Higher acenes by on‐surfacedehydrogenation : from heptacene to undecacene

A unified approach to the synthesis of the series of higher acenes up to previously unreported undecacene has been developed through the on‐surface dehydrogenation of partially saturated precursors. These molecules could be converted into the parent acenes by both atomic manipulation with the tip of a scanning tunneling and atomic force microscope (STM/AFM) as well as by on‐surface annealing. The structure of the generated acenes has been visualized by high‐resolution non‐contact AFM imaging and the evolution of the transport gap with the increase of the number of fused benzene rings has been determined on the basis of scanning tunneling spectroscopy (STS) measurements

Adsorption and self-assembly of large polycyclic molecules on the surfaces of TiO_{2} single crystals

Titanium dioxide is one of the most frequently studied metal oxides, and its (110) rutile surface serves as a prototypical model for the surface science of such materials. Recent studies have also shown that the (011) surface is relatively easy for preparation in ultra-high vacuum (UHV) and that both the (110) and (011) surfaces could be precisely characterized using scanning tunneling microscopy (STM). The supramolecular self-assembly of organic molecules on the surfaces of titanium dioxide plays an important role in nanofabrication, and it can control the formation and properties of nanostructures, leading to wide range of applications covering the fields of catalysis, coatings and fabrication of sensors and extends to the optoelectronic industry and medical usage. Although the majority of experiments and theoretical calculations are focused on the adsorption of relatively small organic species, in recent years, there has been increasing interest in the properties of larger molecules that have several aromatic rings in which functional units could also be observed. The purpose of this review is to summarize the achievements in the study of single polycyclic molecules and thin layers adsorbed onto the surfaces of single crystalline titanium dioxide over the past decade

Fermi level pinning at the Ge(001) surface - A case for non-standard explanation

To explore the origin of the Fermi level pinning in germanium we investigate the Ge(001) and Ge(001):H surfaces. The absence of relevant surface states in the case of Ge(001):H should unpin the surface Fermi level. This is not observed. For samples with donors as majority dopants the surface Fermi level appears close to the top of the valence band regardless of the surface structure. Surprisingly, for the passivated surface it is located below the top of the valence band allowing scanning tunneling microscopy imaging within the band gap. We argue that the well known electronic mechanism behind band bending does not apply and a more complicated scenario involving ionic degrees of freedom is therefore necessary. Experimental techniques involve four point probe electric current measurements, scanning tunneling microscopy and spectroscopy.Comment: 5 pages, 4 figure

Extended iron phthalocyanine islands self-assembled on a Ge(001):H surface

Self-assembly of iron(II) phthalocyanine (FePc) molecules on a Ge(001):H surface results in monolayer islands extending over hundreds of nanometers and comprising upright-oriented entities. Scanning tunneling spectroscopy reveals a transport gap of 2.70 eV in agreement with other reports regarding isolated FePc molecules. Detailed analysis of single FePc molecules trapped at surface defects indicates that the molecules stay intact upon adsorption and can be manipulated away from surface defects onto a perfectly hydrogenated surface. This allows for their isolation from the germanium surface

Wzmacnianie śrub przeznasadowych metodą śródoperacyjnej wertebroplastyki

Background and purpose The aim of the study was to determine the efficacy of posterior spinal stabilization, combined with intraoperative vertebroplasty defined as intraoperative filling of instrumented vertebral bodies (VB) with polymethylmethacrylate (PMMA). Material and methods Seventeen patients with osteoporosis or osteopenia underwent posterior spinal fusions. The surgical procedures included laminectomy, spondylodesis, insertion of pedicular screws, intraoperative vertebroplasty and correction of spinal deformity. Results Postoperative assessment showed improvement of pain in all cases. Motor deficit regressed in 2 of 3 afflicted patients. In 12 vertebrae (27.3%), the mass of PMMA extended from one endplate to another, filling 100% of VB height, in 7 (15.9%) it filled 90–99%, in 14 (31.8%) 80–89%, in 9 (20.4%) 70–79%, and in 2 (4.5%) it filled 50–60% of VB height. In the horizontal plane, PMMA filled central parts of 72.7% of vertebral bodies. PMMA completely surrounded 68.9% of screws, and partially surrounded 18.4% of screws, whereas 12.6% of screws had no contact with cement mass. Spinal stabilization reduced kyphotic deformity in 15 patients (range of reduction: 6°-25°; mean: 13.6°). During follow-up (3–32 months; mean: 16) implants of 11 patients were stable, 1 implant instability was diagnosed 7 months after surgery, 5 patients were lost to follow-up. Asymptomatic cement leaks occurred in 45% of vertebrae. Conclusions Intraoperative vertebroplasty performed after insertion of pedicular screws may be considered as a technical variation useful to stabilize osteoporotic spines. After PMMA hardening, intraoperative manoeuvres to correct spinal deformity were possible without any damage of instrumented vertebrae.Wstęp i cel pracy Celem pracy była ocena przeznasadowej stabilizacji kręgosłupa, wzmocnionej śródoperacyjną werte-broplastyką, czyli śródoperacyjnym podaniem polimetakrylanu metylu (PMMA) do trzonów, w które wkręcono śruby przeznasadowe. Materiał i metody U 17 pacjentów z osteoporozą lub osteopenią wykonano stabilizacje kręgosłupa z dostępu tylnego. Operacje obejmowały: laminektomię, spondylodezę, wkręcenie śrub przeznasadowych, śródoperacyjną wertebroplastykę oraz korekcję deformacji kręgosłupa. Wyniki Ocena kliniczna wykazała zmniejszenie bólu u 17 pacjentów i zmniejszenie niedowładu u 2 z 3 pacjentów. W 12 trzonach (27,3%) masa cementu rozciągała się pomiędzy blaszkami granicznymi, wypełniając 100% wysokości trzonu, w 7 (15,9%) wypełniała 90–99% wysokości trzonu, w 14 (31,8%) – 80–89%, w 9 (20,4%) – 70–79%, a w 2 trzonach (4,5%) – 50–69% wysokości trzonu. Cement usytuowany był w centralnych częściach 72,7% trzonów. Cement całkowicie otaczał obwód 68,9% śrub, częściowo otaczał 18,4% śrub, a 12,6% śrub nie miało kontaktu z cementem. Stabilizacja kręgosłupa zmniejszyła kifotyczną deformację u 15 pacjentów (zakres korekcji: 6°–25°, średnia: 13,6°). Wycieki cementu, klinicznie bezobjawowe, dotyczyły 45% trzonów u 76% pacjentów. W okresie obserwacji wynoszącym od 3 do 32 miesięcy (średnia: 16 miesięcy) u 11 pacjentów nie stwierdzono destabilizacji implantu, u jednej osoby destabilizacja ujawniła się po 7 miesiącach od operacji. Wnioski Śródoperacyjna wertebroplastyka może być stosowana do wzmocnienia śrub przeznasadowych, wkręconych w trzony o obniżonej gęstości kości. Po stwardnieniu cementu możliwa jest korekcja kształtu kręgosłupa bez uszkodzenia osłabionych kręgów

Compositional differences between Besko and Otryt sandstones of the Krosno Beds (Oligocene) in Eastern part of the Silesian Tectonic Unit

The aim of this research was to quantitatively and qualitatively analyse under microscope sandstones representing two lithofacies called Otryt and Besko (or Lesko) facies of the Krosno Formation (Oligocene), Silesian Tectonic Unit in the E part of the Polish Outer Carpathians. Four samples were taken into consideration — two from each lithofacies. Special attention was paid to  structural and textural characteristics and  mineral composition that reflects mainly  provenance. The results have been compared and analysed between and within facies, in terms of source and transport of the material, mineralogical and textural maturity and sedimentary processes that affect the deposition. Ślączka & Unrug (1972) and Shideler at al. (1976) concluded that mineralogical variations exhibited by sandstones in Krosno Formation were attributed to both regional (provenance) and local (sorting) effects.The samples have been taken from the northern (Otryt)  and southern (Besko) limbs of the Otryt Syncline. They represent different sources of the material -  Silesian Ridge in NW in case of Besko facies and Maramures Massif in the the SE in case of Otryt facies (Wendorff 1981). The result of the analysis confirm statement about two different sources.Transport and deposition mechanism results in considerable difference in grain size and its distribution. Besko facies sandstones display classic Bouma sequence at structures (Tb - c) indicative of deposition from normally diluted, waning turbidity currents, with incremental deposition layer-by-layer (Talling 2012) and this results in very fine grained sandstones and in better sorting. Deposits of that lithofacies appear much relatively uniform and well organized (Wendorff 1987). By contrast, sedimentary features of the Otryt facies suggest deposition from rapidly decelerating high density turbidity currents — “sandy debris flows” (Talling 2012), conditions and mechanisms of transportation and deposition must have been very variable (Wendorff 1987). These sandstones are medium grained, but the bottom sample is characterized by coarse tail caused by rapid deposition. The detrital material of the top sample was deposited also of high density turbidity current, however slightly less dense than that of the bottom sample.The diversity of mineral composition between Besko and Otryt lithofacies is very clear. There are probably three reasons for that — completely different source rocks, initially different maturity of the detritus involved in density flows and the depositional processes within the basin . Besko (Leslo) lithofacies is dominated by nonundulatory quartz. Other components are rather minor. The only difference between carbonate components is in the proportion of detrital calcite/limestone (or dolomite) to carbonate cement, which may have resulted from diagenetic processes. Carbonate cements are very rich in both samples. In Otryt facies mineral composition is more differentiated. Quartz predominates, but not as distinctly as in Besko facies. The most abundant and the coarsest are polycrystalline grains. Nonundulatory quartz is similarly abundant. Altered K-feldspars and metamorphic rock fragments are important however they occur less frequently. The bottom and top samples differ in quantity of coarse to very coarse metamorphic rock fragments and polycrystalline quartz — the bottom sample is richer in such grains. This is the result of grain-size sorting — coarser grains have been deposited first and this sorting process affects the mineral composition of the top-of-bed sample in which the coarse tail is absent and the proportion of metamorphic grains is less pronounced. There is very little cement in both samples. Next to high mineralogical maturity, Besko facies sandstones show also high textural and  mineralogical maturity (presence of well-rounded grains and high quartz content). On the other hand, Otryt facies sandstones are immature both texturally and mineralogically, which results from both source area composition and rapid deposition.According to provenance diagrams (Dickinson 1983), source of the Besko facies is recycled orogen, but close to craton interior field. Whereas source of the Otryt facies should be recycled orogen too.Despite the fact that all samples are the same age and occur in one formation,  they are totally different.In summary, differences in mineral composition and textural features, observed under the microscope, between the analysed samples of the Besko/Lesko and Otryt lithofacies turbidite sandstones reveal different mineral composition of the source areas and are comparable to the macroscopically observed sedimentary features. The latter indicate pronounced differences in the transportation and deposition mechanisms – from normally diluted turbidity currents to rapidly decelerating high sandy debris flows

Modification of emission properties of ZnO layers due to plasmonic near-field coupling to Ag nanoislands

A simple fabrication method of Ag nanoislands on ZnO films is presented. Continuous wave and time-resolved photoluminescence and transmission are employed to investigate modifications of visible and UV emissions of ZnO brought about by coupling to localized surface plasmons residing on Ag nanoislands. The size of the nanoislands, determining their absorption and scattering efficiencies, is found to be an important factor governing plasmonic modification of optical response of ZnO films. The presence of the Ag nanoislands of appropriate dimensions causes a strong (threefold) increase in emission intensity and up to 1.5 times faster recombination. The experimental results are successfully described by model calculations within the Mie theory.Comment: 14 pages, 5 figure

Tunneling spectroscopy of close-spaced dangling-bond pairs in Si(001):H

We present a combined experimental and theoretical study of the electronic properties of close-spaced dangling-bond (DB) pairs in a hydrogen-passivated Si(001):H p-doped surface. Two types of DB pairs are considered, called “cross” and “line” structures. Our scanning tunneling spectroscopy (STS) data show that, although the spectra taken over different DBs in each pair exhibit a remarkable resemblance, they appear shifted by a constant energy that depends on the DB-pair type. This spontaneous asymmetry persists after repeated STS measurements. By comparison with density functional theory (DFT) calculations, we demonstrate that the magnitude of this shift and the relative position of the STS peaks can be explained by distinct charge states for each DB in the pair. We also explain how the charge state is modified by the presence of the scanning tunneling microscopy (STM) tip and the applied bias. Our results indicate that, using the STM tip, it is possible to control the charge state of individual DBs in complex structures, even if they are in close proximity. This observation might have important consequences for the design of electronic circuits and logic gates based on DBs in passivated silicon surfaces

Sedimentary response to tectonic uplift of the Dukla basin margin recorded at Skrzydlna – the Menilite Beds (Oligocene), Outer Carpathians, S Poland

The Menilite Beds (Oligocene of Polish Flysch Carpathians) at Skrzydlna crops out in a structurally complex zone of the Fore-Magura Unit, which is tectonically overridden by Magura Nappe thrust form the S. The exposed sedimentary suite, representing the Dukla Basin, consists of fine-grained, well organised strata deposited in a low-energy, deep marine basin, which are abruptly overlain by poorly organised, coarse sandy conglomerate that forms a Mass Transport Deposit (MTD) complex. The MTD contains large boulders of extrabasinal rocks, massive sandstone beds with intrabasinal mudstone clasts, and slump sheets of sandstones. Above rests a fining- upwards sequence of sandstone beds interlayered with mudstones. The fine-grained facies reappear above to terminate the exposed succession. Erosional contacts and rapid facies changes, both vertical and lateral, are characteristic for the MTD unit. The sandstone-mudstone unit above contains laterally migrating erosional channels filled with massive sandy conglomerate in the lower part. Turbidites of varying density and completeness of internal structures that occur above are accompanied by an association of mixed facies including large-scale dune cross-bedding.Mineralogically, the sandstones are quartz arenites, sub-lithic arenites and wackes. Calcarenite grains – bioclasts, micrite and marl occur in substantial proportions only in the uppermost part of the succession. The point-counting data plotted on Qm-F-Lt diagram are clustered within the recycled fields: quartzose and transitional. Mineralogical maturity of the sandstones has the tendency to decrease from the sub-MTD strata upwards via the MTD unit to the lower part of the sandstone-mudstone complex; then it increases to the youngest sandstone beds with carbonate grains. These tendencies, associated with sedimentary features of the succession, reflect rapid uplift, emergence and progressive erosion of the terrigenous detritus source area, followed by tectonic stabilisation reflected by the appearance of the “carbonate factory”