Regioselective Synthesis and Photophysical and Electrochemical Studies of 20‐Substituted Cyanine Dye–Purpurinimide Conjugates: Incorporation of NiII into the Conjugate Enhances its Tumor‐Uptake and Fluorescence‐Imaging Ability

We report herein a simple and efficient approach to the synthesis of a variety of meso‐substituted purpurinimides. The reaction of meso ‐ substituted purpurinimide with N‐bromosuccinimide regioselectively introduced a bromo functionality at the 20‐position, which on further reaction with a variety of boronic acids under Suzuki reaction conditions yielded the corresponding meso‐substituted analogues. Interestingly, the free base and the metalated analogues showed remarkable differences in photosensitizing efficacy (PDT) and tumor‐imaging ability. For example, the free‐base conjugate showed significant in vitro PDT efficacy, but limited tumor avidity in mice bearing tumors, whereas the corresponding Ni^II derivative did not produce any cell kill, but showed excellent tumor‐imaging ability at a dose of 0.3 μmol kg^?1 at 24, 48, and 72 h post‐injection. The limited PDT efficacy of the Ni^II analogue could be due to its inability to produce singlet oxygen, a key cytotoxic agent required for cell kill in PDT. Based on electrochemical and spectroelectrochemical data in DMSO, the first one‐electron oxidation (0.52 V vs. SCE) and the first one‐electron reduction (?0.57–0.67 V vs. SCE) of both the free base and the corresponding Ni^II conjugates are centered on the cyanine dye, whereas the second one‐electron reduction (?0.81 V vs. SCE) of the two conjugates is assigned to the purpurinimide part of the molecule. Reduction of the cyanine dye unit is facile and occurs prior to reduction of the purpurinimide group, which suggests that the cyanine dye unit as an oxidant could be the driving force for quenching of the excited triplet state of the molecules. An interaction between the cyanine dye and the purpurinimide group is clearly observed in the free‐base conjugate, which compares with a negligible interaction between the two functional groups in the Ni^II conjugate. As a result, the larger HOMO–LUMO gap of the free‐base conjugate and the corresponding smaller quenching constant is a reason to decrease the intramolecular quenching process and increase the production of singlet oxygen to some degree.     

Sorption of iron(III)–alginate complexes on cellulose fibres

Multivalent ions take a significant role in the sorption of soluble polysaccharides on solid cellulose substrates and thus demonstrate an important principle in structural polysaccharide organisation. Sorption of Fe(III)–alginate complexes on lyocell fibres as model for the insoluble cellulose matrix has been studied between pH 3–13, at 30 and 60 °C. Sorption maximum of the Fe(III)–alginate complex was observed at pH 3 where the sorbed amounts of alginate and iron were 6,600 and 85 mg iron per kg cellulose respectively. Under the experimental conditions used, a concentration of 0.05 mM Fe(III) is sufficient to achieve surface sorption of Fe(III)–alginate complex. The alginate sorption exhibited minor dependence on molar ratio of Fe(III) to alginate. In environmental scanning electron microscopy no deposition of Fe-hydroxides on the fiber surface was detected. The thickness of the adsorbed Fe(III)–alginate layer on the fiber surface was estimated with 12–22 nm. Tensile strength and abrasion resistance of Fe(III)–alginate treated fibers were not reduced through the sorption treatment. Alginate modified cellulose is of interest as material for medical application, as sorbent and textile finish.     

[2+3] Amide Cages by Oxidation of [2+3] Imine Cages – Revisiting Molecular Hosts for Highly Efficient Nitrate Binding

The pollution of groundwater with nitrate is a serious issue because nitrate can cause several diseases such as methemoglobinemia or cancer. Therefore, selective removal of nitrate by efficient binding to supramolecular hosts is highly desired. Here we describe how to make [2+3] amide cages in very high to quantitative yields by applying an optimized Pinnick oxidation protocol for the conversion of corresponding imine cages. By NMR titration experiments of the eight different [2+3] amide cages with nitrate, chloride and hydrogen sulfate we identified one cage with an unprecedented high selectivity towards nitrate binding vs. chloride (S=705) or hydrogensulfate (S>13500) in CD₂Cl₂/CD₃CN (1 : 3). NMR experiments as well as single-crystal structure comparison of host-guest complexes give insight into structure-property-relationships.     

A Molecular Photosensitizer in a Porous Block Copolymer Matrix-Implications for the Design of Photocatalytically Active Membranes

Recently, porous photocatalytically active block copolymer membranes were introduced, based on heterogenized molecular catalysts. Here, we report the integration of the photosensitizer, i. e., the light absorbing unit in an intermolecular photocatalytic system into block copolymer membranes in a covalent manner. We study the resulting structure and evaluate the orientational mobility of the photosensitizer as integral part of the photocatalytic system in such membranes. To this end we utilize transient absorption anisotropy, highlighting the temporal reorientation of the transition dipole moment probed in a femtosecond pump-probe experiment. Our findings indicate that the photosensitizer is rigidly bound to the polymer membrane and shows a large heterogeneity of absolute anisotropy values as a function of location probed within the matrix. This reflects the sample inhomogeneity arising from different protonation states of the photosensitizer and different intermolecular interactions of the photosensitizers within the block copolymer membrane scaffold.     

Extraction of cellulose fibers from flax and hemp: a review

Cellulose - The paper is a review on the extraction processes of cellulosic fibers from flax and hemp. The two lignocellulosic crops have a long history of use by humans for extraction of the bast...     

Switching the Mechanism of NADH Photooxidation by Supramolecular Interactions

A series of three Ru(II) polypyridine complexes was investigated for the selective photocatalytic oxidation of NAD(P)H to NAD(P)⁺ in water. A combination of (time-resolved) spectroscopic studies and photocatalysis experiments revealed that ligand design can be used to control the mechanism of the photooxidation: For prototypical Ru(II) complexes a ¹O₂ pathway was found. Rudppz ([(tbbpy)₂Ru(dppz)]Cl₂, tbbpy=4,4'-di-tert-butyl-2,2'-bipyridine, dppz=dipyrido[3,2-a:2′,3′-c]phenazine), instead, initiated the cofactor oxidation by electron transfer from NAD(P)H enabled by supramolecular binding between substrate and catalyst. Expulsion of the photoproduct NAD(P)⁺ from the supramolecular binding site in Rudppz allowed very efficient turnover. Therefore, Rudppz permits repetitive selective assembly and oxidative conversion of reduced naturally occurring nicotinamides by recognizing the redox state of the cofactor under formation of H₂O₂ as additional product. This photocatalytic process can fuel discontinuous photobiocatalysis.     

Evolution of a dust void in a radio-frequency plasma sheath

The onset and growth of a dust void are investigated in a radio-frequency (rf) sheath of a capacitively coupled argon plasma. A circularly symmetric void emerges and grows with increasing rf power and pressure in the central region of the dust cloud levitating in the sheath. Experimental measurements of the void diameter are compared with the predictions of a simple phenomenological theory, based on a balance of forces on dust grains.     

Nonlinear theory of void formation in colloidal plasmas

A nonlinear time-dependent model for void formation in colloidal plasmas is proposed. For experimentally relevant initial conditions, the model describes the nonlinear evolution of a zero-frequency linear instability that grows rapidly in the nonlinear regime and subsequently saturates to form a void. A number of features of the model are consistent with experimental observations under laboratory and microgravity conditions.     

The effect of pre-shear on the extensional rheology of wormlike micelle solutions

The effect of initial microstructural deformation, alignment, and morphology on the response of wormlike micelle solutions in transient uniaxial extensional flows is investigated using a pre-shear device attached to a filament stretching rheometer. In filament stretching experiments, increasing the strength and the duration of the pre-shear just before stretch is found to delay the onset of strain hardening. In these experiments, the wormlike micelle solution filaments fail through a rupture near the axial midplane. The value of the elastic tensile stress at rupture is found to decrease with increasing pre-shear rate and duration. The most dramatic effects are observed at shear rates for which shear banding has been independently observed. The reduction in the strain hardening suggests that pre-shear before filament stretching might break down the wormlike micelles reducing their size before stretch. Strain hardening is also observed in capillary breakup rheometry experiments; however, the pre-sheared wormlike micelle solutions strain harden faster, achieve larger steady-state extensional viscosities and an increase in the extensional relaxation time with increasing shear rate and duration. The difference between the response of the wormlike micelles in filament stretching and capillary breakup experiments demonstrates the sensitivity of these self-assembling micelle networks to pre-conditioning.