Scalable Non-Volatile Tuning of Photonic Computational Memories by Automated Silicon Ion Implantation.

Photonic integrated circuits (PICs) are revolutionizing the realm of information technology, promising unprecedented speeds and efficiency in data processing and optical communication. However, the nanoscale precision required to fabricate these circuits at scale presents significant challenges, due to the need to maintain consistency across wavelength-selective components, which necessitates individualized adjustments after fabrication. Harnessing spectral alignment by automated silicon ion implantation, in this work scalable and non-volatile photonic computational memories are demonstrated in high-quality resonant devices. Precise spectral trimming of large-scale photonic ensembles from a few picometers to several nanometres is achieved with long-term stability and marginal loss penalty. Based on this approach, spectrally aligned photonic memory and computing systems for general matrix multiplication are demonstrated, enabling wavelength multiplexed integrated architectures at large scales.

Plasmon energy losses in shear bands of metallic glass.

Shear bands resulting from plastic deformation in cold-rolled Al88Y7Fe5 metallic glass were observed to display alternating density changes along their propagation direction. Electron-energy loss spectroscopy (EELS) was used to investigate the volume plasmon energy losses in and around shear bands. Energy shifts of the peak centre and changes in the peak width (FWHM) reflecting the damping were precisely determined within an accuracy of a few meV using an open source python module (Hyperspy) to fit the shapes of the plasmon and zero-loss peaks with Lorentzian functions. The maximum bulk plasmon energy shifts were calculated for the bright and dark shear band segments relative to the matrix to be about 38 and 14 meV, respectively. The damping was observed to be larger for the denser regions. The analysis presented here suggests that the changes in the plasmons are caused by two contributions: (i) Variable damping in the shear band segments due to changes in the medium-range order (MRO). This affects the static structure factor S(k), which, in turn, leads to either reduced or increased damping according to the Ziman-Baym formula. (ii) The ionic density and the effective electron mass appearing in the zero-momentum plasmon frequency formula Ep(q=0) are coupled and give rise to small variations in the plasmon energy. The model predicts plasmon energy shifts in the order of meV.

Deformation-driven catalysis of nanocrystallization in amorphous Al alloys.

Nanocrystals develop in amorphous alloys usually during annealing treatments with growth- or nucleation-controlled mechanisms. An alternative processing route is intense deformation and nanocrystals have been shown to develop in shear bands during the deformation process. Some controversy surrounded the idea of adiabatic heating in shear bands during their genesis, but specific experiments have revealed that the formation of nanocrystals in shear bands has to be related to localized deformation rather than thermal effects. A much less debated issue has been the spatial distribution of deformation in the amorphous alloys during intense deformation. The current work examines the hypothesis that intense deformation affects the regions outside shear bands and even promotes nanocrystal formation in those regions upon annealing. Melt-spun amorphous Al88Y7Fe5 alloy was intensely cold rolled. Microcalorimeter measurements at 60 °C indicated a slight but observable growth of nanocrystals in shear bands over the annealing time of 10 days. When the cold-rolled samples were annealed at 210 °C for one hour, transmission electron images did not show any nanocrystals for as-spun ribbons, but nanocrystals developed outside shear bands for the cold rolled samples. X-ray analysis indicated an increase in intensity of the Al peaks following the 210 °C annealing while the as-spun sample remained "X-ray amorphous". These experimental observations strongly suggest that cold rolling affects regions (i.e., spatial heterogeneities) outside shear bands and stimulates the formation of nanocrystals during annealing treatments at temperatures well below the crystallization temperature of undeformed ribbons.

Antiproliferative/cytotoxic effects of molecular iodine, povidone-iodine and Lugol's solution in different human carcinoma cell lines.

Clinical trials have revealed that molecular iodine (I2) has beneficial effects in fibrocystic breast disease and in cyclic mastalgia. Likewise, povidone-iodine (PVP-I), which is widely used in clinical practice as an antiseptic agent following tumour surgery, has been demonstrated to have cytotoxic effects on colon cancer and ascites tumour cells. Our previous study indicated that the growth of breast cancer and seven other human malignant cell lines was variably diminished by I2 and iodolactones. With the intention of developing an iodine-based anticancer therapy, the present investigations extended these studies by comparing the cytotoxic capacities of I2, potassium iodide (KJ), PVP-I and Lugol's solution on various human carcinoma cell lines. Upon staining the cell nuclei with Hoechst 33342, the cell densities were determined microscopically. While KJ alone did not affect cell proliferation, it enhanced the antiproliferative activity of I2. In addition, PVP-I significantly inhibited the proliferation of human MCF-7 breast carcinoma, IPC melanoma, and A549 and H1299 lung carcinoma cells in a concentration corresponding to 20 µM I2. Likewise, Lugol's solution in concentrations corresponding to 20-80 µM I2 were observed to reduce the growth of MCF-7 cells. Experiments with fresh human blood samples revealed that the antiproliferative activity of PVP-I and I2 is preserved in blood plasma to a high degree. These findings suggest that PVP-I, Lugol's solution, and a combination of iodide and I2 may be potent agents for use in the development of antitumour strategies.

Quantitative Measurement of Density in a Shear Band of Metallic Glass Monitored Along its Propagation Direction.

Quantitative density measurements from electron scattering show that shear bands in deformed Al88Y7Fe5 metallic glass exhibit alternating high and low density regions, ranging from -9% to +6% relative to the undeformed matrix. Small deflections of the shear band from the main propagation direction coincide with switches in density from higher to lower than the matrix and vice versa, indicating that faster and slower motion (stick slip) occurs during the propagation. Nanobeam diffraction analyses provide clear evidence that the density changes are accompanied by structural changes, suggesting that shear alters the packing of tightly bound short- or medium-range atomic clusters. This bears a striking resemblance to the packing behavior in granular shear bands formed upon deformation of granular media.

Self-organization of mesoscopic silver wires by electrochemical deposition.

Long, straight mesoscale silver wires have been fabricated from AgNO3 electrolyte via electrodeposition without the help of templates, additives, and surfactants. Although the wire growth speed is very fast due to growth under non-equilibrium conditions, the wire morphology is regular and uniform in diameter. Structural studies reveal that the wires are single-crystalline, with the [112] direction as the growth direction. A possible growth mechanism is suggested. Auger depth profile measurements show that the wires are stable against oxidation under ambient conditions. This unique system provides a convenient way for the study of self-organization in electrochemical environments as well as for the fabrication of highly-ordered, single-crystalline metal nanowires.

Density changes in shear bands of a metallic glass determined by correlative analytical transmission electron microscopy.

Density changes between sheared zones and their surrounding amorphous matrix as a result of plastic deformation in a cold-rolled metallic glass (melt-spun Al88Y7Fe5) were determined using high-angle annular dark-field (HAADF) detector intensities supplemented by electron-energy loss spectroscopy (EELS), energy-dispersive X-ray (EDX) and nano-beam diffraction analyses. Sheared zones or shear bands were observed as regions of bright or dark contrast arising from a higher or lower density relative to the matrix. Moreover, abrupt contrast changes from bright to dark and vice versa were found within individual shear bands. We associate the decrease in density mainly with an enhanced free volume in the shear bands and the increase in density with concomitant changes of the mass. This interpretation is further supported by changes in the zero loss and Plasmon signal originating from such sites. The limits of this new approach are discussed.

Mimics of the self-assembling chlorosomal bacteriochlorophylls: regio- and stereoselective synthesis and stereoanalysis of acyl(1-hydroxyalkyl)porphyrins.

Diacylation of copper 10,20-bis(3,5-di-tert-butylphenylporphyrin) using Friedel-Crafts conditions at short reaction times, high concentrations of catalyst, and 0-4 degrees C affords only the 3,17-diacyl-substituted porphyrins, out of the 12 possible regioisomers. At longer reaction times and higher temperatures, the 3,13-diacyl compounds are also formed, and the two isomers can be conveniently separated by normal chromatographic techniques. Monoreduction of these diketones affords in good yields the corresponding acyl(1-hydroxyalkyl)porphyrins, which after zinc metalation are mimics of the natural chlorosomal bacteriochlorophyll (BChl) d. Racemate resolution by HPLC on a variety of chiral columns was achieved and further optimized, thus permitting easy access to enantiopure porphyrins. Enantioselective reductions proved to be less effective in this respect, giving moderate yields and only 79% ee in the best case. The absolute configuration of the 3(1)-stereocenter was assigned by independent chemical and spectroscopic methods. Self-assembly of a variety of these zinc BChl d mimics proves that a collinear arrangement of the hydroxyalkyl substituent with the zinc atom and the carbonyl substituent is not a stringent requirement, since both the 3,13 and the 3,17 regioisomers self-assemble readily as the racemates. Interestingly, the separated enantiomers self-assemble less readily, as judged by absorption, fluorescence, and transmission electron microscopy studies. Circular dichroism spectra of the self-assemblies show intense Cotton effects, which are mirror-images for the two 3(1)-enantiomers, proving that the supramolecular chirality is dependent on the configuration at the 3(1)-stereocenter. Upon disruption of these self-assemblies with methanol, which competes with zinc ligation, only very weak monomeric Cotton effects are present. The favored heterochiral self-assembly process may also be encountered for the natural BChls. This touches upon the long-standing problem of why both 3(1)-epimers are encountered in BChls in ratios that vary with the illumination and culturing conditions.

Flavonoid glucuronides and a chromone from the aquatic macrophyte Stratiotes aloides.

The first phytochemical analysis of the aquatic macrophyte Stratiotes aloides afforded two new flavonoid glucuronides, luteolin 7-O-beta-D-glucopyranosiduronic acid-(1-->2)-beta-D-glucopyranoside (1) and chrysoeriol 7-O-beta-D-glucopyranosiduronic acid-(1-->2)-beta-D-glucopyranoside (2), as well as the new 2-(2-hydroxypentyl)-5-carboxy-7-methoxychromone (5) and chrysoeriol 7-O-beta-(6-O-malonyl)glucopyranoside (3), which has been assigned via NMR data for the first time. Additionally, free amino acids such as tryptophan, arginine, leucine, isoleucine, phenylalanine, and tyrosine along with choline, cis-aconitic acid, the phenolic glycoside alpha-arbutine, the chlorophyll derivative phaeophorbide a, and the flavonoid glycoside luteolin 7-O-beta-(6-O-malonyl)glucopyranoside (4) were isolated. Despite the low quantities obtained in some cases (between 50-300 microg), the structures of all compounds were unambiguously elucidated by extensive NMR and MS experiments. With a delay of 2 days compound 1 (10 and 50 microM test concentration) strongly inhibited the growth of human SH-SY5Y neuroblastoma cells in a dose-dependent manner, whereas only a moderate growth inhibition of human Patu 8902 carcinoma cells could be observed. Compounds 1 and 2 showed no activities against the bacteria Escherichia coli BW25113, Pseudomonas pudida KT2440, and Enterobacter cloacae subsp. dissolvens.

Novel carbon nanosheets as support for ultrahigh-resolution structural analysis of nanoparticles.

The resolution in transmission electron microscopy (TEM) has reached values as low as 0.08 nm. However, these values are not accessible for very small objects in the size range of a few nanometers or lower, as they have to be placed on some support, which contributes to the overall electron-scattering signal, thereby blurring the contrast. Here, we report on the use of nanosheets made from cross-linked aromatic self-assembled monolayers as TEM sample supports. When transferred onto a copper grid, a single 1.6-nm-thick nanosheet can cover the grid and is free standing within the micron-sized openings. Despite its thinness, the sheet is stable under the impact of the electron beam. Micrographs taken from nanoclusters onto these nanosheets show highly increased contrast in comparison to the images taken from amorphous carbon supports. In scanning transmission electron microscopy with nanosheet support, a size analysis of sub-nanometer Au clusters was performed and single Au atoms were resolved.

Attenuation of actinomyosinII contractile activity in growth cones accelerates filopodia-guided and microtubule-based neurite elongation.

The myosinII-specific inhibitor blebbistatin was used to attenuate actinomyosinII contractility in E7-chicken retina explant, medulla and spinal cord neuronal cell cultures. Addition of 20-100 microM blebbistatin, a concentration range that reversibly disrupts actin stress fibers, led to a reduction of growth cone lamellipodial areas and to an elongation of filopodia within 5 to 10 min. These morphological changes were completely reversed after removing the inhibitor. In the continued presence of blebbistatin for several hours, a dose-dependent acceleration (up to 6-fold) of neurite outgrowth was observed. The rapidly elongating neuritic processes displayed narrowed growth cones with one to three long filopodia at the leading edge. At the same time, thin neuritic branches emerged in a "push"-like fashion guided by filopodial extensions. Immunocytochemical characterization of these thin sprouts revealed that they contained actin filaments, myosinIIA, phosphorylated neurofilament/tau epitopes, MAP2, NCAM-PSA, and microtubules, demonstrating that these processes presented neurites and not filopodia. The crucial involvement of microtubules in blebbistatin-induced accelerated neurite extension was confirmed by its inhibition in the presence of nocodazole or taxol. The promotion by blebbistatin of neurite outgrowth occurred on polylysine, laminin, as well as on fibronectin as substrate. The presence of the Rho/ROCK-inhibitor Y-27632 also caused a dose-dependent promotion of neurite growth which was, however, 3-fold less pronounced as compared to blebbistatin. In contrast to blebbistatin, Y-27632 led to the enlargement of growth cone lamellipodial extensions. Our data demonstrate that neurite outgrowth and branching are inversely correlated with the degree of actinomyosinII contractility which determines the speed of retrograde flow and turnover of actin filaments and, by this, microtubule extension.

Neuroma formation in a rat median nerve model: influence of distal stump and muscular coating.

BACKGROUND: The purpose of this study was to investigate neuroma formation in a rat median nerve model. METHODS: In three groups, the median nerve was exposed and a gap was created. In the first group, a short gap of 1 cm (n = 12) was created; in the second, a long gap of 2 cm (n = 12) was created in the nerve. Another group was used to analyze the development of neuroma formation when the proximal stump was buried in adjacent muscle with an additional gap of 2 cm (n = 12). The use of different lengths should allow one to gain information about dilution effects of distal stump factors that may contribute to neuroma formation. Nine months later, specimens were gathered and histologically analyzed. The cross-sectional areas of neuromas were measured and the neural/connective tissue ratios were estimated. RESULTS: The cross-sectional areas demonstrated that neuroma formation was significantly higher in the short-gap group than in the long-gap group, and smallest in the muscle-covered group. The percentage of neural tissue was highest in the muscle-covered and long-gap groups and lowest in the short-gap group. CONCLUSIONS: These results demonstrate an association between neuroma formation and distal stump distance. This observation may be explained by the factors originating from the distal stump that were blocked when the proximal nerve stump was completely buried in the muscle. For clinical application, the authors recommend not only burying the proximal stump in a muscle but also surgically augmenting the gap between the proximal and distal stumps.

Efficient synthesis of substituted 7-methyl-2H,5H-pyrano[4,3-b]pyran-5-ones and evaluation of their in vitro antiproliferative/cytotoxic activities.

Substituted 7-methyl-2H,5H-pyrano[4,3-b]pyran-5-ones and related heterocycles 3 were synthesized through an efficient domino Knoevenagel condensation/6pi-electron electrocyclization. In vitro antiproliferative/cytotoxic activity evaluation was performed with human SH-SY5Y neuroblastoma cells and revealed IC(50) values ranging from 6.7 to >200microM. The compound that was most cytotoxic to the neuroblastoma cells, that is, 2-isobutyl-3-isopropyl-7-methyl-2H,5H-pyrano[4,3-b]pyran-5-one (3a), also exhibited necrotic effects on the human IPC melanoma cells.

Integerrimides A and B, cyclic heptapeptides from the latex of Jatropha integerrima.

Two new cyclic heptapeptides, integerrimides A and B, have been isolated from the latex of Jatropha integerrima. Their structures were elucidated by using extensive 1D and 2D NMR, MS, and chemical degradation. At 50 microM both peptides 1 and 2 significantly inhibited neurite outgrowth in neuronal cell culture. They also partially inhibited proliferation of human IPC-298 melanoma cells as well as migration of human Capan II pancreatic carcinoma cells, but were inactive in HSV-1, antifungal, and antimalarial assays.

Characterization of ZnE (E = S, Se, or Te) materials synthesized using silylated chalcogen reagents in mesoporous MCM-41.

The binary materials ZnS, ZnSe, and ZnTe have been successfully prepared within the mesoporous framework of MCM-41 at room temperature through the use of silylated chalcogen reagents. Postsynthesis grafting of ethylenediamine facilitates the complexation of anhydrous zinc acetate to the pore surface via a ligand exchange process between monodentate 3,5-lutidine ligands and the anchored chelating moiety. Coordinated zinc acetate readily reacts with E(SiMe(3))(2) (E = S, Se, or Te), thereby encapsulating zinc chalcogenides in the mesoporous channels. ZnE-MCM-41 materials have been characterized by EDX analysis, nitrogen sorption analysis, and Raman, UV-vis, and solid-state NMR spectroscopy. The observed blue shift in the absorption maximum is in agreement with the expected quantum confinement of these materials given the nanometer dimensions of the mesoporous architecture of the silicate host.

Cross-chest median nerve transfer: a new model for the evaluation of nerve regeneration across a 40 mm gap in the rat.

A new animal model for the study of nerve regeneration in rats across a 40 mm gap between both median nerves is described. For autologous grafting, the ulnar nerves were dissected and sutured together. From the left median nerve, they were transplanted across the chest to the right median nerve. Animals having undergone this operation were observed for 12 months and periodically assessed using the grasping test and measurements of body-weight. For histological analysis rats were sacrificed after this period and axon counts were determined at the suture points of operated animals and in the median nerve of non-operated animals. Functional recovery could be seen, although partially, beginning as early as the fifth postoperative month, as demonstrated by the grasping test. Quantification of the number of axons demonstrated axonal regeneration across all three coaptation points. This model provides a new approach for analysis of long distance peripheral nerve regeneration without impairment of behaviour.

Control of metal-ion composition in the synthesis of ternary II-II'-VI nanoparticles by using a mixed-metal cluster precursor approach.

The ternary molecular nanoclusters [Zn(x)Cd(10-x)Se4(SePh)12(PnPr3)4] (x = 1.8, 1 a; x = 2.6, 1 b) were employed as single-source precursors for the synthesis of high-quality hexagonal Zn(x)Cd(1-x)Se nanocrystals. The tellurium clusters [Zn(x)Cd(10-x)Te4(TePh)12(PnPr3)4] (x = 1.8, 2 a; x = 2.6, 2 b) are equally convenient precursors for the synthesis cubic Zn(x)Cd(1-x)E nanoparticles. The thermolysis of the cluster molecules in hexadecylamine provides an efficient system in which the inherent metal-ion stoichiometry of the clusters is retained in the nanocrystalline products, whilst also affording control of particle size within the 2-5 nm range. In all cases, the nanoparticles are monodisperse, and luminescence spectra exhibit emission energies close to the absorption edge. Analysis of the optical spectra and X-ray diffraction patterns of these materials indicates a metal-ion concentration gradient within the structures of the nanocrystals, with Zn(II) ions predominantly located near the surface of the particles.

Nerve regeneration across a 2-cm gap in the rat median nerve using a resorbable nerve conduit filled with Schwann cells.

OBJECT: In a rat model, nerve regeneration was evaluated across a 2-cm defect in the median nerve by using a resorbable artificial nerve conduit. The aim of this study was to develop an artificial, biocompatible nerve guide to induce regeneration in the peripheral nervous system. METHODS: The authors compared a nerve conduit of trimethylenecarbonate-co-epsilon-caprolactone (TMC/CL) filled with autologous Schwann cells with both an empty hollow conduit and an autologous nerve graft. Animals that did not undergo surgery served as the control group. Nerve regeneration was evaluated with the grasping test, histological analysis of the nerve, muscle weight analysis (flexor digitorum superficialis muscle), and electrophysiological examination. After an observation period of 9 months, regeneration occurred only in animals that had received an autologous graft or a Schwann cell containing nerve conduit. No signs of regeneration were found in animals supplied with the empty conduit. CONCLUSIONS: Results of this study reveal the important role of Schwann cells in the regeneration process across a 2-cm defect in the rat median nerve. Furthermore, Schwann cell-filled nerve conduits induced functional recovery, as demonstrated in the grasping test, that was comparable with that of the autologous graft 9 months after implantation.

Structural characterization of artificial self-assembling porphyrins that mimic the natural chlorosomal bacteriochlorophylls c, d, and e.

We report two crystal structures of a synthetic porphyrin molecule which was programmed for self-assembly. The same groups which ensure that bacteriochlorophylls c, d, and e can self-assemble into the chlorosomal nanorods, the photosynthetic antenna system of some green bacteria, have been engineered into desired positions of the tetrapyrrolic macrocycle. In the case of the 5,15-meso-substituted anchoring groups, depending upon the concentration, by using the same crystallization solvents, either a tetragonal or a layered structure of porphyrin stacks were encountered. Surprisingly, pi-pi interactions combined with extensive dispersive interactions, which also encompass cyclohexane, one of the crystallization solvents, win over putative hydrogen bonding. We are aware that our compounds differ considerably from the natural bacteriochlorophylls, but based upon our findings, we now question the hydrogen-bonding network, previously proposed to organize stacks of bacteriochlorophylls. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS) on various isomeric compounds support our challenge of current models for the chlorosomal antenna as these show structures, astonishingly similar to those of chlorosomes.

Enhancement of neurite outgrowth-promoting activity by heparin derivatives in sodium chlorate-treated explant cultures of rat central neurons.

Periodate-oxidized/borohydride-reduced 2-O-desulfated heparin (OR2DSH) was prepared using intact heparin from pig intestine as the starting material. Successive treatments of the heparin by oxidation with sodium periodate and reduction with sodium borohydride yielded periodate-oxidized/borohydride-reduced heparin (OR-heparin). Subsequent 2-O-desulfation of OR-heparin, according to a previously established method, yielded OR2DSH. Digestion of OR2DSH with heparitinases generated unsaturated disaccharides, comprising 86.5% DeltaDiHS-(6,N)S (DeltaUA1-->4GlcNS(6S)) and 13.5% DeltaDiHS-NS (DeltaUA1-->4GlcNS), as well as undigested oligosaccharides in which uronate moieties were derivatized by the cleavage of the covalent bond between the C-2 and C-3 positions by periodate-oxidation. The molecular mass of OR2DSH was determined to be 11 kDa, which is almost the same as those of other heparin derivatives such as 2-O-desulfated heparin (2DSH), 6-O-desulfated heparin (6DSH) and N-desulfated N-reacetylated heparin (NDSNAc-heparin). The ability of OR2DSH to enhance neurite outgrowth-promoting activity was evaluated using the explant culture of neocortical tissue from rat embryo in which endogenous heparan sulfate at the cell surface lost substantial numbers of sulfate groups by the action of 40 micro M sodium chlorate. The maximum activity of OR2DSH (29.7%) was achieved at 10 micro g/ml, and those of OR-heparin (21.7%), 2DSH (18.7%) and intact heparin (16.3%) were 100 micro g/ml, whereas that of NDSNAc-heparin (16.5%) was 1,000 micro g/ml. Completely 6-O-desulfated heparin (100:6DSH) exhibited very weak activity (3.3%) at 1,000 micro g/ml. These results suggest that the potency of OR2DSH to enhance neurite outgrowth-promoting activity is exerted synergetically by two different components in OR2DSH, i.e., the IdoA alpha1-->4GlcNS(6S) unit, which contains 6-O- and 2-N-sulfate groups, and the uronate moiety in which the covalent bond between C-2 and C-3 is cleaved, although the mode of action remains to be clarified.