Vague objects and phenomenal wholes

We consider the so-called problem of the many, formulated by Peter Unger. It arises because ordinary material things do not have precise boundaries: it is always possible to find borderline parts of which it is not true to say either that they are parts or that they are not. Unger’s conclusion is that there are no ordinary things at all. We describe the solutions of Peter van Inwagen and David Lewis, and make some critical comments upon them. After that we present our own suggestion which is based on ideas developed by Leibniz in connection with problems of unity and plurality. We suggest that what the problem of the many teaches us is that in order to understand what ordinary things are, we have to take seriously the Leibnizian-Kantian distinction between phenomena and things-in-themselves.     

Effect of pH on hydrophilicity and charge and their effect on the filtration efficiency of NF membranes at different pH

In this work the effect of pH on membrane structure, its permeability and retention was studied. In addition, we studied whether the possible changes in the membrane properties due to the pH change are reversible. This is important for understanding the performance of nanofiltration membranes at different conditions and for the selection of cleaning processes. Moreover, the results facilitate the choice of membrane for specific applications.

Several commercial NF membranes were studied at different pH values. Their retention and flux were explained by the charge and the hydrophilic characteristics of the membranes. The filtrations were made with uncharged sugar and salt solutions.

The lower the membrane contact angle (i.e., a more hydrophilic membrane) the higher was the change in apparent zeta potential when pH was increased from 4 to 7. As a result, the retention of ions with more hydrophilic membranes changed more than hydrophobic ones when the pH was increased in the feed solution. However, some membranes retained ions well at high pH although their apparent zeta potential or hydrophilicity was relatively low. These membranes had charge inside the pores and it was not detected by streaming potential measurement along the surface or by measuring the contact angle of the surface. Thus, the apparent zeta potential of the exterior membrane surface did not sufficiently describe the ionic transport through the membrane. In addition, some membranes became significantly more open at high pH (i.e., flux increased). This was explained by the chemical nature of the polymer chains in the membrane skin layer, i.e., dissociating groups in the polymer made the surface more hydrophilic and looser when charges of the polymer chains started to repel each other at elevated pH. Generally, the retention of uncharged glucose decreased more at high pH than the salt retention. The changes in permeabilities and retentions were found to be mostly reversible in the pH range studied (very slowly in some cases, however).     

Bis(6‐thioxo‐1,6‐dihydro­purinium) tetra­chloro­zincate(II)

The title salt, (C₅H₅N₄S)₂[ZnCl₄], consists of two 6‐thioxo‐1,6‐dihydro­purinium (6mpH₂⁺) cations (A and B) and a tetra­chloro­zincate anion, which are held together by N—H⋯Cl and C—H⋯Cl inter­actions. There is an anion–π inter­action between one Cl atom of the [ZnCl₄]⁻ anion and the pyrimidine ring of the 6mpH₂⁺(B) cation. Inter­molecular π–π stacking inter­actions allow 6mpH₂⁺(A) cations to form anti­parallel pairs. One inter­esting structural feature is the double N—H⋯N inter­molecular hydrogen bonds between two 6mpH₂⁺(A) cations. This kind of inter­action, mimicking that of natural nucleobases, can be very valuable in designing new therapeutic purine derivatives.     

Conformations and energetics of sulfur and selenium diimides

The geometries and energetics of different conformations of sulfur and selenium diimides E(NR)(2) (E = S, Se; R = H, Me, (t)Bu, C(6)H(3)Me(2)-2,6, SiMe(3)) have been studied by using various ab initio and DFT molecular orbital techniques. The syn,syn conformation is found to be most stable for parent E(NH)(2), but in general, the preferred molecular conformation for substituted chalcogen diimides is syn,anti. In the case of E(NH)(2) the present calculations further confirm that syn,syn and syn,anti conformations lie energetically close to each other. From the three different theoretical methods used, B3PW91/6-31G proved to be the most suitable method for predicting the geometries of chalcogen diimides. The optimized geometrical parameters are in a good agreement with all available experimental data. While qualitative energy ordering of the different conformations is independent of the level of theory, the quantitative energy differences are dependent on the method used. The performance and reliability of higher level ab initio calculations and DFT methods using large basis sets were tested and compared with experimental information where available. All of the higher level ab inito methods give very similar results, but the use of large basis sets with the B3PW91 method does not increase the reliability of the results. The combination of CCSD(T)/cc-pVDZ with the B3PW91/6-31G-optimized geometries is found to be the method of choice to study energetic properties of chalcogen diimides.     

Comparison of calculated DFT/B3LYP and experimental C and O NMR chemical shifts, ab initio HF/6-31G* optimised structures, and single crystal X-ray structures of some substituted methyl 5β-cholan-24-oates

Single crystal X-ray structures (monoclinic space group P2₁) for methyl 3-oxo-5β-cholan-24-oate and methyl 3,12-dioxo-5β-cholan-24-oate have been solved and compared with HF/6-31G* optimised structures. In the crystalline packings the side chains are connected with weak OC(sp³)HO-type of interactions between C25–H and C24–O–C25 and the keto ends with weak C(sp³)HO=C-type of interactions between C4–H and O=C3. The orientations of the side chains, which steric configurations are of great importance to the biological activity of the molecules, are compared with the experimental structure of methyl 3-hydroxy-5β-cholan-24-oate. Probable reasons for the observed differences are discussed. In addition, ¹³C and ¹⁷O NMR chemical shifts of methyl 3-oxo-5β-cholan-24-oate and methyl 3,12-dioxo-5β-cholan-24-oate as well as the epimeric methyl 3-hydroxy-5β-cholan-24-oate and methyl 3β-hydroxy-5β-cholan-24-oate have been calculated (DFT/B3LYP/6-311G*) and compared with the experimental values by linear regression analyses. In general, the correspondence between the theoretical and experimental parameters is good or excellent.     

Occupational and environmental laboratory medicine: A network of EQAS organisers

Most people in any community come into contact with chemicals that are potentially harmful to their health. Some elements are essential to health and inadequate amounts in food may also lead to ill health. Measurement of chemicals in blood, urine or other specimens is a fundamental feature of studies undertaken in the field of Occupational and Environmental Laboratory Medicine (OELM). Results are used to assess the risk for either overexposure or deficiency of essential nutrients. External Quality Assessment Schemes (EQAS) aid laboratories to achieve accurate and consistent data and 11 organisers of EQAS in Europe and North America are working to improve the effectiveness of their activities.The aims of the Network of EQAS Organisers in OELM are to stimulate improvements in analytical results, establish equivalence of assessment among Schemes, collaborate to enhance the practice of EQA including whenever possible to warrant traceability of EQAS to primary standards.Presented at the Eurachem PT Workshop September 2005, Portorož, Slovenia.     

Gold(I)‐Catalyzed Generation of the Two Components of a Formal [4+2] Cycloaddition Reaction for the Synthesis of Tetracyclic Pyrano[2,3,4‐de]chromenes

Ortho‐Alkynylbenzaldehydes have been widely used to generate isochromenylium derivatives through gold‐catalyzed cycloisomerization. These isochromenylium derivatives have been exploited as formal diene derivatives for reactions with different dienophiles. Herein, we describe the behavior of ortho‐alkynylsalicylaldehydes, a particular case of ortho‐alkynylbenzaldehydes. The gold‐catalyzed cycloisomerization of ortho‐alkynylsalicylaldehydes delivers an unusual heterodiene derivative that reacts with electron‐rich alkenes through a formal [4+2] cycloaddition. In this reaction, both the diene and dienophile are generated in situ through gold‐catalyzed cycloisomerization of appropriate alkynamines or alkynols. This reaction was used to synthesize complex tetracyclic pyrano[2,3,4‐de]chromenes from two very simple starting materials (an ortho‐alkynylsalicylaldehyde and an alkynamine or alkynol) with complete atom economy and with selective formation of bonds, cycles, and stereocenters.     

Fully automated microchip system for the detection of quantal exocytosis from single and small ensembles of cells

A lab-on-a-chip device that enables positioning of single or small ensembles of cells on an aperture in close proximity to a mercaptopropionic acid (MPA) modified sensing electrode has been developed and characterized. The microchip was used for the detection of Ca(2+)-dependent quantal catecholamine exocytosis from single as well as small assemblies of rat pheochromocytoma (PC12) cells. The frequency of events increased considerably upon depolarization of the PC12 cell membrane using a high extracelluar concentration of potassium. The number of recorded events could be correlated with the number of cells immobilized on the electrode. Quantal characteristics, such as the number of released molecules per recorded event, are equivalent to data obtained using conventional carbon fiber microelectrodes. The detection sensitivity of the device allows for the detection of less than 10 000 dopamine molecules in a quantal release. The distribution of peak rise-time and full width at half maximum was constant during measurement periods of several minutes demonstrating the stability of the MPA modified surface.