High-pressure neutron diffraction study of superhydrated natrolite

Neutron powder diffraction data were collected on a sample of natrolite and a 1:1 (v/v) mixture of perdeuterated methanol and water at a pressure of 1.87(11) GPa. The natrolite sample was superhydrated, with a water content double that observed at ambient pressure. All of the water deuterium atoms were located and the nature and extent of the hydrogen bonding elucidated for the first time. This has allowed the calculation of bond valence sums for the water oxygen atoms, and from this, it can be deduced that the key energetic factor leading to loss of the additional water molecule upon pressure release is the poor coordination to sodium cations within the pores.     

Infrared power generation in an insulated compartment

The mechanism that activates a bi‐junction power generator under the effects of heat is the Seebeck effect, that is, the production of voltage difference ΔV(t) is directly proportional to the temperature difference ΔT(t) between the “hot” and “cold” junctions of the device. This phenomenon is well established and is known as thermoelectric power generation. Here, it is shown that, instead, the causal and linear relationship between ΔV(t) and ΔT(t) is lost when continuous broadband infrared (CB‐IR) radiation illuminates a bi‐junction power generator in an insulated compartment. The observed phenomenon is IR power generation. Heat transfer calculations fail in explaining the experimental trends. The interaction between CB‐IR radiation and the charge carriers in the bi‐junction power generator might play a role in the ΔV(t) production, depending upon the geometry of the experimental setup. The longitudinal propagation of collective oscillations, for example, polaritons, in the plates protecting the “hot” and “cold” junctions of the bi‐junction power generator could explain the ΔV(t) production and the characteristic time constants. The findings should be considered in the design, fabrication, and improvement of thermopiles, power meters, and IR energy‐harvesting devices. © 2013 Wiley Periodicals, Inc. Complexity 19: 44–55, 2014     

库仑加线性位基态解析解

应用新发展的单一轨迹积分方法求解库仑加线性位的基态量子波函数,得到基态能量和波函数的一般解析表达式,并讨论了解的收敛性.应用此方法讨论了重夸克偶素系统.     

The Plasma Membrane as a Reservoir,Protective Shield,and Light‐Triggered Launch Pad for Peptide Therapeutics

Although peptide‐based therapeutics are finding increasing application in the clinic, extensive structural modification is typically required to prevent their rapid degradation by proteases in the blood. We have evaluated the ability of erythrocytes to serve as reservoirs, protective shields (against proteases), and light‐triggered launch pads for peptides. We designed lipidated peptides that are anchored to the surface of red blood cells, which furnishes a protease‐resistant environment. A photocleavable moiety is inserted between the lipid anchor and the peptide backbone, thereby enabling light‐triggered peptide release from erythrocytes. We have shown that a cell‐permeable peptide, a hormone (melanocyte stimulating hormone), and a blood‐clotting agent can be anchored to erythrocytes, protected from proteases, and photolytically released to create the desired biological effect.     

Dehydration-induced water disordering in a synthetic potassium gallosilicate natrolite

A new potassium gallosilicate zeolite with a natrolite topology (approximate formula K8.2Ga8.2Si11.8O40.11.5H2O) was synthesized under hydrothermal conditions and characterized as a function of temperature using monochromatic synchrotron X-ray powder diffraction and Rietveld analyses. Unlike the previously known tetragonal K8Ga8Si12O40.6H2O phase, the as-synthesized material contains twice the amount of water molecules in an ordered arrangement throughout the channels in an orthorhombic (I212121) symmetry. The ordered configuration of water molecules is stabilized below 300 K, whereas heating above 300 K results in a selective dehydration and subsequent disordering of water molecules in a tetragonal (I2d) symmetry. Above 400 K, the material transforms to a fully dehydrated tetragonal phase with a concomitant volume reduction of ca. 15%. The fully dehydrated material transforms back to its original state when rehydrated over a period of up to 2 weeks. The distribution of potassium cations within the channels remains largely unperturbed during the water rearrangements and their order-disorder transition within the channels.     

Quantitative determination of the cytidine deaminase inhibitor tetrahydrouridine (THU) in mouse plasma by liquid chromatography/electrospray ionization tandem mass spectrometry

A number of anticancer drugs are cytidine analogues that undergo metabolic deactivation catalyzed by cytidine deaminase (CD). 3,4,5,6-Tetrahydrouridine (THU) is a potent inhibitor of CD, by acting as a transition-state analogue of its natural substrate cytidine. However, to date its pharmacokinetic properties have not been fully characterized, which has impaired its optimal preclinical evaluation and clinical use. We report a liquid chromatography/tandem mass spectrometry (LC/MS/MS) assay for the sensitive, accurate and precise quantitation of THU in mouse plasma. Validation was performed according to FDA guidelines. The assay employed deuterated THU as the internal standard and an acetonitrile protein precipitation step. Separation, based on hydrophilic interaction chromatography, was achieved with an amino column and an isocratic mobile phase of 0.1% formic acid in acetonitrile and water followed by a wash. Chromatographic separation was followed by positive-mode electrospray ionization MS/MS detection in the multiple reaction monitoring (MRM) mode. The assay was accurate (92.5-109.9%) and precise (2.1-9.0%) in the concentration range of 0.2-50 microg/mL. Recovery from plasma was near-complete (92.9-119.3%) and ion suppression was negligible (-17.5 to -0.2%). Plasma freeze/thaw stability (93.1-102.1%), stability for 3 months at -80 degrees C (99.5-110.9%), and stability for 4 h at room temperature (92.1-102.4%) were all in order. This assay is currently being used to quantitate THU in ongoing pharmacokinetic studies. In addition, the assay is expected to be a useful tool in any future studies involving co-administration of THU with cytidine analogues.     

Anionic gallium-based metal-organic framework and its sorption and ion-exchange properties

A gallium-based metal-organic framework Ga(6)(C(9)H(3)O(6))(8)·(C(2)H(8)N)(6)(C(3)H(7)NO)(3)(H(2)O)(26) [1, Ga(6)(1,3,5-BTC)(8)·6DMA·3DMF·26H(2)O], GaMOF-1; BTC = benzenetricarboxylate/trimesic acid and DMA = dimethylamine], with space group I43d, a = 19.611(1) ?, and V = 7953.4(6) ?(3), was synthesized using solvothermal techniques and characterized by synchrotron-based X-ray microcrystal diffraction. Compound 1 contains isolated gallium tetrahedra connected by the organic linker (BTC) forming a 3,4-connected anionic porous network. Disordered positively charged ions and solvent molecules are present in the pore, compensating for the negative charge of the framework. These positively charged molecules could be exchanged with alkali-metal ions, as is evident by an ICP-MS study. The H(2) storage capacity of the parent framework is moderate with a H(2) storage capacity of ~0.5 wt % at 77 K and 1 atm.