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A convenient method for the synthesis of gamma-spirolactams in only three steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of chloroacetonitrile affords nitriles in moderate to good yields. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and anthroic acid. Subsequent catalytic hydrogenation proceeds smoothly with PtO2 or Raney Ni as catalysts and lactams are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation at different pressures, affording products with 0, 1, or 2 double bonds. Overall, more than 15 new gamma-spirolactams have been synthesized in analytically pure form.
Influence of functional groups on the ene reaction of singlet oxygen with 1,4-cyclohexadienes
(2021)
The photooxygenation of 1,4-cyclohexadienes has been studied with a special focus on regio- and stereoselectivities. In all examples, only the methyl-substituted double bond undergoes an ene reaction with singlet oxygen, to afford hydroperoxides in moderate to good yields. We explain the high regioselectivities by a "large-group effect" of the adjacent quaternary stereocenter. Nitriles decrease the reactivity of singlet oxygen, presumably by quenching, but can stabilize proposed per-epoxide intermediates by polar interactions resulting in different stereoselectivities. Spiro lactams and lactones show an interesting effect on regio- and stereoselectivities of the ene reactions. Thus, singlet oxygen attacks the double bond preferentially anti to the carbonyl group, affording only one regioisomeric hydroperoxide. If the reaction occurs from the opposite face, the other regioisomer is exclusively formed by severe electrostatic repulsion in a perepoxide intermediate. We explain this unusual behavior by the fixed geometry of spiro compounds and call it a "spiro effect" in singlet oxygen ene reactions.
In this paper, we introduce a fluorescent dye 1, which is able to detect selectively Pd2+ by a clear fluorescence enhancement (FE) in THF. In the presence of eight Pd2+ equivalents, we observed a fluorescence enhancement factor (FEF) of 28.3. The high Pd2+ induced FEF can be explained by an off switching of multiple quenching processes within 1 by Pd2+. In the free dye 1 a photoinduced electron transfer (PET) and energy transfer (ET) takes place and quenches the anthracenic fluorescence. The coordination of eight Pd2+ units by the alkylthio-substituted porphyrazine receptor suppresses the PET and ET quenching process and the anthracenic fluorescence is switched on.
The palladium-catalyzed oxidative Heck-reaction, also referred to as Fujiwara-Moritani-reaction, has been investigated for the synthesis of styrenylsulfonyl compounds. Acetanilides and vinylsulfonyl compounds undergo dehydrogenative coupling reactions in moderate to quantitative yields, using benzoquinone as the oxidant of choice. Potassium peroxodisulfate, which had previously been identified as a superior oxidant for the coupling with acrylates, did not provide any coupling products with these olefins. Traceless removal of the catalyst directing group through a deacetylation-diazotation-coupling (DDC) sequence was demonstrated for 2-arylethene sulfones.
Janus droplets were prepared by vortex mixing of three non-mixable liquids, i.e., olive oil, silicone oil and water, in the presence of gold nanoparticles (AuNPs) in the aqueous phase and magnetite nanoparticles (MNPs) in the olive oil. The resulting Pickering emulsions were stabilized by a red-colored AuNP layer at the olive oil/water interface and MNPs at the oil/oil interface. The core–shell droplets can be stimulated by an external magnetic field. Surprisingly, an inner rotation of the silicon droplet is observed when MNPs are fixed at the inner silicon droplet interface. This is the first example of a controlled movement of the inner parts of complex double emulsions by magnetic manipulation via interfacially confined magnetic nanoparticles.
In this paper the development, use, and evaluation of tasks based on the construct of school-related content knowledge are described. The tasks were used in seminars on organic chemistry for bachelor and master preservice chemistry teachers at a German university. For the evaluation a questionnaire with open and closed items was used. The tasks were rated by the preservice chemistry teachers as relevant for their future profession as a chemistry teacher if the content of the tasks is part of the school curriculum. If the content does not belong to the school curriculum, they rated the nature of the tasks still as relevant; they seem to recognize the importance of conceptual knowledge for their future profession. However, the master's preservice teachers argued with this conceptual knowledge more often than the bachelor's preservice teachers. Although the study is cross-sectional, a certain shift from the focus on the content to conceptual knowledge from bachelor's to master's preservice teachers can be observed.
The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of bent cyclobutylcarbene 8, 1,2-diboretane-3-ylidene 9, and some carbene analogues of boron 14-18 as most intriguing examples of carbenes, which can be stabilized as homoaromatic systems with 3c,2e bonding, have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values (actually, ring current effect/anisotropy effects as measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the degree of present 3c,2e-homoaromaticity. Results are confirmed by geometry (bond angles and bond lengths) and spectroscopic data, the delta(B-11)/ppm data and the C-13 chemical shifts of the carbene electron-deficient centre.
The photoinduced nonadiabatic dynamics of the enol-keto isomerization of 10-hydroxybenzo[h]quinoline (HBQ) are studied computationally using high-dimensional quantum dynamics. The simulations are based on a diabatic vibronic coupling Hamiltonian, which includes the two lowest pi pi* excited states and a n pi* state, which has high energy in the Franck-Condon zone, but significantly stabilizes upon excited state intramolecular proton transfer. A procedure, applicable to large classes of excited state proton transfer reactions, is presented to parametrize this model using potential energies, forces and force constants, which, in this case, are obtained by time-dependent density functional theory. The wave packet calculations predict a time scale of 10-15 fs for the photoreaction, and reproduce the time constants and the coherent oscillations observed in time- resolved spectroscopic studies performed on HBQ. In contrast to the interpretation given to the most recent experiments, it is found that the reaction initiated by 1 pi pi* <- S-0 photoexcitation proceeds essentially on a single potential energy surface, and the observed coherences bear signatures of Duschinsky mode-mixing along the reaction path. The dynamics after the 2 pi pi* <- S-0 excitation are instead nonadiabatic, and the n pi* state plays a major role in the relaxation process. The simulations suggest a mainly active role of the proton in the isomerization, rather than a passive migration assisted by the vibrations of the benzoquinoline backbone. <br /> [GRAPHICS] <br /> .
The spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of stable O, S and Hal analogues of N-heterocyclic carbenes (NHCs) have been calculated using the GIAO perturbation method employing the nucleus-independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSSs) of various sizes and directions. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the position of the present mesomeric equilibria (carbenes <-> ylides). The results are confirmed by geometry (bond angles and bond lengths), IR spectra, UV spectra, and C-13 chemical shifts of the electron-deficient carbon centers.
In this paper, we describe a study on tasks following the construct of school-related content knowledge. We know from previous studies that such tasks were rated by the preservice chemistry teachers as important for their future profession. Those studies were conducted in a traditional course on organic chemistry which was organized around chemical families. Therefore, we used and evaluated the tasks again in a new course on organic chemistry which is organized around basic concepts in organic chemistry. The results of this evaluation show that the students rate the tasks equally well but use other arguments for their rating. They do not focus only on the content of the tasks and whether this content belongs to the school curriculum or not. The students of the conceptual course rated the content more often (95%) as important for their future profession compared with the students in the traditional course (57%). Both groups of students rated the importance of the nature of the task the same way.
Educational Scaffolding was first mentioned in 1976 by Wood et al. Several examples for scaffolding in chemistry are also known from the literature. As written scaffolds, stepped supporting tools to support students while solving problems in organic chemistry were developed, applied, and evaluated. Although the students rated the tool as very helpful, a think-aloud study showed that the support given by this scaffold was not sufficient. As a further development of stepped supporting tools, task navigators were therefore developed, applied, and evaluated. This new scaffold gives tips on strategy, knowledge, and application of knowledge after the STRAKNAP concept. The evaluation of this tool shows that the students rated the tool as being very helpful. A think-aloud study showed that the scaffold supports the students while they solve a problem. Because of the stepwise construction of the task navigators and the providing of the knowledge needed for the application, the students can solve parts of the task successfully even if they do not solve all parts correctly; the students can always start from scratch. When students use the tool regularly, their knowledge of organic chemistry increases compared to students who did not use the tool at all. The task navigator is not only a scaffold for the content of the task but also for the development of methodological competences on the field of strategies and applying knowledge.
A convenient method for the synthesis of γ-spirolactones in only 2–3 steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of ethylene oxide affords hydroxy acids, which undergo direct lactonization during work-up. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and dicarboxylic acids. Subsequent hydrogenation proceeds smoothly with Pd/C as catalyst and saturated γ-spirolactones are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation with Raney nickel or Wilkinson's catalyst to obtain products with 1 double bond. Overall, more than 30 new γ-spirolactones have been synthesized in analytically pure form.
Ethylene oxide sterilization of electrospun poly(L-lactide)/poly(D-lactide) core/shell nanofibers
(2021)
The application of polymers in medicine requires sterilization while retaining material structure and properties. This demands detailed analysis, which we show exemplarily for the sterilization of PLLA/PDLA core-shell nanofibers with ethylene oxide (EtO). The electrospun patch was exposed to EtO gas (6 vol% in CO2, 1.7 bar) for 3 h at 45 degrees C and 75% rel. humidity, followed by degassing under pressure/vacuum cycles for 12 h. GC-MS analysis showed that no residual EtO was retained. Fiber diameters (similar to 520 +/- 130 nm) of the patches remained constant as observed by electron microscopy. Young's modulus slightly increased and the elongation at break slightly decreased, determined at 37 degrees C. No changes were detected in H-1-NMR spectra, in molar mass distribution (GPC) or in crystallinity measured for annealed samples with comparable thermal history (Wide Angle X-Ray Scattering). Altogether, EtO emerged as suitable sterilization method for polylactide nanofibers with core-shell morphology.
The numerous applications of rare earth elements (REE) has lead to a growing global demand and to the search for new REE deposits. One promising technique for exploration of these deposits is laser-induced breakdown spectroscopy (LIBS). Among a number of advantages of the technique is the possibility to perform on-site measurements without sample preparation. Since the exploration of a deposit is based on the analysis of various geological compartments of the surrounding area, REE-bearing rock and soil samples were analyzed in this work. The field samples are from three European REE deposits in Sweden and Norway. The focus is on the REE cerium, lanthanum, neodymium and yttrium. Two different approaches of data analysis were used for the evaluation. The first approach is univariate regression (UVR). While this approach was successful for the analysis of synthetic REE samples, the quantitative analysis of field samples from different sites was influenced by matrix effects. Principal component analysis (PCA) can be used to determine the origin of the samples from the three deposits. The second approach is based on multivariate regression methods, in particular interval PLS (iPLS) regression. In comparison to UVR, this method is better suited for the determination of REE contents in heterogeneous field samples. View Full-Text
Label-free optical sensors are attractive candidates, for example, for detecting toxic substances and monitoring biomolecular interactions. Their performance can be pushed by the design of the sensor through clever material choices and integration of components. In this work, two porous materials, namely, porous silicon and plasmonic nanohole arrays, are combined in order to obtain increased sensitivity and dual-mode sensing capabilities. For this purpose, porous silicon monolayers are prepared by electrochemical etching and plasmonic nanohole arrays are obtained using a bottom-up strategy. Hybrid sensors of these two materials are realized by transferring the plasmonic nanohole array on top of the porous silicon. Reflectance spectra of the hybrid sensors are characterized by a fringe pattern resulting from the Fabry–Pérot interference at the porous silicon borders, which is overlaid with a broad dip based on surface plasmon resonance in the plasmonic nanohole array. In addition, the hybrid sensor shows a significant higher reflectance in comparison to the porous silicon monolayer. The sensitivities of the hybrid sensor to refractive index changes are separately determined for both components. A significant increase in sensitivity from 213 ± 12 to 386 ± 5 nm/RIU is determined for the transfer of the plasmonic nanohole array sensors from solid glass substrates to porous silicon monolayers. In contrast, the spectral position of the interference pattern of porous silicon monolayers in different media is not affected by the presence of the plasmonic nanohole array. However, the changes in fringe pattern reflectance of the hybrid sensor are increased 3.7-fold after being covered with plasmonic nanohole arrays and could be used for high-sensitivity sensing. Finally, the capability of the hybrid sensor for simultaneous and independent dual-mode sensing is demonstrated.
Training OC
(2021)
The course design "Training OC" for training the application of basic concepts consists of four topics: formula language, structure-property relations, reaction mechanisms, and complex tasks that the students should solve with the conceptual knowledge they acquired in the first three topics. A main goal of the course was to enable the students to solve reaction mechanisms. To achieve the goals of the course, several games were specially designed and used. The course was conducted at a German university with ca. 30 students who participated voluntarily. The course was evaluated by several tools: students' products were collected in the course, there were two pre/post-tests, and additionally, interviews on the strategy of designing reaction mechanisms were conducted. The performance of the teacher and the self-assessment of the students were also part of the evaluation. The results of the written exam were compared with the results of the bachelor chemistry major students. The course "Training OC" was rated very well by the students. They were of the opinion that they learned the application of basic concepts taught in this course. This is supported by the results of the evaluation and the written exams. The course concept of Training OC will therefore become a permanent part of the course "Organic Chemistry I" which will be redesigned for the next round in 2020-21.
The reaction of flavanones with hypervalent iodine reagents was investigated with a view to the synthesis of naturally occurring isoflavones. In contrast to several previous reports in the literature, we did not observe the formation of any benzofurans via a ring contraction pathway, but could isolate only isoflavones, resulting from an oxidative 2,3-aryl rearrangement, and flavones, resulting from an oxidation of the flavanones. Although the 2,3-oxidative rearrangement allows a synthetically useful approach toward some isoflavone natural products due to the convenient accessibility of the required starting materials, the overall synthetic utility and generality of the reaction appear to be more limited than previous literature reports suggest.
The photooxygenation of naphthalene to the corresponding endoperoxide (EPO) under various conditions is described. Substantial conversion is only observed at -10 degrees C and after more than two days, indicating that the [4+2] cycloaddition of singlet oxygen to this acene proceeds much more slowly than corresponding reactions of substituted naphthalenes, a rate constant of k = 5.4 +/- 0.3 M(-1)s(-1) was determined by competition kinetics. Another problem is the thermal lability and photochemical cleavage of the naphthalene EPO. We investigated the mechanism of this radical process depending on the light source and sensitizer in comparison to known cyclohexadiene EPO. Thus, bisepoxides and keto epoxides are formed after homolysis of the O-O bond by irradiation with sodium lamps or blue LEDs and subsequent cyclization. This process is accelerated by the sensitizers methylene blue and 9,10-dicyanoanthracene, indicating an electron transfer mechanism. Finally, the cleavage of the peroxidic bond is inhibited with red LEDs, and photooxygenation under such conditions affords 20 % EPO. Thus, we could demonstrate that contrary to literature statements singlet oxygen does indeed react with naphthalene.
Stereoselective [4+2] Cycloaddition of Singlet Oxygen to Naphthalenes Controlled by Carbohydrates
(2021)
Stereoselective reactions of singlet oxygen are of current interest. Since enantioselective photooxygenations have not been realized efficiently, auxiliary control is an attractive alternative. However, the obtained peroxides are often too labile for isolation or further transformations into enantiomerically pure products. Herein, we describe the oxidation of naphthalenes by singlet oxygen, where the face selectivity is controlled by carbohydrates for the first time. The synthesis of the precursors is easily achieved starting from naphthoquinone and a protected glucose derivative in only two steps. Photooxygenations proceed smoothly at low temperature, and we detected the corresponding endoperoxides as sole products by NMR. They are labile and can thermally react back to the parent naphthalenes and singlet oxygen. However, we could isolate and characterize two enantiomerically pure peroxides, which are sufficiently stable at room temperature. An interesting influence of substituents on the stereoselectivities of the photooxygenations has been found, ranging from 51:49 to up to 91:9 dr (diastereomeric ratio). We explain this by a hindered rotation of the carbohydrate substituents, substantiated by a combination of NOESY measurements and theoretical calculations. Finally, we could transfer the chiral information from a pure endoperoxide to an epoxide, which was isolated after cleavage of the sugar chiral auxiliary in enantiomerically pure form.