Ultrafast Infrared Laser Crystallization of Amorphous Ge Films on Glass Substrates.

Amorphous germanium films on nonrefractory glass substrates were annealed by ultrashort near-infrared (1030 nm, 1.4 ps) and mid-infrared (1500 nm, 70 fs) laser pulses. Crystallization of germanium irradiated at a laser energy density (fluence) range from 25 to 400 mJ/cm2 under single-shot and multishot conditions was investigated using Raman spectroscopy. The dependence of the fraction of the crystalline phase on the fluence was obtained for picosecond and femtosecond laser annealing. The regimes of almost complete crystallization of germanium films over the entire thickness were obtained (from the analysis of Raman spectra with excitation of 785 nm laser). The possibility of scanning laser processing is shown, which can be used to create films of micro- and nanocrystalline germanium on flexible substrates.

Ultrafast Infrared Laser Crystallization of Amorphous Si/Ge Multilayer Structures.

Silicon-germanium multilayer structures consisting of alternating Si and Ge amorphous nanolayers were annealed by ultrashort laser pulses at near-infrared (1030 nm) and mid-infrared (1500 nm) wavelengths. In this paper, we investigate the effects of the type of substrate (Si or glass), and the number of laser pulses (single-shot and multi-shot regimes) on the crystallization of the layers. Based on structural Raman spectroscopy analysis, several annealing regimes were revealed depending on laser fluence, including partial or complete crystallization of the components and formation of solid Si-Ge alloys. Conditions for selective crystallization of germanium when Si remains amorphous and there is no intermixing between the Si and Ge layers were found. Femtosecond mid-IR laser annealing appeared to be particularly favorable for such selective crystallization. Similar crystallization regimes were observed for both single-shot and multi-shot conditions, although at lower fluences and with a lower selectivity in the latter case. A theoretical analysis was carried out based on the laser energy absorption mechanisms, thermal stresses, and non-thermal effects.

Fast Recombination of Charge-Transfer State in Organic Photovoltaic Composite of P3HT and Semiconducting Carbon Nanotubes Is the Reason for Its Poor Photovoltaic Performance.

Although the photovoltaic performance of the composite of poly-3-hexylthiophene (P3HT) with semiconducting single-walled carbon nanotubes (s-SWCNT) is promising, the short-circuit current density jSC is much lower than that for typical polymer/fullerene composites. Out-of-phase electron spin echo (ESE) technique with laser excitation of the P3HT/s-SWCNT composite was used to clarify the origin of the poor photogeneration of free charges. The appearance of out-of-phase ESE signal is a solid proof that the charge-transfer state of P3HT+/s-SWCNT- is formed upon photoexcitation and the electron spins of P3HT+ and s-SWCNT- are correlated. No out-of-phase ESE signal was detected in the same experiment with pristine P3HT film. The out-of-phase ESE envelope modulation trace for P3HT/s-SWCNT composite was close to that for the polymer/fullerene photovoltaic composite PCDTBT/PC70BM, which implies a similar distance of initial charge separation in the range 2-4 nm. However, out-of-phase ESE signal decay with delay after laser flash increase for P3HT/s-SWCNT composite was much faster, with a characteristic time of 10 µs at 30 K. This points to the higher geminate recombination rate for the P3HT/s-SWCNT composite, which may be one of the reasons for the relatively poor photovoltaic performance of this system.

Investigation of the Densification Behavior of Alumina during Spark Plasma Sintering.

The article presents the results of the investigation of the mechanism of the densification behavior of alumina-based ceramics during spark plasma sintering. The role of the heating rates and additives were investigated. The first (initial) stage of sintering was investigated by the Young-Cutler model. The second (intermediate) stage of sintering was investigated as a process of plastic deformation of a porous body under external pressure. It was shown that, at the initial stage, the formation of necks between the particles is controlled by grain boundary diffusion (the activation energy is Qb ≈ 20 kTm). At this stage, accommodation of the shape of the alumina particles is also occurring (an increase in the packing density). The accommodation process facilitates the shrinkage of the powder, which is reflected in a decrease in the effective activation energy of shrinkage at low heating rates (10 °C/min) to Qb ≈ 17 kTm. At heating rates exceeding 10 °C/min, the intensity of the processes of accommodation of alumina particles turns out to be much slower than the existing diffusion processes of growth of necks between the alumina particles. It was shown that the grain boundary sliding mechanism that occurs in the second stage of sintering can play a decisive role under conditions of spark plasma sintering with a high heating rate. The found value of the activation energy at the second stage of sintering is also close to the activation energy of grain-boundary diffusion of alumina (Qb ≈ 20 kTm). The influences of the second phase particles of MgO, TiO2, and ZrO2 on densification behavior of alumina-based ceramics were investigated. Since at the first stage of sintering the densification relates with the formation of necks between the particles of alumina, the additives (0.5% vol) have no noticeable effect on this process. It was also shown that the second phase particles which are located at the grain boundaries of alumina are not involved in the slip process during the second sintering stage. Analysis shows that additives act only in the final (third) stage of spark plasma sintering of alumina.

Development and in vitro assessment of a bi-layered chitosan-nano-hydroxyapatite osteochondral scaffold.

An innovative approach was developed to engineer a multi-layered chitosan scaffold for osteochondral defect repair. A combination of freeze drying and porogen-leaching out methods produced a porous, bioresorbable scaffold with a distinct gradient of pore size (mean = 160-275 µm). Incorporation of 70 wt% nano-hydroxyapatite (nHA) provided additional strength to the bone-like layer. The scaffold showed instantaneous mechanical recovery under compressive loading and did not delaminate under tensile loading. The scaffold supported the attachment and proliferation of human mesenchymal stem cells (MSCs), with typical adherent cell morphology found on the bone layer compared to a rounded cell morphology on the chondrogenic layer. Osteogenic and chondrogenic differentiation of MSCs preferentially occurred in selected layers of the scaffold in vitro, driven by the distinct pore gradient and material composition. This scaffold is a suitable candidate for minimally invasive arthroscopic delivery in the clinic with potential to regenerate damaged cartilage and bone.

Robotic sacrocolpopexy in pelvic organ prolapse: a review of current literature.

PURPOSE OF REVIEW: Recently, robotic sacrocolpopexy has become the gold standard for treating genital prolapse. Despite this, there is still much interest in this procedure, and many questions remain unanswered. This review focuses on the most critical articles on this issue that have been published in the last 2 years. RECENT FINDINGS: A summary of 23 articles is provided. There were no differences in total postoperative complications, postoperative stress incontinence, mesh erosion, and the success of the two surgical techniques in long-term investigations. Obesity modestly increases robotic approach difficulty and does not raise the mesh erosion rate or prolapse recurrence rate. Ultra-light and preprepared meshes with alternative fixation techniques can be applied with these procedures. Another emerging trend is alternative robotic approaches and the use of single-port surgery. SUMMARY: For women with pelvic organ prolapse, especially the elderly and obese, robotic sacrocolpopexy is well tolerated and effective. Despite highly restricted and heterogeneous data, recent investigations have included single incision methods and new mesh/fixation materials. Randomized trials with large sample size and excellent quality are necessary before the practical implementation of new techniques.

One-Pot Synthesis of 2-R-Naphtho[2,3-b]thiophene-4,9-diones via Cyclization of 2-(R-Ethynyl)-1,4-naphthoquinones with Na2S2O3.

The concise and efficient one-pot synthesis of 2-R-naphtho[2,3-b]thiophene-4,9-diones from 2-bromo-1,4-naphthoquinone and alkynes has been developed. The reaction proceeds through the formation of 2-(R-ethynyl)-1,4-naphthoquinones, which undergo transformation with Na2S2O3 to 2-R-naphtho[2,3-b]thiophene-4,9-diones via C-H sulfuration, accompanied by the formation of the aromatic Bunte salt, followed by its air oxidation and 5-endo-dig cyclization. The protocol is characterized by simplicity, good tolerance for functional groups, relatively mild conditions, and commercially available starting compounds.

Time-domain shape of electron spin echo signal of spin-correlated radical pairs in polymer/fullerene blends.

Temporal shape of electron spin echo (ESE) signal of photoinduced spin-correlated radical pairs (SCRP) in composite of conductive polymer P3HT and substituted fullerene PCBM is studied in details. ESE signals of radical pairs (RP) P3HT+/PCBM- are calculated in realistic model, taking into account finite microwave pulse length. Inhomogeneous broadening of resonant lines and interradical distance distribution are included. Experimentally observed ESE time-domain shape was found to contradict predictions of conventional SCRP theory, which would be valid in the case of very fast electron transfer. Thus, instantaneous formation of singlet SCRP is not the case for P3HT+/PCBM- pair, and spin system has enough time to evolve coherently during sequential electron transfer. While it is impossible to reproduce experimental data within simple singlet SCRP model, assumption of presence of additional - with respect to what is predicted by singlet SCRP theory - AE (absorption/emission) spin polarization gives convincing accordance with the experiment. Density matrix of RP P3HT+/PCBM- is a superposition of two contributions, namely the parts reflecting (i) antiphase polarization of original singlet-born SCRP and (ii) additional AE-polarization which is generated during initial stage of charge separation. AE-polarization affects experimental ESEEM (electron spin echo envelope modulation) traces, as well as ESE shape, making impossible their interpretation via simple singlet SCRP model. However, this effect can be eliminated by averaging of ESEEM traces over EPR spectral positions. Finally, choosing the optimal gate for ESE time-domain integration and proper microwave detection phase tuning are considered.

Light-induced charge separation in a P3HT/PC70BM composite as studied by out-of-phase electron spin echo spectroscopy.

A composite material of semiconducting polymer P3HT and fullerene derivative PC70BM was studied by means of electron spin echo (ESE) spectroscopy. The out-of-phase ESE signal was observed under laser irradiation of the composite at low temperature. We assume that during the charge separation process firstly the spin-correlated radical pairs in the singlet-polarized spin state are formed, and then the net polarization of radical pairs arises due to spin evolution. Both types of polarizations contribute to the out-of-phase ESE signal in the case of non-ideal microwave pulses. Analytical calculation of the echo shape for both types of initial polarization revealed that the contribution of the net polarization becomes zero after averaging over the whole EPR spectrum of the radical pair. This behavior was experimentally confirmed; thus the analysis of the out-of-phase ESE signal was simplified. Interspin distance distributions in the charge transfer state were obtained by modeling the out-of-phase ESE envelope modulation measured at different delays after laser flash TDAF from 300 ns to 3.3 µs at a temperature of 65 K. Due to geminate recombination and diffusion of the radicals from the interface the distribution becomes significantly broader with larger distances prevailing at longer TDAF values. The average distance between charges increases from 3.5 nm to 5.6 nm with an increase in TDAF.

Out-of-Phase Electron Spin Echo Studies of Light-Induced Charge-Transfer States in P3HT/PCBM Composite.

The light-induced charge-transfer (CT) state in the composite of the conductive polymer poly(3-hexylthiophene) (P3HT) and the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has been studied by electron spin echo (ESE) spectroscopy. The out-of-phase ESE signal corresponding to the spin-correlated radical pair P3HT(+)/PCBM(-) has been observed in this composite material. The time-domain ESE shape for different delays between the laser flash and the microwave pulse sequence has been analyzed. In order to explain the evolution of the out-of-phase ESE signal as a function of the delay between the microwave pulses, a model of the CT state is proposed. The hole is assumed to be delocalized on the P3HT chain over several thiophene subunits, while the point-dipole approximation is used to describe the interaction with the electron on PCBM. The distribution of distances between the positive and negative charges in the CT state has been evaluated.

Mesh-related and intraoperative complications of pelvic organ prolapse repair.

INTRODUCTION: To evaluate the rates of complications of pelvic organ prolapse repair and to determine their risk factors. MATERIAL AND METHODS: The study included 677 patients operated for pelvic organ prolapse with trocar guided Prolift mesh. Patients were followed up within 1 and 3 months. A phone interview was conducted and patients with complaints were invited and evaluated in office settings. RESULTS: Mean age was 60 years. For the phone interview, 86.5% of patients were available. Overall complication rates were 22.5% (152/677). Fifteen patients (2.2%) developed bleeding over 500 cc; pelvic hematomas - 5.5%; perineal hematomas - 2.5%; urethral injuries - 0.3%; bladder injury in 1.6%; rectal damage in 0.7% and ureteral trauma in 0.2%. MESH RELATED COMPLICATIONS INCLUDED: erosions in 4.8%; vaginal synechiae - 0.3%; protrusion of mesh into the bladder - 0.15%; vesicovaginal fistula with mesh protrusion - 0.3%; mesh shrinkage - 1%; dyspareunia and pain in 2.4% cases. Pelvic abscess was found in 0.6% including one case of lethal necrotizing fasciitis. The risk factors of complications were assessed via logistic regression analysis. CONCLUSIONS: Younger age, less prominent prolapse, hematomas and concomitant hysterectomies are associated with higher risk of complications.