Tuning the aspect ratio of arrays of silica nanochannels

Arrays of silica nanochannels (ASNCs) are ordered mesoporous silica particles with hexagonal prismatic shape. The entrances of the well-defined one-dimensional nanochannels are located on the base surfaces of the hexagonal prisms. The aspect ratio of the micrometer-sized particles (length-to-diameter ratio) can be tuned in the range of 0.8 to 2.2 by the addition of co-ions (K+ and Ca2+) to the hexadecyltrimethylammonium bromide (CTAB) templated synthesis and by an adjustment of the relative amounts of silica precursor (tetraethoxysilane) and CTAB. The length of the nanochannels can be varied between 2 and 9 μm. Co-ions thereby not only improve the regularity of the hexagonal prismatic particle shape, but also affect the diameter of the nanochannels, which lies at approximately 2.6 nm (with K+ as co-ion) and 3.2 nm (with Ca2+ as co-ion)

Functionalization of arrays of silica nanochannels by post-condensation

Functionalized arrays of silica nanochannels (ASNCs) were prepared by post-condensation of amino-functional alkoxysilanes (NH-silanes). The method of post-condensation combines postsynthetic grafting and co-condensation – the classical pathways for the functionalization of mesoporous silica – to afford a convenient one-pot reaction in aqueous medium. The structure of the NH-silanes determines the distribution of the surface-bound groups in the ASNCs. Accumulation at the channel entrances was observed by confocal laser scanning microscopy in the case of sterically hindered NH-silanes, whereas smaller NH-silanes led to a more uniform distribution. In all cases, the channels remained accessible for additional postsynthetic treatment or introduction of guests after extraction of the structure-directing agent. The particle size and morphology, as well as the pore size and the degree of ordering of the amino-functionalized ASNCs were comparable to pristine ASNCs

Massgeschneiderte Nanokanäle

https://www.zhaw.ch/de/lsfm/forschung/projekte-und-publikationen/transfer

Indigo in the nanochannels of zeolite L : towards a new type of colorant

A host-guest based colorant was synthesized by intercalating indigo molecules into the nanochannels of zeolite L (ZL). Reductive washing thereby ensured the efficient and selective removal of non-intercalated indigo molecules. The UV-vis diffuse reflectance spectrum of the product after intercalation and reductive washing (designated as indigo-ZL) was found to resemble the solution spectrum of indigo, leading to the conclusion that the formation of indigo aggregates is prevented due to the steric constraints imposed by the microporous structure of ZL. The application of indigo-ZL on cotton was tested by roll coating. The light absorption properties of the resulting textile prints showed no significant alteration when compared to the pure indigo-ZL powder. The UV-vis diffuse reflectance spectra of mixtures consisting of indigo-ZL and a further ZL-based colorant were successfully predicted by the weighted addition of the respective primary spectra

The structure of mesoporous silica obtained by pseudomorphic transformation of SBA-15 and SBA-16

Mesoporous silica with bimodal pore size distributions was prepared by pseudomorphic transformation of SBA-15 and SBA-16 in the presence of hexadecyltrimethylammonium ions as a structure-directing agent. The characteristic particle morphology of the starting materials was retained after the transformation. Analysis of the products by gas sorption and small-angle X-ray scattering (SAXS) revealed hybrid pore structures, which featured – depending on the degree of transformation – variable contributions from the original and the newly introduced pore systems. In the case of SBA-15, it was found that a high degree of transformation leads to a seemingly complete conversion of the original pores with a diameter of 7.1 nm to pores with a diameter of 4.0 nm. The SAXS pattern of the product shows additional peaks that can be assigned to the original SBA-15 pore spacing. Similarly, a cubic phase could be observed in the samples prepared by pseudomorphic transformation of SBA-16, despite an almost complete conversion of the SBA-16 cavities. This leads to the conclusion that the pore structure of the starting material significantly affects the outcome of the pseudomorphic transformation, thus opening possibilities for the synthesis of new porous materials with complex pore systems

IGLV3-21*01 is an inherited risk factor for CLL through the acquisition of a single-point mutation enabling autonomous BCR signaling

The prognosis of chronic lymphocytic leukemia (CLL) depends on different markers, including cytogenetic aberrations, oncogenic mutations, and mutational status of the immunoglobulin (Ig) heavy-chain variable (IGHV) gene. The number of IGHV mutations distinguishes mutated (M) CLL with a markedly superior prognosis from unmutated (UM) CLL cases. In addition, B cell antigen receptor (BCR) stereotypes as defined by IGHV usage and complementarity-determining regions (CDRs) classify ∼30% of CLL cases into prognostically important subsets. Subset 2 expresses a BCR with the combination of IGHV3-21-derived heavy chains (HCs) with IGLV3-21-derived light chains (LCs), and is associated with an unfavorable prognosis. Importantly, the subset 2 LC carries a single-point mutation, termed R110, at the junction between the variable and constant LC regions. By analyzing 4 independent clinical cohorts through BCR sequencing and by immunophenotyping with antibodies specifically recognizing wild-type IGLV3-21 and R110-mutated IGLV3-21 (IGLV3-21R110), we show that IGLV3-21R110-expressing CLL represents a distinct subset with poor prognosis independent of IGHV mutations. Compared with other alleles, only IGLV3-21*01 facilitates effective homotypic BCR-BCR interaction that results in autonomous, oncogenic BCR signaling after acquiring R110 as a single-point mutation. Presumably, this mutation acts as a standalone driver that transforms IGLV3-21*01-expressing B cells to develop CLL. Thus, we propose to expand the conventional definition of CLL subset 2 to subset 2L by including all IGLV3-21R110-expressing CLL cases regardless of IGHV mutational status. Moreover, the generation of monoclonal antibodies recognizing IGLV3-21 or mutated IGLV3-21R110 facilitates the recognition of B cells carrying this mutation in CLL patients or healthy donors

Prolonged higher dose methylprednisolone vs. conventional dexamethasone in COVID-19 pneumonia: a randomised controlled trial (MEDEAS)

Dysregulated systemic inflammation is the primary driver of mortality in severe COVID-19 pneumonia. Current guidelines favor a 7-10-day course of any glucocorticoid equivalent to dexamethasone 6 mg·day-1. A comparative RCT with a higher dose and a longer duration of intervention was lacking

Strategies for localizing multiple functional groups in mesoporous silica particles through a one-pot synthesis

The process of postcondensation for the functionalization of mesoporous silica is based on the cooperation between the end-on growth of arrays of silica nanochannels and the steric hindrance of the functional silanes (R-silanes). To obtain particles with differently functionalized surfaces (thiol and amino groups), the delayed addition of another R-silane was introduced. This tandem postcondensation approach allows for three selective functionalization strategies, depending on the mobility and the steric hindrance of the R-silanes. Following these one-pot synthesis strategies, functional groups can be placed independently on the pore entrances and on the internal surface of the mesoporous silica particles. Confocal laser scanning microscopy was used to image the functional group distribution after selective coupling with a fluorescent dye. Nitrogen sorption measurements were conducted to confirm the well-defined mesoporosity of the functionalized products

Synthesis of advanced mesoporous materials by partial pseudomorphic transformation

The structure of porous silica particles can be reorganized without alteration of the particle size and shape by the process of pseudomorphic transformation. Partial pseudomorphic transformation leads to ordered mesoporous silica with bimodal pore size distributions and bottleneck pores. Compared to the classical pathways of mesoporous silica synthesis, pseudomorphic transformation implies less compromise between pore structure and particle shape, while enabling the preparation of complex pore architectures