Conversion of solid amorphous zirconium and hafnium phosphates into alpha crystalline form via molten oxalic acid

Solid amorphous zirconium phosphate /ZPa/ and hafnium phosphate /HPa/ are mixed with an excess of solid oxalic acid dihydrate and are digested in molten oxalic acid. Then oxalic acid is removed by extraction or by heating. The residue is washed with dilute HCl /0.01M/ and redistilled water. By this method -ZP and -HP is formed from amorphous ones.     

Measurements of sub-nanosecond lifetimes from biphotonic fluorescence produced by nanosecond laser pulses

When the absorption of light from nanosecond laser pulses gives rise to a short-lived biphotonic fluorescence the lifetime of the excited state can be derived from the dependence of the intensity of the fluorescence on the energy of the laser pulse. The results of investigations by Müller and Pflüger on cryptocyanine in methanol and glycerol are used to illustrate the principle of the method. An analysis of their data leads to a lifetime for the lowest singlet excited state of about 15 psec and 200 psec for methanol and glycerol, respectively.     

Reappraisal of four different approaches for finding the mean reaction time in the multi-trap variant of the Adam-Delbrück problem

Adam and Delbrück argued that the dimensionality of the diffusion space determines the average lifetime of a diffusing particle confined to a region with a central trap. Doubts have often been aired as to whether their calculation is relevant to real biological systems, where the number of traps is usually much larger than unity; or whether the rate enhancement is merely a manifestation of an increase in the concentration of the traps; or whether the diverse multi-trap versions of their expression for the mean lifetime in two dimensions are trustworthy. These issues are addressed, and the long-standing problem of finding the low-density limit of trapping time in two dimensions solved, by examining previous treatments of the problem, and by carrying out simulations of two-dimensional systems in which the particles undergo a Pearsonian random walk, and the traps are distributed randomly or on a square lattice. The mean lifetimes are found to be different in the two situations, and it is concluded that the neglect of this aspect lies at the root of the conflict between some of the existing expressions for the mean lifetime. Relations expressing the mean lifetime as a function of the concentration of the traps are presented together with a discussion of their applicability.     

Bacteriochlorophyll e monomers,but not aggregates,sensitize singlet oxygen: implications for a self-photoprotection mechanism in chlorosomes

Sensitization of singlet delta oxygen (O2(1delta(g))) by bacteriochlorophyll e (BChle) has been investigated to gain a better understanding of the photoprotection mechanism(s) operating in chlorosomes of green photosynthetic bacteria. The sensitization process has been studied in media where BChle forms monomers (acetone and aqueous solutions containing 0.5% Triton X-100 [TX]) and in systems where BChle aggregates, namely, aqueous solutions containing 0.003% monogalactosyl diglyceride (MGDG) and chlorosomes(control as well as hexanol perturbed) from Chlorobium phaeobacteroides strain CL1401. In Ar-purged acetone, BChle triplets (BChle triplets) have a lifetime of a few tens of microseconds; however, in air-saturated acetone, quenching of BChle triplets by ground-state oxygen (O2(3sigma(-)g)) and formation of O2(1delta(g)) take place. The O2(1delta(g)) so formed is susceptible to quenching by BChle0, a ground-state BChle molecule. A Stern-Volmer analysis reveals a linear fit between the decay rate of O2(1delta(g)) and the BChle concentration. The rate constants for the quenching of O2(1delta(g)) by BChle0 and for the deactivation of O2(1delta(g)) by the solvent come out to be kq = (1.4 +/- 0.1) x 10(9) M(-1) s(-1) and k0 = (18.5 +/- 0.7) x 10(3) s(-1), respectively. The absolute quantum yield of O2(1delta(g)) sensitization by BChle monomers is 0.65 +/- 0.15 in air-saturated acetone. In aqueous phase, the triplet lifetime of BChle aggregates in native or hexanol-perturbed chlorosomes shortens by more than two orders of magnitude when compared with the triplet lifetime of BChle monomers in 0.5% TX solution (a few hundreds of microseconds). Quenching by carotenoids (Car) makes only a minor contribution to the decay of BChle triplets in aggregates. Because O2(1delta(g)) sensitization by BChle triplets could be detected neither in MGDG aggregates nor in chlorosomes (control as well as hexanol perturbed), it is concluded that (1) this process is highly likely when BChle is present as a monomer but not when it is tightly packed in artificial aggregates or in chlorosomes; and (2) Car, though vital for the baseplate BChla, are dispensable for BChle.     

On recording the true absorption spectrum and the scattering spectrum of a turbid sample: application to cell suspensions of the cyanobacterium Anabaena variabilis

An integrating sphere is often used for recording the absorption spectrum of a turbid sample. If the sample is placed inside the sphere, scattering losses are eliminated, but the recorded spectrum suffers from other distortions. These distortions can be avoided by positioning the sample outside the sphere; but, since some of the scattered light escapes the detector, the recorded spectrum suffers from residual scattering losses. A method proposed by Latimer and Eubanks more than 30 years ago (Arch. Biochem. Biophys. 98 (1962) 274), is put to a quantitative examination, which has shown that one can obtain, by recording two spectra at different distances from the sphere, not only the true absorption spectrum but also the scattering spectra of the sample. Conditions for the validity of the basic assumption underlying the method are investigated by examining suspensions containing various concentrations of cells of the cyanobacterium Anabaena variabilis, and it is shown that the calculated absorbance is proportional to the number density of the cells. The application of the method for quantitative spectrophotometric analysis of pigments in cell suspensions is discussed.     

Quenching of chlorophyll a singlets and triplets by carotenoids in light-harvesting complex of photosystem II: comparison of aggregates with trimers

Laser-induced changes in the absorption spectra of isolated light-harvesting chlorophyll a/b complex (LHC II) associated with photosystem II of higher plants have been recorded under anaerobic conditions and at ambient temperature by using multichannel detection with sub-microsecond time resolution. Difference spectra (ΔA) of LHC II aggregates have been found to differ from the corresponding spectra of trimers on two counts: (i) in the aggregates, the carotenoid (Car) triplet–triplet absorption band (ΔA>0) is red-shifted and broader; and (ii) the features attributable to the perturbation of the Q_y band of a chlorophyll a (Chla) by a nearby Car triplet are more pronounced, than in trimers. Aggregation, which is known to be accompanied by a reduction in the fluorescence yield of Chla, is shown to cause a parallel decline in the triplet formation yield of Chla; on the other hand, the efficiency (100%) of Chla-to-Car transfer of triplet energy and the lifetime (9.3 μs) of Car triplets are not affected by aggregation. These findings are rationalized by postulating that the antenna Cars transact, besides light-harvesting and photoprotection, a third process: energy dissipation within the antenna. The suggestion is advanced that luteins, which are buried inside the LHC II monomers, as well as the other, peripheral, xanthophylls (neoxanthin and violaxanthin) quench the excited singlet state of Chla by catalyzing internal conversion, a decay channel that competes with fluorescence and intersystem crossing; support for this explanation is presented by recalling reports of similar behaviour in bichromophoric model compounds in which one moiety is a Car and the other a porphyrin or a pyropheophorbide.     

Characterization of a planar NID chiral interface under negative and/or positive phase velocity conditions

Using positive and/or negative phase velocity conditions, characteristics of a planar non-integer dimensional (NID) chiral interface are explored for specific values of NID parameter. For this purpose, discussion is divided into four cases. It is noted how characteristics of the interface changes when the situation is changed from one case to another. Impact of variation of NID parameter on the reflected power is also noted for each case.     

Nucleophilic ring opening reactions of aziridines

Aziridine ring opening reactions have gained tremendous importance in the synthesis of nitrogen containing biologically active molecules. During recent years, a great effort has been put forward by scientists toward unique bond construction methodologies via ring opening of aziridines. In this regard, a wide range of chiral metal- and organo-catalyzed desymmetrization reactions of aziridines have been reported with carbon, sulfur, oxygen, nitrogen, halogen, and other nucleophiles. In this review, an outline of methodologies adopted by a number of scientists during 2013–2017 for aziridine ring opening reactions as well as their synthetic applications is described.     

Synthesis,Crystal Structure,and Enhancement of the Efficacy of Metronidazole Against Entamoeba histolytica by Complexation with Palladium(II), Platinum(II), or Copper(II)

Reaction of trans‐[PdCl₂(DMSO)₂], cis‐[PtCl₂(DMSO)₂], and [Cu(OAc)₂]⋅H₂O with metronidazole (mnz) leads to the formation of new complexes, i.e., trans‐[PdCl₂(mnz)₂] ( 1 ), trans‐[PtCl₂(mnz)₂] ( 2 ), and trans‐[Cu₂(OAc)₄(mnz)₂] ( 3 ), respectively. Complexes 1 – 3 crystallize all in the centrosymmetric monoclinic space group P2₁/c with Z=8. Unit‐cell parameters for these complexes are: 1 , a=7.1328(14) Å, b=20.699(4) Å, c=7.1455(14) Å, and β=116.17(3)°; 2 , a=6.9169(14) Å, b=21.853(4) Å, c=6.7218(13) Å, and β=110.79(3)°; 3 , a=9.1663(18) Å, b=19.129(4) Å, c=8.9446(18) Å, and β=116.44(3)°. The complexes 1 and 2 maintain an ideal square‐planar geometry. In complex 3 , the H₂O molecules of the starting complex are replaced by metronidazole while maintaining a dimeric structure of [Cu(OAc)₂]. Each Cu ion has an ideal octahedral structure, though distortion occurs in the equatorial position where the acetato ligands are attached. The Cu Cu separation of 2.6343(8) Å indicates considerable metal‐metal interaction. The testing of the antiamoebic activity of these complexes against the protozoan parasite Entamoeba histolytica suggests that compound 1 – 3 might be endowed with important antiamoebic properties since they showed IC₅₀ values in a μM range better than metronidazole (Table 2). Thus, compound 1 displayed more effective amoebicidal activity than metronidazole (IC₅₀ values of 0.103 μM vs. 1.50 μM , resp.).     

Angular distribution measurements of Li(p,α)He reaction at 140 keV proton energy using nuclear track detectors

Angular distributions of a ⁶Li(p,α) ³He reaction were measured at six angles for 140 keV proton energy using nuclear track detectors (NTDs). The measurements were carried out over 60°–160° lab. angles in 20° increments using a scattering chamber of 80° beam line of the 350 kV accelerator. A semiconductor silicon surface barrier (SSB) detector was placed at +160° and was used as a monitor. The results have shown that the CR-39 detector has excellent capabilities to distinguish 1.4–2.7 MeV α+ ³He particles from the ⁶Li(p,α) ³He reaction and 8–9.4 MeV α-particles from the ⁷Li(p,α) ⁴He reaction through their track diameters. However, it was not possible to distinguish between the 2.3 MeV ³He ions and the 1.7 MeV ⁴He ions from the ⁶Li(p,α) ³He reaction from their track diameter measurements, but it was possible to differentiate between the two, from the darker contrast of the ³He particles caused by its deeper tracks as compared to those of ⁴He.