Reliable glycosylation reactions that allow for the stereo- and regioselective installation of glycosidic linkages are paramount to the chemical synthesis of glycan chains. The stereoselectivity of glycosylations is exceedingly difficult to control due to the reaction's high degree of sensitivity and its shifting, simultaneous mechanistic pathways that are controlled by variables of unknown degree of influence, dominance, or interdependency. An automated platform was devised to quickly, reproducibly, and systematically screen glycosylations and thereby address this fundamental problem. Thirteen variables were investigated in as isolated a manner as possible, to identify and quantify inherent preferences of electrophilic glycosylating agents (glycosyl donors) and nucleophiles (glycosyl acceptors). Ways to enhance, suppress, or even override these preferences using judicious environmental conditions were discovered. Glycosylations involving two specific partners can be tuned to produce either 11:1 selectivity of one stereoisomer or 9:1 of the other by merely changing the reaction conditions.

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Abstract. Deformation microstructures of albitic plagioclase and K-feldspar were investigated in mylonitic pegmatites from the Austroalpine basement south of the western Tauern Window by polarized light microscopy, electron microscopy and electron backscatter diffraction to evaluate feldspar deformation mechanisms at greenschist facies conditions. The main mylonitic characteristics are alternating almost monophase quartz and albite layers, surrounding porphyroclasts of deformed feldspar and tourmaline. The dominant deformation microstructures of K-feldspar porphyroclasts are intragranular fractures at a high angle to the stretching lineation. The fractures are healed or sealed by polyphase aggregates of albite, K-feldspar, quartz and mica, which also occur along intragranular fractures of tourmaline and strain shadows around other porphyroclasts. These polyphase aggregates indicate dissolution–precipitation creep. K-feldspar porphyroclasts are partly replaced by albite characterized by a cuspate interface. This replacement is interpreted to take place by interface-coupled dissolution–precipitation driven by a solubility difference between K-feldspar and albite. Albite porphyroclasts are replaced at boundaries parallel to the foliation by fine-grained monophase albite aggregates of small strain-free new grains mixed with deformed fragments. Dislocation glide is indicated by bent and twinned albite porphyroclasts with internal misorientation. An indication of effective dislocation climb with dynamic recovery, for example, by the presence of subgrains, is systematically missing. We interpret the grain size reduction of albite to be the result of coupled dislocation glide and fracturing (low-temperature plasticity). Subsequent growth is by a combination of strain-induced grain boundary migration and formation of growth rims, resulting in an aspect ratio of albite with the long axis within the foliation. This strain-induced replacement by nucleation (associated dislocation glide and microfracturing) and subsequent growth is suggested to result in the observed monophase albite layers, probably together with granular flow. The associated quartz layers show characteristics of dislocation creep by the presence of subgrains, undulatory extinction and sutured grain boundaries. We identified two endmember matrix microstructures: (i) alternating layers of a few hundred micrometres' width, with isometric, fine-grained feldspar (on average 15 µm in diameter) and coarse-grained quartz (a few hundred micrometres in diameter), representing lower strain compared to (ii) alternating thin layers of some tens of micrometres' width composed of fine-grained quartz (<20 µm in diameter) and coarse elongated albite grains (long axis of a few tens of micrometres) defining the foliation, respectively. Our observations indicate that grain size reduction by strain-induced replacement of albite (associated dislocation glide and microfracturing) followed by growth and granular flow simultaneous with dislocation creep of quartz are playing the dominating role in formation of the mylonitic microstructure.

Abstract. Epidote/allanite–fluorapatite coronae around monazite and xenotime are investigated in Permian pegmatites deformed under greenschist-facies conditions during Alpine tectonometamorphism in the Austroalpine basement, Eastern Alps. The aim was to evaluate the replacement reactions involved in the formation of a corona microstructure, its age and relation to deformation. In the corona core, monazite and xenotime single crystals show domains with different composition and age. Monazite (Mnz1) and xenotime (Xen1) dating by electron microprobe (EPM) reveals an age of 250–287 Ma, consistent with the Permian magmatic age of the pegmatites. These are partly replaced by secondary monazite (Mnz2) and xenotime (Xen2) compositions yielding younger Mesozoic (170–210 Ma) and Alpine (30–120 Ma) ages. The same crystallographic orientation of the primary and secondary monazite and xenotime indicates interface-coupled dissolution–precipitation reactions. Allanite U–Th–Pb dating by laser ablation inductively coupled mass spectrometry in the corona revealed an age of 60±6 Ma, interpreted as the age of corona formation. The coronae around monazite consist of an inner zone of equant fluorapatite grains surrounded by prismatic allanite, which are surrounded by epidote enriched in heavy rare earth elements (HREEs) and REE-poor epidote grains. Compared to coronae around monazite, fluorapatite has higher REE contents and no allanite occurs in the coronae surrounding the xenotime. General reactions for monazite and xenotime breakdown can be written as follows: Mnz1+(Si,Ca,Al,Fe,F)fluid→Mnz2+LREE-Ap+Aln+HREE-Ep+Ep+(Th,U)O2+(Th,U)SiO4,Xen1+(Si,Ca,Al,Fe,F)fluid→Xen2+HREE-Ap+HREE-Ep+Ep+(Th,U)O2. The amount of replacement (judged by the relative proportions of monazite and fluorapatite) is low for monazite included in tourmaline but high within the mylonitic foliation. This dependence on the degree of replacement on the local surrounding microfabric indicates that fluid availability along grain boundaries in the matrix and cracks controlled reaction advancement, allowing the elementary mass transfer required for corona formation (e.g. input of Ca, Al, Si, Fe, F). The oblate shape of the coronae aligned within the foliation of the pegmatites and the deflected foliation around the coronae, without an outer rim of prismatic epidote showing signs of deformation, indicate that the main stage of corona formation took place during deformation and reactions were still ongoing after the main stage of deformation. The corona microstructure documents replacement reactions of a single reactant into multiple distinct mineral growth zones by dissolution and precipitation processes at non-isostatic, greenschist-facies conditions, which prevailed in the area to the north of the Defereggen–Antholz–Vals shear zone between the middle Cretaceous and the Oligocene. These reactions ceased before being completed, and REE gradients within single grains within the corona and on the thin-section scale are preserved, which suggests restricted and/or episodic transport of REE in the fluid phase and/or availability of fluid.