Optimisation of a sol-gel synthesis route for the preparation of MgF2 particles for a large scale coating process.

A synthesis route for the preparation of optically transparent magnesium fluoride sols using magnesium acetate tetrahydrate as precursor is described. The obtained magnesium fluoride sols are stable for several months and can be applied for antireflective coatings on glass substrates. Reaction parameters in the course of sol synthesis are described in detail. Thus, properties of the precursor materials play a crucial role in the formation of the desired magnesium fluoride nanoparticles, this is drying the precursor has to be performed under defined mild conditions, re-solvation of the dried precursor has to be avoided and addition of water to the final sol-system has to be controlled strictly. Important properties of the magnesium fluoride sols like viscosity, particle size distribution, and structural information are presented as well.

Nanoscopic yttrium oxide fluorides: non-aqueous fluorolytic sol-gel synthesis and structural insights by 19F and 89Y MAS NMR.

Nanoscopic yttrium acetate fluorides Y(CH(3)COO)(3-z)F(z) and yttrium oxide fluorides YO(3-z)/(2)F(z )were prepared with tunable Y/F molar ratios via the fluorolytic sol-gel route. All samples were characterized by X-ray diffraction, elemental analysis and thermal analysis. In addition, local structures of all samples were studied by (19)F MAS, (19)F-(89)Y CP MAS and (1)H-(89)Y CP MAS NMR spectroscopy and the respective chemical shifts are given. For both classes of compounds, only the fluorination using one equivalent of F (z = 1) leads to defined, well crystalline matrices: yttrium acetate fluoride Y(CH(3)COO)(2)F and r-YOF.

A new approach to prepare nanoscopic rare earth metal fluorides: the fluorolytic sol-gel synthesis of ytterbium fluoride.

A new approach for the preparation of approx. 5 nm sized ytterbium fluoride nanoparticles based on the fluorolytic sol-gel route is reported. DLS, TEM, IR and XRD were used to characterize the particles as well as the aging behavior of the sols. Furthermore, a new Yb(III) complex was isolated from the precursor solution and characterized by X-ray single crystal structure determination.

Preparation and stabilization of aluminium trifluoroacetate fluoride sols for optical coatings.

For the first time, aluminium fluorides in liquid phase are available for optical applications. By modifying the conditions of the fluorolytic sol-gel synthesis of aluminium fluorides transparent sols with low viscosities were obtained. These sols consist mainly of small oligomeric or cluster units of aluminium fluoride which are not measurable by DLS, WAXS, SAXS and show unusual narrow signals in solid state NMR. Isolated particles with diameters up to five nanometers can be identified by TEM measurements and allow the use of their sols in optical and anti reflecting coatings. The sol particles were modified by trifluoroacetic acid to prevent agglomeration, and as a result, the obtained xerogels can be re-dispersed transparently in organic solvents.

Mechanistic insight into formation and changes of nanoparticles in MgF2 sols evidenced by liquid and solid state NMR.

The fluorolytic sol-gel reaction of magnesium methoxide with HF in methanol was studied by (19)F, (1)H and (13)C liquid and solid state NMR. In (19)F NMR five different species were identified, three of which belong to magnesium fluoride nanoparticles, i.e. NMR gave access to local structures of solid particles in suspensions. The long-term evolution of (19)F signals was followed and along with (19)F MAS NMR experiments of sols rotating at 13 kHz mechanistic insights into the ageing processes were obtained.

New crystalline aluminum alkoxide oxide fluorides: evidence of the mechanism of the fluorolytic sol-gel reaction.

This study reports three new crystalline aluminum isopropoxide oxide fluorides with molar ratios of Al:F equal to 1:1 and 1:1.25. These are the first three representatives isolated without the incorporation of external donor molecules. Compound 1 Al(4)F(4)(µ(4)-O)(µ-O(i)Pr)(5)[H(O(i)Pr)(2)] contains a tetranuclear unit consisting of two different five fold coordinated AlFO(4)-units, with F exclusively in the terminal position. Compound 2, Al(4)F(4)(µ(4)-O)(µ-O(i)Pr)(5)[H(O(i)Pr)(2)]·Al(5)F(5)(µ(5)-O)(µ-O(i)Pr)(8), contains both a tetranuclear unit (as in 1) and a pentanuclear Al-unit. Al-atoms in the latter are five- and six fold coordinated. Compound 3, Al(16)F(20)(µ(4)-O)(4)(µ-O(i)Pr)(20)·2((i)PrOH), exhibits a slightly higher fluorination degree and contains an oligomeric chain of four F-linked tetranuclear Al-units. In addition to X-ray structure analysis, compound 1 was characterized by different solid state MAS NMR techniques, including (27)Al triple quantum MAS NMR and (1)H, (1)H→(13)C CP, (19)F and (27)Al MAS NMR. On the basis of the collected data, a reliable decomposition of (27)Al single pulse MAS NMR spectra and an unambiguous assignment of the resonances to the respective structural AlFO(4)-units are given. The new crystalline aluminum isopropoxide oxide fluorides are direct evidence of the fluorolytic sol-gel mechanism previously discussed.

New inserts and low temperature--two strategies to overcome the bottleneck in MAS NMR on wet gels.

MAS NMR experiments on wet and dry aluminium alkoxide fluoride gels are presented here for the first time. For the MAS studies on wet jelly like gels special inserts were developed which fit perfectly a 4mm rotor and allow rotation frequencies up to 12 kHz. Six different insert materials were tested concerning their suitability including different organic polymers ((poly(methyl methacrylate) (PMMA), poly(ether ether ketone) (PEEK), poly(vinylchloride) (PVC) and poly(tetrafluorethylene) (PTFE)), glass as well as pure quartz (SiO(2)). Alternatively, low-temperature MAS NMR experiments taken at 150K with the wet gel frozen directly in the rotor led to comparable results. (27)Al, (19)F, (13)C, (1)H were used as nuclear spin probes to identify local structures in the wet as well as in the dry xerogels. Both wet and dry gels consist of a network structure of AlF(6-x)OiPr(x) species (x: 0-3). The main structural units of the dried gel are already preformed in the jelly like gel and change only little at aging and drying processes.

Impact of patient- and disease-specific factors on SLNB in breast cancer patients. Are current guidelines justified?

BACKGROUND: The evidence on which to base guidelines for sentinel lymph node biopsy (SLNB) in breast cancer is still limited. In order to facilitate the further implementation of renewed guidelines, we evaluated patient- and disease-specific factors for their impact on the results of SLNB. MATERIALS AND METHODS: Prospective data acquisition from patients undergoing surgery for primary invasive breast cancer was performed. All patients underwent SLNB using the radiocolloid or the combined technique. The association of patient- and disease-specific factors to detection rate and false-negative rate was calculated using univariate and multivariate analyses (P < 0.05 considered as significant). Calculation of the false-negative rate was based on patients who underwent a backup axillary dissection. RESULTS: Among 455 consecutively enrolled patients, a significant inverse association to the detection rate was found for extracapsular extension of non-SLN metastases, body mass index (BMI), number of involved lymph nodes, pT category, tumor size, and age. A significant association to the false-negative rate to identify macrometastases was found for pT category, tumor size, and grading. Other factors, such as prior surgery, multicentric tumor growth, or vascular invasion, showed no influence. A cut-point analysis revealed that a tumor size of 2 cm separated the collective of patients with the highest significance in regard to the false-negative rate (9% vs. 25%). CONCLUSION: Our results indicate that SLNB can be safely used in elderly and obese patients with multicentric tumors and those having undergone prior surgery for benign breast disease. However, the method should be applied with caution in patients with tumors larger than 2 cm.

Perfluorocarbons useful tools for medicine.

Perfluorocarbons (PFCs) combine rather unique chemical and physical properties together with physiological inertness. Due to this, they have become useful tools in medicine. Whereas the majority of applications benefit from their excellent oxygen solubility, there are several applications making use of other PFC properties. The great importance of PFC ultra-purity is especially emphasized.