Fundamental mechanisms of surface photochemistry

The fundamental mechanisms of photochemistry of molecules adsorbed on solid surfaces are revealed from results obtained by a combination of optical techniques, surface probes, and gas phase analysis. While photon-induced processes similar to those in the gas and liquid phase are observed for the adsorbed molecules, the presence of the substrate introduces important channels for energy exchange, dissipation, and adsorbate photochemistry.     

Water-soluble oligomer dimers based on paracyclophane: a new optical platform for fluorescent sensor applications

Water soluble paracyclophane chromophore dimers provide optical reporters that show little sensitivity to surfactants and thus are ideal for biosensor design. Strong intramolecular delocalization circumvents complications from intermolecular delocalization in spontaneously formed aggregates. The synthesis of 2 involves a novel TBAT deprotection/butane sultone ring-opening sequence, which should be general for the preparation of water-soluble conjugated oligomers and polymers.     

Synthesis and magnetic properties of liquid crystalline lanthanide complexes with alkylsulfate counterions

The reaction of Schiff"s base L with lanthanide alkylsulfates affords liquid crystalline complexes with the general formula L₃Ln(C_nH_2n+1OSO₃)₃. The liquid crystalline structure and magnetic properties are studied by polarization thermal microscopy, differential scanning calorimetry, X-ray diffraction, and measurement of magnetic susceptibility. The temperatures of the existence of the mesophase and magnetic anisotropy of the complexes with the same lanthanide depend on the chain length of the alkyl fragment in the sulfate anion.     

Swelling of physically cross-linked copolymers in water vapour

A general thermodynamic equation for the swelling of a cross-linked polymer system in the vapour of a swelling agent has been derived under isothermal and isobaric conditions. The equation is used to describe the equilibrium uptake of water by elastomers Arnitel^® (DSM), which are hard-soft-segment block copolymers in which the hard segments poly(butylene terephthalate) crystallise and are responsible for a physical cross-linking. The gravimetrically determined degrees of swelling of different elastomers in water vapour of various partial pressures are analysed and discussed by the application of an extended semi-empirical swelling equation of Flory-Huggins-Staverman-van Santen.     

Synthesis of halogenated polyhedral phosphaboranes. Crystal structure of closo-1,7-P2B10Cl10

The 12-vertex closo-phosphaborane 1,7-P2B10Cl10 (1) has been prepared in low yield from the pyrolysis reaction of B2Cl4 with PCl3 at temperatures above 400 degrees C. A single-crystal X-ray structure determination of 1 (monoclinic space group P2(1)/n with a = 9.239(2) A, b = 16.786(3) A, c = 15.739(3) a, beta = 93.25(3) degrees, and Z = 4) confirmed that, consistent with its 26 skeletal electron count, the phosphaborane adopts a distorted icosahedral structure with the phosphorus atoms in the 1,7-positions. Crystals of 1 contain toluene in a 1:1 molar ratio embedded between each P atom of neighboring cluster molecules. Alteration of the pyrolytic conditions resulted in the formation of the phosphaboranes P4B8Cl6 (2) and P2B8Cl8 (3), which were characterized spectroscopically. Copyrolysis of B2Cl4 with a mixture of PCl3 and AsCl3 at 450 degrees C generated the six-vertex arsaphosphaborane AsPB4Cl4 (4) and traces of the icosahedral arsaphosphaborane AsPB10Cl10. These compounds are examples of heteroboranes which contain two different group-15 atoms within a single molecule.     

Statistical evaluation of the influence of several sample pretreatment methods on the mercury content detectable by chemical analysis of contaminated soil samples under practical conditions

The estimation of the environmental risk of contaminated sites caused by hazardous components may be obtained, for instance, by means of a soil survey. There unavoidable errors by sampling, sample preparation and chemical analysis occur. Furthermore, in case of mercury contaminations, the mercury content detectable by chemical analysis can be falsified, if between sampling, on the one hand, and sample preparation and sample decomposition for chemical analysis, on the other hand, volatile components or elementary metallic mercury escape from the sample. Thus, in these cases, handling of samples such as air drying, storing in plastic bags or thermal evaporation, generally termed sample pretreatment, is a further source of error in evaluating a material. However, the measuring results are influenced not only by sampling, sample pretreatment, sample preparation by homogenization and splitting, and chemical analysis; they must also reflect the intrinsic properties of the soil sample subject to both global fluctuations and local heterogeneities. The present work shows by example of a non-uniformly contaminated site to what extent the analytically detectable mercury content is changed by the method of handling of soil samples in the period between sampling and chemical analysis. A hierarchical experimental design was realized in order to separately quantify the different sources of variation of the measured mercury contents, which are caused by global variations, local heterogeneities, sample preparation, sample pretreatment as well as chemical analysis. As turned out by variance analysis, the variance portion contributed to the total variance by sample pretreatment is highly significant and lies in the same order of magnitude as the variance caused by local heterogeneities of the soil. That means that the type of sample pretreatment influences the analytical results essentially. In order to quantify the effect of a definite pretreatment method in comparison with the mercury content of the unchanged original soil sample, the probable systematic error of a method was introduced. Investigations were only carried out at two sampling locations of the contaminated site because of the relatively high labour; the mean values and variances obtained cannot be immediately transferred to other sites. However, the general knowledge can be used as methodical basis for further investigations. Particularly, the consequence arises that the regulations existing for the treatment of mercury-contaminated samples between sampling and chemical analysis must be revised to obtain comparable criteria of evaluation.Symbols used level of error in statistical tests, - _i random effect of the i-th sampling location with respect to the mercury content, effect of global fluctuations - _ij random effect of the j-th primary sample (composite sample) at the i-th sampling location, effect of local heterogeneity, sampling error - _ijk random effect of the k-th subsample within the respective j-th primary sample (composite sample) at the i-th sampling location, sample preparation error - _ijkl random effect of the l-th pretreated sample belonging to the respective k-th subsample of the j-th primary or composite sample at the i-th sampling location, sample pretreatment effect - _1– probable relative systematic error of a pretreatment methods as compared with the original material at the coverage probability 1– - overall expected mercury content of the sampling results - _i expected mercury content of the i-th pretreated composite sample at a fixed location - û_{1.1 –} lower limit of a confidence interval for the unknown expected mercury content of unchanged original material at the confidence probability 1– - _i intraclass correlation coefficient - ² , ² , ² , ² , _Z ² variance components caused by global variability, local heterogeneity, sample preparation, sample pretreatment and analytical error, respectively - _total ² total variance of mercury content - D² operator of the variance of a random variable - E operator of the mathematical expectation of a random variable - F_i mean squared sum quotient of the Fisher's F-distribution - F_1–/2(fg_i, fg_j) critical value of the F-distribution at fg_i and fg_j degrees of freedom, respectively - fg_i degree of freedom of a (mean) sum of squared deviations - H_i hypothesis regarding a statistical law - I_1– confidence interval for the unknown expected value difference of two methods compared at the probability 1–, probable systematic error of a pretreatment method as compared with the unchanged original material at the coverage probability 1– - MQ_i, mq_i mean squared deviations as explained in the context - n_i number of sampling locations, primary samples per location, subsamples per primary sample, pretreatment methods and measuring values per pretreated sample, respectively - S _i ² , s _i ² variance estimation obtained by chemical analysis - SQ_i, sq_i sum of squared deviations - S(|Y₁–Y_i|) mean error of the absolute mean value difference |Y₁–Y_i|) - t_1–/2;m critical value of the Student's t-distribution at m degrees of freedom and the probability 1–/2 - Y_ijklm mercury content obtained on the m-th final sample of the l-th pretreated sample belonging to the k-th subsample of the j-th primary sample at the i-th sampling location - Y_i, y_i,... mean values obtained by sampling and chemical analysis - Z_ijklm random error of the ijklm-th measuring value (final sample value) Y_ijklm.     

Metal salt catalyzed carbenoid—XIII: On the mechanisms of cyclopropanation and allylic CH insertions by diazo esters in the presence of olefins and homogeneous copper catalysts

Evidence is presented demonstrating the existence of two paths to the title processes which arise from a common intermediate. A rationale involving catalyzed addition of the diazo compound to the olefin and carbenoid addition to the olefin is proposed. The penultimate intermediate has one new CC bond formed. It is partitioned between products by forming the second CC bond or formation of a hydrocarbenoid allyl complex which collapses to the allylic CH insertion products. Cyclopropanation occurs stereospecifically. The proposed mechanism accounts for the stereospecificity of cyclopropanation, the variance of syn/anti ratios with catalyst concentration when diazoacetic ester is employed and optical inductions with chiral catalysts. The question of whether the alleged carbenoid and/or the penultimate intermediate contain N₂ is not answered although it is felt that a cupro-cyclobutane intermediate is the most probable intermediate before product partitioning.     

Some useful data of continuous variation method

Summary Conditions for the correct application of continuous variation are presented. The data (parameterR _mn , effective stability constant and total concentration) that enable a safe determination of the molar ratio metalligand (m/n) in the complex are computed. The possibility of the determination of true valuesm andn and effective stability constant from one continuous variation curve are discussed and demonstrated on the example of the iron(III)-chrome azurol S complex.

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Einige nützliche Daten zur Methode der kontinuierlichen Variation

Zusammenfassung Bedingungen für die korrekte Anwendung der Methode der kontinuierlichen Variation werden gegeben. Die Daten (ParameterR _mn effektive Stabilitätskonstante und Gesamtkonzentration), die eine zuverlässige Bestimmung des molaren Verhältnisses MetallLigand (m/n) im Komplex ermöglichen, werden berechnet. Die Möglichkeit zur Bestimmung der wahren Werte fürm undn sowie der effektiven Stabilitätskonstanten aus einer Kurve der kontinuierlichen Variation werden erörtert und am Beispiel des Eisen(III)-Chromazurol S-Komplexes demonstriert.

     

Direct spectrophotometric method for determination of traces of boron in iron, steels and other compounds

For the determination of traces of boron in iron, low- and high-alloy steels and other materials a direct spectrophotometric method was developed. In this method the absorbance of the boron-Curcumin complex formed in the sample solution is compared with the absorbance of another aliquot of sample solution wherein the boron is rendered inactive with fluoride before the Curcumin is added.