Insight into stability of dithiocarbamate-modified adsorbents: Oxidation of dithiocarbamate.

We previously reported that monoalkyl dithiocarbamate-modified cellulose (DMC) exhibited excellent adsorption performance for arsenite (AsIII), cadmium (CdII), lead (PbII), gold (AuIII), silver (AgI), platinum (PtIV), and palladium (PdII). However, its adsorption capability for AsIII decreased by 96.4% after two weeks of storage at 40 °C under an air atmosphere. This decrease in adsorption ability could occur for other metals that dithiocarbamates can extract. In this study, we investigated the adsorption performance of DMC for various metals before and after storage and proposed a possible mechanism for this decrease. We found significant decreases in the adsorption abilities of PbII (11.4%), AgI (39.5%), PtIV (65.5%), and PdII (69.6%), whereas AuIII and CdII adsorption was largely retained, with decreases of 1.1% and 4.0%, respectively. FTIR analysis of the stored DMC revealed the formation of S-S bonds and the retention of dithiocarbamate peaks, indicating the formation of dithiocarbamate dimers (thiuram disulfides). To further support thiuram disulfide formation, dialkyl thiuram disulfides were tested for the adsorption of the seven employed metals. The metal adsorption behavior of dialkyl thiuram disulfides was almost identical to that of the stored adsorbent, ensuring thiuram disulfide formation. In conclusion, the loss of adsorption capability can be mainly attributable to the formation of thiuram disulfide.

A surface-grafted hydrogel demonstrating thermoresponsive adhesive strength change.

Here, we designed a surface-grafted hydrogel (SG gel) that exhibits thermoresponsive changes in surface properties. Quantitative measurements using a self-made device showed that the adhesive strength between the SG gel surface and a Bakelite plate due to hydrophobic interaction changed significantly with temperature.

Cross-linked dithiocarbamate-modified cellulose with enhanced thermal stability and dispersibility as a sorbent for arsenite removal.

Numerous reports have described dithiocarbamate (DTC)-modified cellulose sorbents that can selectively separate metal ions from water. We have previously synthesized a novel sorbent modified with DTC containing N-heterocycles in the backbone for the selective removal of hazardous metal ions. The sorbent was found to partially dissolve and aggregate in solution, reducing its sorption capacity. In this study, to prepare the sorbent for use as a soli-phase extraction material for the removal of arsenite (AsIII) ions, we attempted to decrease the solubility of the sorbent. The sorbent was cross-linked with epoxy or complexed with iron, and the quantities of the modifiers were varied between 3.0 and 10 mol%. As a result, the iron-complexed sorbents were still partially soluble, and cross-linkage with 6.0 mol% of epoxy made the sorbent almost insoluble and dispersed in solution. This sorbent also exhibited the highest AsIII sorption performance among the sorbents synthesized in this study. Although DTC-modified polymers are reported to lose their sorption capability after storage at 40 °C, the sorbent was found to be thermally stable. The optimum contact time and pH for AsIII removal were 20 min and 3.0, respectively. The maximum sorption capacity of the epoxy-cross-linked sorbent, calculated from the Langmuir isotherm equation, was 600 µmol g-1 (45 mg g-1) at 25 °C. Additionally, the sorbent was highly selective toward AsIII compared with previously reported sorbents and capable of removing approximately 97% of AsIII from environmental water. In conclusion, cross-linking enhances the stability of the sorbents in solutions, which facilitates the removal of AsIII from environmental water.

Speciation analysis of inorganic selenium in wastewater using a highly selective cellulose-based adsorbent via liquid electrode plasma optical emission spectrometry.

Speciation of selenium (Se) is typically carried out using a sophisticated technique such as ICP-MS after preconcentration using an adsorbent; however, the separation and preconcentration of inorganic Se has not been realized in the solutions containing high concentrations of SO42-. A dithiocarbamate-modified cellulose (DMC) was used in this study for the selective extraction and preconcentration of inorganic Se in wastewater, with a portable liquid electrode plasma-optical emission spectrometry (LEP-OES) being employed for quantification. DMC was found to selectively and quantitatively adsorb selenite (SeIV) over a wide range of pH (1.0-8.0); however, less than 3.0% of selenate (SeVI) was adsorbed in a pH range of 3.0-11. Quantitative extraction of SeIV was achieved even in the presence of 3.5 mol L-1 SO42-. The maximum sample volume from which 10 mg of DMC could quantitatively extract SeIV was found to be 500 mL. KOH (0.60 mL, 1.5 mol L-1) was found to quantitatively desorb SeIV retained on the adsorbent and yielded an enrichment factor of 833. The recovery of Se species from synthetic flue-gas desulfurization wastewater containing SeIV and SeVI at concentrations of 5.0 µmol L-1 was 96.2 ± 1.8% and 105.8 ± 1.8%, respectively.

Comparative evaluation of dithiocarbamate-modified cellulose and commercial resins for recovery of precious metals from aqueous matrices.

Economic and ecological issues motivate the recovery of precious metals (PMs: Ag, Au, Pd, and Pt) from secondary sources. From the viewpoint of eco-friendliness and cost-effectiveness, biomass-based resins are superior to synthetic polymer-based resins for PM recovery. Herein, a detailed comparative study of bio-sorbent dithiocarbamate-modified cellulose (DMC) and synthetic polymer-based commercial resins (Q-10R, Lewatit MonoPlus TP 214, Diaion WA30, and Dowex 1X8) for PM recovery from waste resources was conducted. The performances and applicability of the selected resins were investigated in terms of sorption selectivity, effect of competing anions, sorption isotherms, impact of temperature, and PM extractability from industrial wastes. Although the sorption selectivity toward PMs in acidic solutions by DMC and other resins was comparable, the sorption efficiency of commercial resins was adversely affected by competing anions. The sorption of PMs fitted the Langmuir model for all the studied resins, except Q-10R, which followed the Freundlich model. The maximum sorption capacity of DMC was 2.2-42 times higher than those of the resins. Furthermore, the PM extraction performance of DMC from industrial wastes exceeded that of the commercial resins, with a sorption efficiency ≥99% and a DMC dosage of 5-40 times lower.

Highly selective and straightforward recovery of gold and platinum from acidic waste effluents using cellulose-based bio-adsorbent.

Recovery of precious metals (PMs: AuIII and PtIV) from waste resources is of high importance due to the environmental concern and imbalance in the supply-demand ratio. A new approach has been explored for the recovery of PM using earlier developed bio-adsorbent, dithiocarbamate-modified cellulose (DMC). The adsorbent exhibits excellent adsorption efficiency (~99%) over a wide range of pH (< 1-6) and high selectivity towards AuIII and PtIV extraction from acidic solutions ([H+]: ≥ 0.2 mol L-1). The adsorption capacity (mmol g-1; AuIII: 5.07, PtIV: 2.41) and rate to reach equilibrium (≤ 30 min) were significantly higher than most of the reported bio-adsorbents. The AuIII or PtIV, after captured in DMC, was subsequently recovered as Au0 and Pt0 (yield > 99%) via incineration. The protocol was verified using real waste samples containing AuIII and PtIV in a mixed matrix of base metal ions, and a quantitative (~100%) and selective extraction of AuIII and PtIV were observed. The proposed technique is more effective and straightforward than the typical adsorption-desorption-reduction based method, because of the advantages like no-use of toxic eluents, and no-addition of any reductants to collect the PMs in elemental form.

Dithiocarbamate-modified cellulose-based sorbents with high storage stability for selective removal of arsenite and hazardous heavy metals.

A series of cellulose derivatives bearing dialkyl dithiocarbamate (DTC) groups were synthesized. Their ability of sorption of arsenite (As(iii)) and heavy metals and their storage stability in the solid state were investigated. Among them, DTC-modified cellulose derived from l-proline showed the highest sorption capacity for As(iii) and heavy metals to selectively remove them from aqueous media. It also showed exellent storage stability in air at 40 °C.

Donor-acceptor polymers containing thiazole-fused benzothiadiazole acceptor units for organic solar cells.

Two p-type semiconducting donor-acceptor polymers were designed and synthesized for use in organic solar cells. The polymers combine a benzodithiophene (BDT) donor and a thiazole-fused benzothiadiazole (TzBT) acceptor. Two TzBT acceptor units are compared, one with an alkylthio group (P1) and the other with a more strongly electron-withdrawing alkylsulfonyl group (P2) at the fused thiazole ring. The strongly electron-accepting nature of the TzBT unit lowers the lowest unoccupied molecular orbital (LUMO) energy of P1 and P2 relative to that of the BT analog (PBDT-BT), without altering the energy of the highest occupied molecular orbital (HOMO). Despite the smaller optical band gaps, bulk heterojunction organic solar cells fabricated using these polymers in a PC71BM blend showed high open-circuit voltages. The power conversion efficiency (PCE) of the P1-based device reached 6.13%. Though efficiency of the P2-based device was lower, photoelectric conversion extended into the near-IR region up to 950 nm.

Origin of Open-Circuit Voltage Loss in Polymer Solar Cells and Perovskite Solar Cells.

Herein, the open-circuit voltage (VOC) loss in both polymer solar cells and perovskite solar cells is quantitatively analyzed by measuring the temperature dependence of VOC to discuss the difference in the primary loss mechanism of VOC between them. As a result, the photon energy loss for polymer solar cells is in the range of about 0.7-1.4 eV, which is ascribed to temperature-independent and -dependent loss mechanisms, while that for perovskite solar cells is as small as about 0.5 eV, which is ascribed to a temperature-dependent loss mechanism. This difference is attributed to the different charge generation and recombination mechanisms between the two devices. The potential strategies for the improvement of VOC in both solar cells are further discussed on the basis of the experimental data.

[Safe and Effective Analgesia with Bilateral Continuous TAP Block for a Patient with Marfan Syndrome after Open Abdominal Aortic Aneurysm Repair].

A patient with Marfan syndrome underwent emergency open abdominal aortic aneurysm repair. She was referred to our department for postoperative analgesia. Taking the risk of possible dural ectasia into consideration, we avoided epidural block. Alternatively, we performed bilateral continuous transversus abdominis plane (TAP) block with sufficient analgesia. Lumbosacral dural ectasia is frequently observed in patients with Marfan syndrome. A few reports described that their fragile dura may contribute to an increased risk of dural puncture and postdural puncture headache (PDPH). Thus, in planning neuraxial block for a patient with Marfan syndrome, the possible consequences of lumbosacral dural ectasia should be considered. A case we herein present shows bilateral continuous TAP block could be a safe and effective alternative to epidural block.

Highly stable perovskite solar cells with an all-carbon hole transport layer.

Nano-carbon materials (carbon nanotubes, graphene, and graphene oxide) have potential application for photovoltaics because of their excellent optical and electronic properties. Here, we demonstrate that a single-walled carbon nanotubes/graphene oxide buffer layer greatly improves the photovoltaic performance of organo-lead iodide perovskite solar cells. The carbon nanotubes/graphene oxide buffer layer works as an efficient hole transport/electron blocking layer. The photovoltaic conversion efficiency of 13.3% was achieved in the organo-lead iodide perovskite solar cell due to the complementary properties of carbon nanotubes and graphene oxide. Furthermore, the great improvement of photovoltaic performance stability in the perovskite solar cells using carbon nanotubes/graphene oxide/polymethyl methacrylate was demonstrated in comparison with that using a typical organic hole transport layer of 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene.

Photo-excitation intensity dependent electron and hole injections from lead iodide perovskite to nanocrystalline TiO2 and spiro-OMeTAD.

Photo-excitation intensity dependent electron and hole injections from CH3NH3PbI3 perovskite to nanocrystalline TiO2 and spiro-OMeTAD are presented with the electron injection yield decrease from 95% to 10% and the hole injection yield decrease from 99% to 50% by increasing the excitation intensity from 10 nJ cm(-2) to 50 µJ cm(-2).

Spontaneous Defect Annihilation in CH3NH3PbI3 Thin Films at Room Temperature Revealed by Time-Resolved Photoluminescence Spectroscopy.

We utilized time-resolved photoluminescence (PL) spectroscopy to investigate the photocarrier recombination dynamics in CH3NH3PbI3 thin films as a function of the time elapsed from the film's fabrication. We found that the PL lifetime gradually increased and began to level out once the age of the film reached ∼30 h. Even under weak excitation, the PL dynamics depended on the excitation intensity in the fresh sample, while the mature sample displayed no excitation-intensity dependence associated with the PL dynamics. We submit that this can be explained by the fact that a significant number of defects are initially formed in CH3NH3PbI3 thin films fabricated by the sequential method and are spontaneously reduced by room-temperature annealing. Our results provide important insights for reducing the nonradiative recombination centers, which improves the power conversion efficiency of perovskite solar cells.

Photocarrier recombination dynamics in perovskite CH3NH3PbI3 for solar cell applications.

Using time-resolved photoluminescence and transient absorption measurements at room temperature, we report excitation-intensity-dependent photocarrier recombination processes in thin films made from the organo-metal halide perovskite semiconductor CH3NH3PbI3 for solar-cell applications. The photocarrier dynamics are well described by a simple rate equation including single-carrier trapping and electron-hole radiative recombination. This result provides clear evidence that the free-carrier model is better than the exciton model for interpreting the optical properties of CH3NH3PbI3. The observed large two-carrier recombination rate suggests the promising potential of perovskite semiconductors for optoelectronic device applications. Our findings provide the information about the dynamical behaviors of photoexcited carriers that is needed for developing high-efficiency perovskite solar cells.

[Extradural en bloc removal and in situ replacement of the anterior clinoid process].

Extradural removal of the anterior clinoid process (ACP) is useful and essential for approaching aneurysmal and tumor lesions in and around the cavernous sinus. A safe, rapid and less invasive technique is beneficial for this basic skull base surgery. We developed a new technique by sharply cutting the ACP together with the part of the sphenoid ridge bone followed by complete replacement. A series of patients with either basilar top or internal carotid artery aneurysms underwent the present technique. After frontotemporal craniotomy, the lateral frontal and anterior middle cranial fossae are exposed extradurally. The bone was cut using a cutting steel burr from the sphenoid ridge to the superior orbital fissure and to the optic canal. By sharply separating the meningo-orbital band between the dura propria and the periorbital fascia, the ACP is exposed. The cutting burr runs underneath the ACP. By leaving a very thin sheet of bone, the entire bone piece was elevated after fracturing the thin bone using a chisel. By severing the carotid ring, the internal carotid artery is freed and mobile either laterally or medially to obtain an ample basal cistern. After operation, the once removed clinoid process is replaced in situ using a titanium plate screw. Extradural en bloc removal and in situ replacement of the ACP can be safely done by this cutting procedure. This can provide a good cosmetic result without causing enophthalmos or transient oculomotor palsy.

[Transposition technique of microvascular decompression for hemifacial spasm without using a brain retractor].

A unique transposition technique in microvascular decompression for hemifacial spasm (HFS) was employed in patients with compression by either the peripheral artery or the main trunk of the vertebral artery. Complete transposition that secured free space between the offending artery and the root exit zone (REZ) was accomplished by introducing GORE-TEX tape around the artery and suturing it to the petrous dura. An adequate working space, as if operating in a shallow basin, was essential. Throughout the procedure, it was not necessary to use a brain retractor. Instead, a gentle wrapping retraction technique using a sucker was employed over the brain covered by a sheet of Gelfoam (Pfizer Japan Inc., Tokyo) and cotton. All patients showed complete cure of HFS immediately after surgery with this technique. The difficulty of transposing the vertebral artery can be overcome by well-designed surgical strategy and skillfulness.

Tilting operating table with self-control foot switch: a new neurosurgical tool.

BACKGROUND: Observation of the surgical field from all directions is essential in microneurosurgery. A tilting operating table operated by the surgeon can satisfy this need. METHODS: A tilting operating table operated by the surgeon using a foot switch was developed by modifying the Sugita table incorporating the X-Y shifter. RESULTS AND CONCLUSIONS: The modified operating table allows the surgeon to move the patient in the head up or down directions, as well as the left side down or right side down directions, so the surgical field can be inspected from all aspects without changing the vertical axis of the operating microscope.

Snare technique of vascular transposition for microvascular decompression--technical note.

Recurrence of trigeminal neuralgia (TN) or hemifacial spasm (HFS) after microvascular decompression (MVD) is not rare. The prosthesis material eventually adheres to the neurovascular structures and again transmits arterial pulsation to the nerve. A snare ligature technique using a Gore-Tex tape can be used for the transposition of the offending artery. No prosthesis is necessary once the transposition is complete. This technique requires introduction of either Gore-Tex tape or thread around the artery and suture over the petrous dura, so an adequate working space as if operating in a shallow basin is essential. Therefore, the osteoplastic craniotomy is a little larger than usual with the scalp flap entirely reflected using a semicircular skin incision. The Gore-Tex tape can be directly snared around the artery and sutured over the petrous dura. If this procedure is difficult, a thread can be attached to both ends of the Gore-Tex tape to pass the tape around the vessel. Seven patients with TN and 13 patients with HFS have undergone this surgery. Although the follow-up period is not yet long enough, there has been no case of recurrence. The present technique for MVD can provide complete and permanent transposition of the offending artery.

[Surgery of AVM of the inferior medullary velum by the uvulotonsillar approach--advantage of moving of the cerebellar tonsil: technical case report].

An incidentally found arteriovenous malformation (AVM) of the inferior medullary velum behind the medulla was removed by the lateral approach to the fourth ventricle originally described by Seeger in 1980. A wide posterior fossa craniotomy was performed to move the cerebellar tonsil laterally with C-1 laminectomy. The tela chroidea and inferior medullary velum, the two main sheets of tissue that form the lower half of the roof of the fourth ventricle can be exposed by gently displacing the tonsils laterally without splitting the vermis. Both the cerebellomedullary and uvulotonsillar spaces were exposed. Because the lateral cerebellomedullary cistern was also exposed, the moving of the cerebellar tonsil in a lateral direction was easy to do without injuring the cerebellar tissues. The nidus was located mainly in the extrapial plane that received feeding arteries from the posterior inferior cerebellar artery. The nidus was removed in a dry field without bleeding. This report is the first report of surgical removal of unruptured AVM of the inferior medullary velum through the so-called telovelar or transcerebellomedullary fissure approach. We propose to call this approach the uvulotonsillar approach to emphasize the dissecting plane between the uvula and the tonsil.