The pseudo‐square‐planar complexes [Rh(cod)(Hbbtm)]BF4 ( 3 ), [Rh(bbte)(cod)]BF4 ( 4 ), [Rh(CO)2(Hbbtm)]BF4 ( 5 ), [Rh(bbte)(CO)2]BF4 ( 6 ), [Rh(bbtm)(cod)] ( 7 ) and [Rh(bbtm)(CO)2] ( 8 ) (Hbbtm=bis(benzothiazol‐2‐yl)methane=2,2′‐methylenebis[benzothiazole], bbte=bis(benzothiazol‐2‐yl)ethane=2,2′‐(ethane‐1,2‐diyl)bis[benzothiazole], and cod=cycloocta‐1,5‐diene) were synthesized and characterized. Diastereotopic protons were observed for the protons at the bridge in the 1H‐NMR of 3 and 5 . Twisting of the ethane‐1,2‐diyl bridge in 4 and 6 effects chemical equivalence of the CH2 groups in solution. Unusually large downfield shifts occur on coordination of the deprotonated ligand Hbbtm as the negative charge is delocalized in 7 and 8 . The NMR signals of the cod ligand in 4 could be differentiated. The X‐ray crystal structures of 3, 4 , and 6 are reported. 相似文献
Swelling curves of chain end-linked polyurethane networks in mesogenic swelling agents were determined gravimetrically. Different slopes of the swelling curves are observed above and below the transition temperature of the liquid-crystalline to the isotropic state. From the sign of the slope it can be derived that the swelling agent is not in the liquid-like state in the gel if the pure swelling agent is liquid-crystalline. 相似文献
Summary: Applying a dialysis process, new nanoparticles based on well‐defined dextran esters of furan‐2‐carboxylic‐ and pyroglutamic acids were prepared, which can undergo cross‐linking by UV irradiation. The highly functionalized products (total DS > 2) avoid the collapse of nanoparticles due to the prevention of hydrogen bond formation. The major fraction of the dextran ester nanospheres exhibits narrow size distribution down to 250 nm as mean diameter investigated by SEM.
SEM images of dextran furoate pyroglutamate nanospheres. 相似文献
The tangent cones of an inner metric Alexandrov space with finite Hausdorff dimension and a lower curvature bound are always inner metric spaces with nonnegative curvature. In this paper we construct an infinite-dimensional inner metric Alexandrov
space of nonnegative curvature which has in one point a tangent cone whose metric is not an inner metric.
Received: 20 October 1999 / Revised version: 8 May 2000 相似文献
Activity coefficients for HCl in HCl + GaCl3 + H2O at eleven different temperatures from 5 to 55°C have been determined at total experimental ionic strengths from 0.01 to 3.0 mol-kg–1 using a cell of the type: Pt; H2(g, 1 atm)|HCl (mA) + GaCl3(mB)|AgCl, Ag (A) The results for the 770 experimental emf data points have been used to determine the variation of the activity coefficients of HCl with the change in molality of GaCl3 in the solution. It is found that the linear form of Harned's rule is not obeyed for this system. 相似文献
The preparation of highly modified mRNAs and visualization of their cellular distribution are challenging. We report in-cell application of in vitro transcribed mRNA containing natural base modifications and site-specifically introduced artificial nucleotides. Click chemistry on mRNA allows visualization in cells with excellent signal intensities. While non-specific introduction of reporter groups often leads to loss in mRNA functionality, we combined the benefits from site-specificity in the 3′-UTR incorporated unnatural nucleotides with the improved translation efficiency of the natural base modifications Ψ and 5mC. A series of experiments is described to observe, quantify and verify mRNA functionality. This approach represents a new way to visualize mRNA delivery into cells and monitor its spread on a cellular level and translation efficiency. We observed increased protein expression from this twofold chemically modified, artificial mRNA counterbalancing a reduced transfection rate. This synergetic effect can be exploited as a powerful tool for future research on mRNA therapeutics.Introducing unnatural base modifications site-specifically into the 3′-UTR of an mRNA bearing natural base modifications allows efficient visualization in cells by click chemistry. An enhanced protein expression in cells is observed from this twofold modified mRNA.相似文献
Isomeric states have been observed in fission-fragments produced by spontaneous fission of 252Cf. These states are found in neutron rich nuclei of different structure and deformations. About 50 isomeric nuclei have been
observed using coincidences between γ-rays identified in EUROGAM II and fission fragments detected in photovoltaic cells (SAPhIR).
Lifetimes in the range from 20 ns to 2μs have been measured. Presented calculations based on HFB +D1S force on new measured
isomeric states in the 152,154,156Nd show evidence for K-isomers.
Received: 3 November 1997 / Revised version: 15 December 1997 相似文献
In combining the high peak concentrations of capillary liquid chromatography (CapLC) with the high mass sensitivity of micro scale nuclear magnetic resonance (NMR) the hyphenation of CapLC to micro NMR offers a substantial gain in overall sensitivity. This paper deals with our experiences gained using a commercial CapLC-NMR system which has very recently become available. The limits of detection (SNR > 3) for a test compound of a molecular weight of M 318 were found to be approximately 100 ng (0.35 nmol) within an hour acquisition time and approximately 25 ng over night (85 pmol). Practical aspects such as the feasibility of stopped-flow experiments and sample handling issues are discussed in detail and first possible drug metabolite applications to hepatocyte incubations and direct analysis of plasma samples are presented. 相似文献
High-performance liquid chromatography-solid phase extraction-NMR spectroscopy (HPLC-SPE-NMR) has recently become commercially available and has been evaluated with regard to its applicability in a pharmaceutical environment. The addition of an automated SPE unit to an HPLC-NMR system for peak trapping results in an improved NMR signal-to-noise ratio (S/N) and also has other practical advantages. The trapping efficiency is shown to depend on compound polarity and is highest for compounds eluting late on reversed-phase HPLC systems. Multiple peak trapping further increases the S/N, again with the best results for less polar compounds. For polar compounds, multiple peak trapping resulted in no S/N gain as the amount of material retained on the SPE cartridge was equivalent to that from a single injection. When compared with conventional HPLC-NMR, a S/N gain of up to five-fold could be achieved for some compounds in a single trapping step. A major advantage of the technique is the independence of the chromatographic step from the NMR step, resulting in greater versatility than conventional HPLC-NMR in the HPLC solvents and NMR solvents that can be used. Practical applications from both drug metabolite and drug impurity identification are presented. 相似文献