also run normally at -60 °C and exhibit competent performance (a capacity retention of 45 mAh g−1 at 0.1 A g−1 after 540 cycles). Such green low corrosive electrolyte will be fully compatible with conventional battery fabrication process, and open brand new avenue for the development of aqueous proton battery.

Large enrichments in fatty acid 2H/1H ratios distinguish respiration from aerobic fermentation in yeast Saccharomyces cerevisiae

Shifts in the hydrogen stable isotopic composition (2H/1H ratio) of lipids relative to water (lipid/water 2H-fractionation) at natural abundances reflect different sources of the central cellular reductant, NADPH, in bacteria. Here, we demonstrate that lipid/water 2H-fractionation (2εfattyacid/water) can also constrain the relative importance of key NADPH pathways in eukaryotes. We used the metabolically flexible yeast Saccharomyces cerevisiae, a microbial model for respiratory and fermentative metabolism in industry and medicine, to investigate 2εfattyacid/water. In chemostats, fatty acids from glycerol-respiring cells were >550‰ 2H-enriched compared to those from cells aerobically fermenting sugars via overflow metabolism, a hallmark feature in cancer. Faster growth decreased 2H/1H ratios, particularly in glycerol-respiring cells by 200‰. Variations in the activities and kinetic isotope effects among NADP+-reducing enzymes indicate cytosolic NADPH supply as the primary control on 2εfattyacid/water. Contributions of cytosolic isocitrate dehydrogenase (cIDH) to NAPDH production drive large 2H-enrichments with substrate metabolism (cIDH is absent during fermentation but contributes up to 20 percent NAPDH during respiration) and slower growth on glycerol (11 percent more NADPH from cIDH). Shifts in NADPH demand associated with cellular lipid abundance explain smaller 2εfattyacid/water variations (<30‰) with growth rate during fermentation. Consistent with these results, tests of murine liver cells had 2H-enriched lipids from slower-growing, healthy respiring cells relative to fast-growing, fermenting hepatocellular carcinoma. Our findings point to the broad potential of lipid 2H/1H ratios as a passive natural tracker of eukaryotic metabolism with applications to distinguish health and disease, complementing studies that rely on complex isotope-tracer addition methods.

Enhancement of ferroelectricity in chemical-solution-deposited ZrO2 thin films through fine phase transition control

Recent studies have highlighted the ferroelectric potential of ZrO2 thin films, which offer advantages over HfO2-based ferroelectric materials, such as lower thermal budget and greater natural abundance. In this research, pure ZrO2 ferroelectric thin films were fabricated on Si substrates using chemical solution deposition with all-inorganic precursors. We explored the impacts of film thickness and HfO2 seed layers on phase transition and ferroelectric properties. Notably, an 11 nm thick ZrO2 film exhibited ferroelectric behavior with a remanent polarization of 12.6 μC/cm2. Due to the combined effects of tensile stress and surface energy, the increase in thickness to 30 nm led to a phase transition from the orthorhombic phase to the monoclinic phase and a resultant decrease in remanent polarization. Additionally, the introduction of a HfO2 seed layer facilitated the crystallization of the ferroelectric o-phase, enhancing the remanent polarization to 16.5 μC/cm2 in our ∼8 nm thick ZrO2 thin film with a ∼2 nm thick HfO2 seed layer. These findings provide valuable insights into optimizing ferroelectric properties in ZrO2 thin films through phase transition control.

Active Media Perfusion in Bioprinted Highly Concentrated Collagen Bioink Enhances the Viability of Cell Culture and Substrate Remodeling.

The bioprinting of high-concentrated collagen bioinks is a promising technology for tissue engineering and regenerative medicine. Collagen is a widely used biomaterial for bioprinting because of its natural abundance in the extracellular matrix of many tissues and its biocompatibility. High-concentrated collagen hydrogels have shown great potential in tissue engineering due to their favorable mechanical and structural properties. However, achieving high cell proliferation rates within these hydrogels remains a challenge. In static cultivation, the volume of the culture medium is changed once every few days. Thus, perfect perfusion is not achieved due to the relative increase in metabolic concentration and no medium flow. Therefore, in our work, we developed a culture system in which printed collagen bioinks (collagen concentration in hydrogels of 20 and 30 mg/mL with a final concentration of 10 and 15 mg/mL in bioink) where samples flow freely in the culture medium, thus enhancing the elimination of nutrients and metabolites of cells. Cell viability, morphology, and metabolic activity (MTT tests) were analyzed on collagen hydrogels with a collagen concentration of 20 and 30 mg/mL in static culture groups without medium exchange and with active medium perfusion; the influence of pure growth culture medium and smooth muscle cells differentiation medium was next investigated. Collagen isolated from porcine skins was used; every batch was titrated to optimize the pH of the resulting collagen to minimize the difference in production batches and, therefore, the results. Active medium perfusion significantly improved cell viability and activity in the high-concentrated gel, which, to date, is the most limiting factor for using these hydrogels. In addition, based on SEM images and geometry analysis, the cells remodel collagen material to their extracellular matrix.

Highly dispersed cobalt clusters/nanoparticles embedded in cellulose nanocrystal derived carbon aerogel as efficient sulfur host for high performance lithium sulfur batteries

Exploring multifunctional sulfur host materials with high immobilization ability and catalytic activity is of great significance for realizing high-performance Lithium-sulfur (Li–S) batteries. Recently, cellulose nanocrystals (CNCs) receive extensive attention for advanced energy storage applications owing to their intrinsically exceptional physical/chemical properties and natural abundance. Herein, a highly dispersed cobalt clusters/nanoparticles embedded into CNC derived carbon aerogel composite (CA/Co-2) is for the first time synthesized. Benefiting from the interconnected hierarchical porous structure, homogeneously anchored Co clusters/nanoparticles and N-doped species, the designed CA/Co-2 could enable rapid electron/ion transport, efficient sulfur utilization, effective suppression of the shuttle effect and fast catalytic conversion of polysulfides, thereby contributing to outstanding electrochemical performance. Consequently, CA/Co-2@S cathode delivers high initial discharge capacity (1553.1 mAh g−1 at 0.1C) and superior cycle stability. Moreover, a remarkable rate performance of 681.4 mAh g−1 at 5.0C and exceptional long-term cycling stability with an ultralow capacity decay of 0.028 % per cycle at 5.0C over 1000 cycles could be achieved when coupled with carbon paper interlayer. This work develops a workable strategy for fabricating multifunctional sulfur host derived from the fascinating bio-nanomaterial of CNC, which provides valuable guidance for the future design of high-performance Li–S batteries.

Antimicrobial Properties of Carboxymethyl Cellulose/Starch/N'N Methylenebisacrylamide Membranes Endowed by Ultrasound and Their Potential Application in Antimicrobial Packaging.

Cellulose is used widely in antimicrobial packaging due to its abundance in nature, biodegradability, renewability, non-toxicity, and low cost. However, how efficiently and rapidly it imparts high antimicrobial activity to cellulose-based packaging materials remains a challenge. In this work, Ag NPs were deposited on the surface of carboxymethyl cellulose/starch/N'N Methylenebisacrylamide film using ultrasonic radiation. Morphology and structure analysis of as-prepared films were conducted, and the antibacterial effects under different ultrasonic times and reductant contents were investigated. These results showed that Ag NPs were distributed uniformly on the film surface under an ultrasonic time of 45 min. The size of Ag NPs changes as the reducing agent content decreases. The composite film demonstrated a slightly better antibacterial effect against E. coli than against S. aureus. Therefore, this work can provide valuable insights for the research on antimicrobial packaging.

Synergistic Cathode Design for High-Performance Dual-Salt Magnesium/Lithium-Ion Batteries Using 2D/2D 1T/2H-MoS2@Ti3C2Tx MXene Nanocomposite.

Magnesium-ion batteries (MIBs) and dual-salt magnesium/lithium-ion batteries (MLIBs) have emerged as promising contenders for next-generation energy storage. In contrast to lithium metal anode in lithium metal batteries, magnesium metal anode in MIBs and MLIBs presents a safer alternative due to the limited dendrite growth and higher volumetric capacity, along with higher natural abundance. This study explores a MLIB configuration with a novel cathode design by employing a 2D/2D nanocomposite of 1T/2H mixed phase MoS2 and delaminated Ti3C2Tx MXene (1T/2H-MoS2@MXene) to address challenges associated with slow kinetics of magnesium ions during cathode interactions. This cathode design takes advantage of the high electrical conductivity of Ti3C2Tx MXene and the expanded interlayer spacing with enhanced conductivity of the 1T metallic phase in 1T/2H mixed phase MoS2. Through a designed synthesis method, the resulting nanocomposite cathode maintains structural integrity, enabling the stable and reversible storage of dual Mg2+ and Li+ ions. The nanocomposite cathode demonstrates superior performance in MLIBs compared to individual components (253 mAh g-1 at 50 mA g-1, and 36% of capacity retention at 1,000 mA g-1), showcasing short ion transport paths and fast ion storage kinetics. This work represents a significant advancement in cathode material design for cost-effective and safeMLIBs.

Dual-Tuned Coaxial-Transmission-Line RF Coils for Hyperpolarized 13C and Deuterium 2H Metabolic MRS Imaging at Ultrahigh Fields.

Information on the metabolism of tissues in healthy and diseased states plays a significant role in the detection and understanding of tumors, neurodegenerative diseases, diabetes, and other metabolic disorders. Hyperpolarized carbon-13 magnetic resonance imaging (13C-HPMRI) and deuterium metabolic imaging (2H-DMI) are two emerging X-nuclei used as practical imaging tools to investigate tissue metabolism. However due to their low gyromagnetic ratios (ɣ13C = 10.7 MHz/T; ɣ2H = 6.5 MHz/T) and natural abundance, such method required a sophisticated dual-tuned radiofrequency (RF) coil. Here, we report a dual-tuned coaxial transmission line (CTL) RF coil agile for metabolite information operating at 7T with independent tuning capability. The design analysis has demonstrated how both resonant frequencies can be individually controlled by simply varying the constituent of the design parameters. Numerical results have demonstrated a broadband tuning range capability, covering most of the X-nucleus signal, especially the 13C and 2H spectra at 7T. Furthermore, in order to validate the feasibility of the proposed design, both dual-tuned 1H/13C and 1H/2H CTLs RF coils are fabricated using a semi-flexible RG-405 .086" coaxial cable and bench test results (scattering parameters and magnetic field efficiency/distribution) are successfully obtained. The proposed dual-tuned RF coils reveal highly effective magnetic field obtained from both proton and heteronuclear signal which is crucial for accurate and detailed imaging. The successful development of this new dual-tuned RF coil technique would provide a tangible and efficient tool for ultrahigh field metabolic MR imaging.

Phosphorus‐based anodes for fast‐charging alkali metal ion batteries

AbstractAdvancing fast‐charging technology is an important strategy for the development of alkali metal ion batteries (AMIBs). The exploitation of a new generation of anode material system with high‐rate performance, high capacity, and low risk of lithium/sodium/potassium plating is critical to realize fast‐charging capability of AMIBs while maintaining high energy density and safety. Among them, phosphorus‐based anodes including phosphorus anodes and metal phosphide anodes have attracted wide attention, due to their high theoretical capacities, safe reaction voltages, and natural abundance. In this review, we summarize the research progress of different phosphorus‐based anodes for fast‐charging AMIBs, including material properties, mechanisms for storing alkali metal ions, key challenges and solution strategies for achieving fast‐charging capability. Moreover, the future development directions of phosphorus‐based anodes in fast‐charging AMIBs are highlighted.image

Xylans as a promising prebiotic agent: a brief review

Xylans are the most abundant hemicelluloses in nature, constituting components of the secondary cell wall of plant cells. They are polysaccharides with versatile properties, which can be used in various industrial sectors. Several biological activities have been identified in different xylans, such as antioxidant, antitumor, antimicrobial, emulsifying, anticoagulant, and immunomodulatory activities. Among these applications of xylans, its use as a prebiotic stands out, composing functional foods. Xylans form non-digestible dietary fibers that serve as a source of energy for beneficial microorganisms, modifying the intestinal microbiome and bringing a general improvement to the health status of those who consume them. The literature reports the use of xylooligosaccharides as promoters of the growth of probiotic microorganisms, such as species of Lactobacillus and Bifidobacterium, in addition to treating dysbiosis and reducing intestinal inflammation. Due to their structural diversity, abundance in nature, and a wide range of biological properties, xylans are valuable components that can be used to create various products aimed at enhancing human health.

Enhanced Copper Ion Adsorption by Rice Husk and Sugarcane Bagasse-based Magnetic Nanoparticles Biocomposites

Rice husk and sugarcane bagasse are biomass waste by-products of agriculture activities. High cellulose content makes them a potential material to develop. Biomass utilization is more interesting to develop due to its high cellulose content and nature abundance. Cellulose from rice husk and sugarcane bagasse is utilized as fiber in producing magnetic biocomposites. The Biocomposites can adsorb Cu(II) ions in aqueous solutions. A one-step solvothermal reaction was used to synthesize biocomposites. The amine functionalization on biocomposites was also studied for adsorption performance. The magnetic particle was generated on the surface of fiber and verified by XRD as Fe3O4. Amine group on biocomposites is also found on 570 cm-1 and 1636 cm−1 peaks for Fe-O bonds and N-H bending, respectively. Batch isothermal adsorption employing magnetic biocomposites has optimal conditions for Cu(II) ions adsorption at pH 5 for 60 minutes, with an adsorption capacity of 118.26 mg/g. The reusability of biocomposites for the next run showed a good performance at 3rd repetitions with only a decrease in adsorption capacity of 8.81%. The rice husk and sugarcane bagasse-based magnetic nanoparticles biocomposites can adsorb Cu(II) ions and potential material to develop for wastewater treatment.

Synthesis, characterisation, and catalytic application of a soluble molecular carrier of sodium hydride activated by a substituted 4-(dimethylamino)pyridine

Recently main group compounds have stepped into the territory of precious transition metal compounds with respect to utility in the homogeneous catalysis of fundamentally important organic transformations. Inspired by the need to promote more sustainability in chemistry because of their greater abundance in nature, this change of direction is surprising since main group metals generally do not possess the same breadth of reactivity as precious transition metals. Here, we introduce the dihydropyridylsodium compound, Na-1,2-tBu-DH(DMAP), and its monomeric variant [Na-1,2-tBu-DH(DMAP)]·Me6TREN, and demonstrate their effectiveness in transfer hydrogenation catalysis of the representative alkene 1,1-diphenylethylene to the alkane 1,1-diphenylethane using 1,4-cyclohexadiene as hydrogen source [DMAP = 4-dimethylaminopyridine; Me6TREN = tris(N,N-dimethyl-2-aminoethyl)amine]. Sodium is appealing because of its high abundance in the earth’s crust and oceans, but organosodium compounds have been rarely used in homogeneous catalysis. The success of the dihydropyridylsodium compounds can be attributed to their high solubility and reactivity in organic solvents.

Unravelling and reconstructing the biosynthetic pathway of bergenin

Bergenin, a rare C-glycoside of 4-O-methyl gallic acid with pharmacological properties of antitussive and expectorant, is widely used in clinics to treat chronic tracheitis in China. However, its low abundance in nature and structural specificity hampers the accessibility through traditional crop-based manufacturing or chemical synthesis. In the present work, we elucidate the biosynthetic pathway of bergenin in Ardisia japonica by identifying the highly regio- and/or stereoselective 2-C-glycosyltransferases and 4-O-methyltransferases. Then, in Escherichia coli, we reconstruct the de novo biosynthetic pathway of 4-O-methyl gallic acid 2-C-β-D-glycoside, which is the direct precursor of bergenin and is conveniently esterified into bergenin by in situ acid treatment. Moreover, further metabolic engineering improves the production of bergenin to 1.41 g L−1 in a 3-L bioreactor. Our work provides a foundation for sustainable supply of bergenin and alleviates its resource shortage via a synthetic biology approach.

Facile synthesis of TiO2 nanothorn-coated Cu2O nanowires with improved stability and performance for photoelectrochemical water splitting

Copper(I) oxide (Cu2O) based photocathodes are promising in photoelectrochemical (PEC) water splitting due to their bandgap, natural abundance, and low cost. However, the stability issues have impeded their practical application. This study presents a solution through a novel photocathode, TiO2 nanothorns-coated Cu2O nanowires (TCNW), synthesized using simple wet chemical methods. TCNW outperformed pristine Cu2O nanowires (CNW), achieving a stable PEC current density of ∼3.8 mA∙cm−2 at 0 V vs RHE, compared to ∼1.9 mA∙cm−2 of CNW. TCNW also displayed an H2 evolution rate of ∼64.2 μmol∙cm−2∙h−1 with a 93.9% faradaic efficiency, whilst CNW reached only ∼6.8 μmol∙cm−2∙h−1 and 37.3%. These improvements stem from the protective TiO2 nanothorn layer, which enhances light absorption (300–500 nm) and improves charge separation and transfer by forming a p-n junction with Cu2O. This work underscores the importance of well-crafted surface p-n junctions and conformal protective layers in optimizing the efficiency and stability.

Making 1H-1H Couplings More Accessible and Accurate with Selective 2DJ NMR Experiments Aided by 13C Satellites.

1H-1H coupling constants are one of the primary sources of information for nuclear magnetic resonance (NMR) structural analysis. Several selective 2DJ experiments have been proposed that allow for their individual measurement at pure shift resolution. However, all of these experiments fail in the not uncommon case when coupled protons have very close chemical shifts. First, the coupling between protons with overlapping multiplets is inaccessible due to the inability of a frequency-selective pulse to invert just one of them. Second, the strong coupling condition affects the accuracy of coupling measurements involving third spins. These shortcomings impose a limit on the effectiveness of state-of-the-art experiments, such as G-SERF or PSYCHEDELIC. Here, we introduce two new and complementary selective 2DJ experiments that we coin SERFBIRD and SATASERF. These experiments overcome the aforementioned issues by utilizing the 13C satellite signals at natural isotope abundance, which resolves the chemical shift degeneracy. We demonstrate the utility of these experiments on the tetrasaccharide stachyose and the challenging case of norcamphor, for the latter achieving measurement of all JHH couplings, while only a few were accessible with PSYCHEDELIC. The new experiments are applicable to any organic compound and will prove valuable for configurational and conformational analyses.

Induced Aggregation, Solvent Regulation, and Supracluster Assembly of Aluminum Oxo Clusters.

ConspectusRecent years have witnessed the development of cluster materials as they are atomically precise molecules with uniform size and solution-processability, which are unattainable with traditional nanoparticles or framework materials. The motivation for studying Al(III) chemistry is not only to understand the aggregation process of aluminum in the environment but also to develop novel low-cost materials given its natural abundance. However, the Al-related clusters are underdeveloped compared to the coinage metals, lanthanides, and transition metals. The challenge in isolating crystalline compounds is the lack of an effective method to realize the controllable hydrolysis of Al(III) ions. Compared with the traditional hydrolysis of inorganic Al(III) salts in highly alkaline solutions and hydrolysis of aluminum trialkyl compounds conducted carefully in an inert operating environment, we herein developed an effective way to control the hydrolysis of aluminum isopropanol through an alcoxalation reaction. By solvothermal/low melting point solid melting synthesis and using "ligand aggregation, solvent regulation, and supracluster assembly" strategies, our laboratory has established an organic-inorganic hybrid system of aluminum oxo clusters (AlOCs). The employment of organic ligands promotes the aggregation and slows the hydrolysis of Al(III) ions, which in turn improves the crystallization process. The regulation of the structure types can be achieved through the selection of ligands and the supporting solvents. Compared with the traditional condensed polyoxoaluminates, we successfully isolated a broad range of porous AlOCs, including aluminum molecular rings and Archimedes aluminum oxo cages. By studying ring expansion, structural transformation, and intermolecular supramolecular assembly, we demonstrate unique and unprecedented structural controllability and assembly behavior in cluster science. The advancement of this universal synthetic method is to realize materials customization through modularly oriented supracluster assembly. In this Account, we will provide a clear-cut definition and terminology of "ligand aggregation, solvent regulation, and supracluster assembly". Then we will discuss the discovery in this area by using a strategy, such as aluminum molecular ring, ring size expansion, ring supracluster assembly, etc. Furthermore, given the internal and external pore structures, as well as the solubility and modifiability of the AlOCs, we will demonstrate their potential applications in both the solid and liquid phases, such as iodine capture, the optical limiting responses, and dopant in polymer dielectrics. The strategy herein can be applied to extensive cluster science and promote the research of main group element chemistry. The new synthetic method, fascinating clusters, and unprecedented assembly behaviors we have discovered will advance Al(III) chemistry and will also lay the foundation for functional applications.

Analysis of the rotationally-resolved 3.3 µm region of C2H4 in natural isotopic abundance

Ethylene (or ethene) is a natural gas compound present in our atmosphere but also in the atmospheres of outer solar system planets such as Jupiter, Saturn, Uranus, Neptune and Saturn's moon Titan. However, a better knowledge of spectroscopic parameters is needed for this molecule in order to detect its presence and/or to derive its accurate concentration. We present here a detailed analysis and modeling of the strongly absorbing ν9 and ν11 fundamental bands in the 3.3 µm region. Due to the complexity of the observed spectrum, we have built a polyad scheme taking into account some fundamental bands previously analyzed thanks to the tensorial formalism developed in Dijon for asymmetric-top molecules. A four polyad system has been settled and the last P3 polyad contains four vibrational states: ν9, ν11, ν2+ν12 and 2ν10+ν12. A first frequency analysis has been performed, leading to 3328 assignments with a root mean square of 5.927 × 10−3 cm−1 and a standard deviation of 1.965 using 88 adjusted parameters, and we have also adjusted line intensities of 2190 lines by adjusting 14 parameters with an overall Root-Mean-Square (RMS) deviation of about 3.77 %. A new linelist of calculated lines in the 2900−3300 cm−1 region has been added to the ECaSDa and we plan to integrate it to the HITRAN database.