Warum es sich lohnt,Chemie zu studieren: Chemiker ‐ und noch viel mehr!

For young people with inquiring minds and creative ability, a good chemistry qualification still offers an excellent route to an attractive career. Despite today being the age of automation and the Internet, the importance of the chemist's traditional role ‐ that of scientific discovery ‐ in the economy, academia and society will doubtlessly continue to grow. On the other hand, combining chemical expertise with knowledge and practical experience gained in other sought‐after disciplines ‐ economics, information technology, jurisprudence, journalism and educational science for example ‐ can also open the door to other highly attractive professions. Aside from inter‐disciplinary knowledge, certain personal characteristics ‐ social competence, skill at communicating and a readiness to make learning a continuous life‐long process in particular ‐ are decisive for success in such careers.     

Substituent Effects on the Blue—Shifting Hydrogen Bonds between X—C≡C—CF2—H and Water

MP2／6－31 g(d) calculations were performed verifying the existences of blue-shifting X-C≡C-CF2-H…OH2 hydrogen bonds.Detailed analyses revealed that the interaction energy and donor-acceptor distance had good correlations with the substituent Hammett constants.However,the extent of C-H bond contraction and the blue shift of the C-H stretching vibration did not show any good correlation with the traditional substituent constants,indicating that certain more complicated mechanisms might be involved in the present systems.Nevertheless,it was found that highly electron-with-drawing susbtituents were not favorable to the C-H bond contraction,and it was suggested that the attractive interaction between water and the carbon of -CF2H probably played an important role in the blue shift.     

Photoenolization of o‐Methylvalerophenone Ester Derivative

Photolysis of ester 1 in argon‐saturated methanol and acetonitrile does not produce any product, whereas irradiation of 1 in oxygen‐saturated methanol yields peroxide 2 . Laser flash photolysis studies demonstrate that 1 undergoes intramolecular H atom abstraction to form biradical 3 (λ _max ~ 340   nm), which intersystem crosses to form photoenols Z ‐ 4 and E ‐ 4 (λ _max ~ 380   nm). Photoenols 4 decay by regenerating ester 1 . With the aid of density functional theory calculations, it was concluded the photoenol E ‐ 4 does not undergo spontaneous lactonization or electrocyclic ring closure because the transition state barriers for these reactions are too large to compete with reketonization of E ‐ 4 to form 1 .     

Alternating copolymers incorporating cyclopenta[2,1‐b:3,4‐b′]dithiophene unit and organic dyes for photovoltaic applications

We have synthesized six p‐type copolymers, CPDT ‐ co ‐ TPADCN , CPDT ‐ co ‐ TPADTA , CPDT ‐ co ‐ TPATCN , CPDT ‐ co ‐ DFADCN , CPDT ‐ co ‐ DFADTA , and CPDT ‐ co ‐ DFATCN , consisting of a cyclopenta[2,1‐b:3,4‐b′]dithiophene (CPDT) unit and an organic dye in an alternating arrangement. Triphenylamine (TPA) or difluorenylphenyl amine (DFA) units serve as the electron donors, whereas dicyanovinyl (DCN), 1,3‐diethyl‐2‐thiobarbituric acid, or tricyanovinyl (TCN) units act as the electron acceptors in the dyes. The target polymers were prepared via Stille coupling, followed by postfunctionalization to introduce the electron acceptors to the side chains. Because of the strongest withdrawing ability of TCN acceptor to induce efficient intramolecular charge transfer, CPDT ‐ co ‐ TPATCN and CPDT ‐ co ‐ DFATCN exhibit the broader absorption spectra covering from 400 to 900 nm and the narrower optical band gaps of 1.34 eV. However, the CPDT ‐ co ‐ TPATCN :PC₇₁BM and CPDT ‐ co ‐ DFATCN :PC₇₁BM based solar cells showed the power conversion efficiencies (PCEs) of 0.22 and 0.31%, respectively, due to the inefficient exciton dissociation. The DFA‐based polymers possess deeper‐lying HOMO energy levels than the TPA‐based polymer analogues, leading to the higher V_oc values and better efficiencies. The device based on CPDT ‐ co ‐ DFADTA :PC₇₁BM blend achieved the best PCE of 1.38% with a V_oc of 0.7 V, a J_sc of 4.57 mA/cm², and a fill factor of 0.43. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

New routes to [n]‐polyurethanes. [3]‐polyurethane: synthesis,characterization, and polymerization‐depolymerization equilibrium

The ring‐opening polymerization of dimethylene urethane ( 3 ) (systematic name: 2‐oxo‐1,3‐oxazolidine) with methyl trifluoromethane sulfonate as the initiator is inefficient. It was shown that equimolar amounts of dimethylene urethane and trifluoromethane sulfonate result in the expected active species ‐ 2‐methoxy‐4,5‐dihydro‐1,3‐oxazolium trifluoromethane sulfonate ( 5a ) ‐ : propagation, however, does not occur. Poly(dimethylene urethane) ( 4 ), was obtained by means of polycondensation of a linear monomer, i.e., 2‐(2‐phenoxycarbonylimino‐1‐ethoxycarbonylimino)‐ethanol ( 9 ). This [3]‐polyurethane is a semicrystalline material with a melting point of 200.7°C. Heating above its melting point leads to dimethylene urethane by ring‐closing depolymerization. The thermodynamical data support the experimental results with respect to the polymerization/depolymerization equilibrium.     

Behaviors of self‐assembled diblock copolymer with pendant photosensitive azobenzene segments

A novel monomer, ethyl 4‐[4‐(11‐methacryloyloxyundecyloxy)phenyl azobenzoyl‐oxyl] benzoate, containing a photoisomerizable N?N group was synthesized. The monomer was further diblock copolymerized with methyl methacrylate. Amphiphilic diblock copolymer poly(methyl methacrylate‐block‐ethyl 4‐[4‐(11‐methacryloyloxyundecyloxy)phenyl azobenzoyl‐oxyl] benzoate ( PMMA ‐ b ‐ PAzoMA ) was synthesized using atom transfer radical polymerization. The reverse micelles with spherical construction were obtained with 2 wt % of the diblock copolymer in a THF/H₂O mixture of 1:2. Under alternating UV and visible light illumination, reversible changes in micellar structure between sphere and rod‐like particles took place as a result of the reversible E‐Z photoisomerization of azobenzene segments in PMMA ‐ b ‐ PAzoMA . Microphase separation of the amphiphilic diblock copolymer in thin films was achieved through thermal and solvent aligning methods. The microphases of the annealed thin films were investigated using atom force microscopy topology and scanning electron microscopy analyses. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1142–1148, 2010     

Investigation of Functionalized α‐Chloroalkyllithiums for a Stereospecific Reagent‐Controlled Homologation Approach to the Analgesic Alkaloid (−)‐Epibatidine

Four putative functionalized α‐chloroakyllithiums RCH₂CHLiCl, where R=CHCH₂ ( 18 a ), CCH ( 18 b ), CH₂OBn ( 18 c ), and CH[O(CH₂)₂O] ( 18 d ), were generated in situ by sulfoxide–lithium exchange from α‐chlorosulfoxides, and investigated for the stereospecific reagent‐controlled homologation (StReCH) of phenethyl and 2‐chloropyrid‐5‐yl ( 17 ) pinacol boronic esters. Deuterium labeling experiments revealed that α‐chloroalkyllithiums are quenched by proton transfer from their α‐chlorosulfoxide precursors and it was established that this effect compromises the yield of StReCH reactions. Use of α‐deuterated α‐chlorosulfoxides was discovered to ameliorate the problem by retarding the rate of acid‐base chemistry between the carbenoid and its precursor. Carbenoids 18 a and 18 b showed poor StReCH efficacy, particularly the propargyl group bearing carbenoid 18 b , the instability of which was attributed to a facile 1,2‐hydride shift. By contrast, 18 d , a carbenoid that benefits from a stabilizing interaction between O and Li atoms gave good StReCH yields. Boronate 17 was chain extended by carbenoids 18 a , 18 b , and 18 d in 16, 0, and 68 % yield, respectively; α‐deuterated isotopomers D ‐ 18 a and D ‐ 18 d gave yields of 33 and 79 % for the same reaction. Double StReCH of 17 was pursued to target contiguous stereodiads appropriate for the total synthesis of (?)‐epibatidine ( 15 ). One‐pot double StReCH of boronate 17 by two exposures to (S)‐D ‐ 18 a (≤66 % ee), followed by work‐up with KOOH, gave the expected stereodiad product in 16 % yield (d.r.～67:33). The comparable reaction using two exposures to (S)‐D ‐ 18 d (≤90 % ee) delivered the expected bisacetal containing stereodiad (R,R)‐DD ‐ 48 in 40 % yield (≥98 % ee, d.r.=85:15). Double StReCH of 17 using (S)‐D ‐ 18 d (≤90 % ee) followed by (R)‐D ‐ 18 d (≤90 % ee) likewise gave (R,S)‐DD ‐ 48 in 49 % yield (≥97 % ee, d.r.=79:21). (R,S)‐DD ‐ 48 was converted to a dideuterated isotopomer of a synthetic intermediate in Corey’s synthesis of 15 .     

i‐Chemometrics

When I was a young scientist, it was rare for me to read publications that were over 10 years old. How does one know what interesting information lies in publications older than oneself? A great deal of people investigate the roots of their family, likewise a scientist may also be interested in the roots of their science. This account attempts to achieve both: to provide some direction toward old and interesting literature and to share my passion of Chemometrics. Copyright © 2015 John Wiley & Sons, Ltd.     

1,2‐Diaza‐3‐silacyclopent‐5‐ene – Synthese und Reaktionen

1,2‐Diaza‐3‐silacyclopent‐5‐ene – Synthesis and Reactions The dilithium salt of bis(tert‐butyl‐trimethylsilylmethylen)ketazine ( 1 ) forms an imine‐enamine salt. 1 reacts with halosilanes in a molar ratio of 1:1 to give 1,2‐diaza‐3‐silacyclopent‐5‐enes. Me₃SiCH=CCMe₃ [N(SiR,R′)‐N=C‐C]HSiMe₃ ( 2 ‐ 7 ). ( 2 : R,R′ = Cl; 3 : R = CH₃, R′ = Ph; 4 : R = F, R′ = CMe₃; 5 : R = F, R′ = Ph; 6 : R = F, R′ = N(SiMe₃)₂; 7 : R = F, R′ = N(CMe₃)SiMe₃). In the reaction of 1 with tetrafluorosilane the spirocyclus 8 is isolated. The five‐membered ring compounds 2 ‐ 7 and compound 9 substituted on the silicon‐fluoro‐ and (tert‐butyltrimethylsilyl) are acid at the C(4)‐atom and therefore can be lithiated. Experiments to prepare lithium salts of 4 with MeLi, n‐BuLi and PhLi gave LiF and the substitution‐products 10 ‐ 12 . 9 forms a lithium salt which reacts with ClSiMe₃ to give LiCl and the SiMe₃ ring system ( 13 ) substituted at the C(4)‐atom. The ring compounds 3 ‐ 7 and 10 ‐ 12 form isomers, the formation is discussed. Results of the crystal structure and analyses of 8 , 10 , 12 , and 13 are presented.     

Nematic–isotropic phase behaviors of polydisperse polymer/liquid‐crystal systems: Chain‐length‐dependent interaction parameter

Phase behaviors of polydisperse polystyrene (PS)/nematic liquid‐crystal systems [P‐ethoxy ‐ benzylidene ‐ p ‐ n‐butylaniline (EBBA)] are investigated with a thermo‐optical analysis technique. We also develop a thermodynamic framework to describe the phase behaviors of polydisperse PS/EBBA systems. The proposed model is based on a modified double‐lattice model to describe isotropic mixing and Maier–Saupe theory for anisotropic ordering. To correlate the polymer chain length and energy parameters in a nematic–isotropic biphasic region and to apply the primary interaction parameter in an isotropic–isotropic phase‐transition behaviors of polydisperse PS/EBBA systems. The proposed model shows remarkable agreement with experimental data for the model systems in comparison with an existing model. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1031–1039, 2006     

Polymorphism of Amino Acid‐Based Dendrons: From Organogels to Microcrystals

There is a delicate balance for a low‐weight molecule to behave as a gelator or crystal. The synthesis of two novel amino acid‐based naphthalene‐dendrons, Nap ‐ G1 and Nap ‐ G2 is described. Both dendrons display polymorphic properties in organic solvents. Nap ‐ G1 developed a fibrous network with β‐sheet architecture in cyclohexane but exhibited a spherulitic network in mixed solvents (chloroform/petroleum ether 1:5, v/v). On the other hand, Nap ‐ G2 acted as an efficient organogelator in chloroform but formed crystalline fibers in relatively high polarity solvents (such as acetone and methanol). Combinations of characterizations have been employed to study the polymorphism.     

Towards a European Higher Education Area

The higher education system in Europe needs to be harmonised in order to enhance its international competitiveness. In the following article Terence N. Mitchell, professor of chemistry at Dortmund University, comments on the Bologna Declaration ‐ a political paper which affirms the creation of a European Higher Education Area. Does this declaration meet the necessary requirements and how does chemistry fit into the Bologna process?     

Was ist das Seltene an den Seltenen Erden?: Eine chemiedidaktische Reflexion

One of the main questions of science education is the selection of subjects, i.e.: Why do certain chemical subjects have to be taught? The answer implies the proving that the subject is scientifically relevant, has exemplifying features and is significant in every‐day‐life. The subject‐matter „Rare Earths”︁ does not seem to correspond to these criteria at first glance. The adjective „ rare”︁ evokes rather opposite associations. Perhaps rare earths are rare on earth and consequently of less scientific relevance? Perhaps they have rare properties and are therefore less exemplifying? Or they are even not relevant in our every‐day‐life? Definitely they are rare teaching subjects. At second glance the rare earth elements do correspond to the criteria and there are good reasons for including the topic in teacher education.     

The correlation of laboratory performance in proficiency testing with other QA characteristics

Although it seems self-evident that proficiency testing (PT) and accreditation can be expected to improve quality, their relative benefits remain uncertain as does their efficacy. The study reported here examines the following issues: (a) Why do laboratories take part in PT schemes? (b) How does participation in PT fit in with a laboratory's overall quality assurance (QA) system? (c) Is there a link between a laboratory's performance in specific PT and it's QA system? (d) How does PT performance change with time and how do laboratories respond to poor performance? The overall conclusion is that there is no evidence from the present study that laboratories with third-party assessment (accreditation and certification) perform any better in PT than laboratories without. The validity of this conclusion and its significance for the future design and operation of such schemes requires further investigation. In particular, study is required of the degree to which good performance in open PT correlates with blind PT performance, where laboratories are not aware that the samples being analysed are part of a quality assessment exercise.     

Comprehensive Evaluation of the Physicochemical Properties of LnIII Complexes of Aminoethyl‐DO3A as pH‐Responsive T1‐MRI Contrast Agents

N‐Substituted aminoethyl groups were attached to 1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid (DO3A) with the aim to design pH‐responsive Ln^III complexes based on the pH‐dependent on/off ligation of the amine nitrogen to the metal ion. The following ligands were synthesized: AE ‐ DO3A (aminoethyl‐DO3A), MAE ‐ DO3A (N‐methylaminoethyl‐DO3A), DMAE ‐ DO3A (N,N‐dimethylaminoethyl‐DO3A) and MEM ‐ AE ‐ DO3A (N‐methoxyethyl‐N‐methylaminoethyl‐DO3A). The physicochemical properties of the Ln^III complexes were investigated for the evaluation of their potential applicability as magnetic resonance imaging (MRI) contrast agents. In particular, a ¹H and ¹⁷O NMR relaxometric study was carried out for these Gd^III complexes at two different pH values: at basic pH (pendant amino group coordinated to the metal centre) and at acidic pH (protonated amine, not interacting with the metal ion). Eu^III complexes allow one to estimate the number of inner‐sphere water molecules through luminescence lifetime measurements and obtain some structural information through variable‐temperature (VT) high‐resolution ¹H NMR studies. Equilibria between differently hydrated species were found for most of the complexes at both acidic and basic pH. The thermodynamic stability of Ca^II, Zn^II, Cu^II and Ln^III complexes and kinetics of formation and dissociation reactions of Ln^III complexes of AE ‐ DO3A and DMAE ‐ DO3A were investigated showing stabilities comparable to currently approved Gd^III‐based CAs. In detail, higher total basicity (Σlog K_i^H) and higher stability constants of Ln^III complexes were found for AE ‐ DO3A with respect to DMAE ‐ DO3A (i.e., log K_{Gd‐ AE‐DO3A} =22.40 and log K_{Gd‐ DMAE‐DO3A} =20.56). The transmetallation reactions of Gd^III complexes are very slow (Gd‐ AE ‐ DO3A : t_1/2=2.7×10⁴ h; Gd‐ DMAE ‐ DO3A : 1.1×10⁵ h at pH 7.4 and 298 K) and occur through proton‐assisted dissociation.     

A Multifaceted Secondary Structure Mimic Based On Piperidine‐piperidinones

Minimalist secondary structure mimics are typically made to resemble one interface in a protein–protein interaction (PPI), and thus perturb it. We recently proposed suitable chemotypes can be matched with interface regions directly, without regard for secondary structures. Here we describe a modular synthesis of a new chemotype 1 , simulation of its solution‐state conformational ensemble, and correlation of that with ideal secondary structures and real interface regions in PPIs. Scaffold 1 presents amino acid side‐chains that are quite separated from each other, in orientations that closely resemble ideal sheet or helical structures, similar non‐ideal structures at PPI interfaces, and regions of other PPI interfaces where the mimic conformation does not resemble any secondary structure. 68 different PPIs where conformations of 1 matched well were identified. A new method is also presented to determine the relevance of a minimalist mimic crystal structure to its solution conformations. Thus dld ‐ 1 faf crystallized in a conformation that is estimated to be 0.91 kcal mol^?1 above the minimum energy solution state.     

Deutsche Bunsengesellschaft für Physikalische Chemie

Joint Meeting 2000 of Deutsche Bunsen–Gesellschaft für Physikalische Chemie, Koninklijke Nederlandse Chemische Vereniging The Royal Society of Chemistry‐ Faraday Division, Società Chimica Italiana ‐ Divisione di Chimica Fisica, Société Française de Chimie ‐Division de Chimie Physique, ‐ International Bunsen Discussion Meeting ‐„Physical Chemistry in Confining Geometries: From Single Molecules to Mesoscopic Systems”︁ 20. ‐ 22. September, Berlin, Germany.     

Synthesis and Applications of (ONO Pincer)Ruthenium‐Complex‐Bound Norvalines

Two (ONO pincer)ruthenium‐complex‐bound norvalines, Boc?[Ru(pydc)(terpy)]Nva?OMe ( 1 ; Boc=tert‐butyloxycarbonyl, terpy=terpyridyl, Nva=norvaline) and Boc?[Ru(pydc)(tBu‐terpy)]Nva?OMe ( 5 ), were successfully synthesized and their molecular structures and absolute configurations were unequivocally determined by single‐crystal X‐ray diffraction. The robustness of the pincer Ru complexes and norvaline scaffolds against acidic/basic, oxidizing, and high‐temperature conditions enabled us to perform selective transformations of the N‐Boc and C?OMe termini into various functional groups, such as alkyl amide, alkyl urea, and polyether groups, without the loss of the Ru center or enantiomeric purity. The resulting dialkylated Ru‐bound norvaline, n‐C₁₁H₂₃CO?l ‐[Ru(pydc)(terpy)]Nva?NH‐n‐C₁₁H₂₃ (l ‐ 4 ) was found to have excellent self‐assembly properties in organic solvents, thereby affording the corresponding supramolecular gels. Ru‐bound norvaline l ‐ 1 exhibited a higher catalytic activity for the oxidation of alcohols by H₂O₂ than parent complex [Ru(pydc)(terpy)] ( 11 a ).     

On‐chip generation of monodisperse giant unilamellar lipid vesicles containing quantum dots

Monodispersed lipid vesicles have been used as a drug delivery vehicle and a biochemical reactor. To generate monodispersed lipid vesicles in the nano‐ to micrometer size range, an extrusion step should be included in conventional hand‐shaking method of lipid vesicle synthesis. In addition, lipid vesicles as a drug carrier still need to be improved to effectively encapsulate concentrated biomolecules such as cells, proteins, and target drugs. To overcome these limitations, this paper reports a new microfluidic platform for continuous synthesis of small‐sized (～10 μm) giant unilamellar vesicles (GUVs) containing quantum dots (QDs) as a nanosized model drug. To generate GUVs, we introduced an additional cross‐flow to break vesicles into small size. 1,2 ‐ dimyristoyl‐sn‐glycero ‐ 3 ‐ phosphocholine (DMPC) in an octanol–chloroform mixture was used in the construction of self‐assembled membrane. Consequently, we have successfully demonstrated the fabrication of monodispersed GUVs with 7?12 μm diameter containing QDs. The proposed synthesis method of cell‐sized GUVs would be highly desirable for applications such as multipurpose drug encapsulation and delivery.