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Publication Open Access Emergence of near-infrared photoluminescence via ZnS shell growth on the AgBiS2 nanocrystals(American Chemical Society, 2024) Department of Chemistry; Department of Electrical and Electronics Engineering; Önal, Asım; Kaya, Tarık Safa; Metin, Önder; Nizamoğlu, Sedat; Department of Chemistry; Department of Electrical and Electronics Engineering; Graduate School of Sciences and Engineering; College of Sciences; College of EngineeringAgBiS2 nanocrystals (NCs), composed of nontoxic, earth-abundant materials and exhibiting an exceptionally high absorption coefficient from visible to near-infrared (>105 cm(-1)), hold promise for photovoltaics but have lack of photoluminescence (PL) due to intrinsic nonradiative recombination and challenging shell growth. In this study, we reported a facile wet-chemical approach for the epitaxial growth of ZnS shell on AgBiS2 NCs, which triggered the observation of PL emission in the near-infrared (764 nm). Since high quality of the core is critical for epitaxial shell growth, we first obtained rock-salt structured AgBiS2 NCs with high crystallinity, nearly spherical shape and monodisperse size distribution (<6%) via a dual-ligand approach reacting Ag-Bi oleate with elemental sulfur in oleylamine. Next, a zincblende ZnS shell with a low-lattice mismatch of 4.9% was grown on as-prepared AgBiS2 NCs via a highly reactive zinc (Zn(acac)(2)) precursor that led to a higher photoluminescence quantum yield (PLQY) of 15.3%, in comparison with a relatively low reactivity precursor (Zn(ac)(2)) resulting in reduced PLQY. The emission from AgBiS2 NCs with ultrastrong absorption, facilitated by shell growth, can open up new possibilities in lighting, display, and bioimaging.Publication Open Access Hydrothermal-electrochemical growth of heterogeneous zno: co films(SpringerOpen, 2017) Department of Chemistry; Akkaya, Ceren Yılmaz; Ünal, Uğur; PhD Student; Faculty Member; Department of Chemistry; Koç University Surface Science and Technology Center (KUYTAM) / Koç Üniversitesi Yüzey Teknolojileri Araştırmaları Merkezi (KUYTAM); College of Sciences; Graduate School of Sciences and EngineeringBACKGROUND: Central venous cannulation is a necessary invasive procedure for fluid management, haemodynamic monitoring and vasoactive drug therapy. The right internal jugular vein (RIJV) is the preferred site. Enlargement of the jugular vein area facilitates catheterization and reduces complication rates. Common methods to enlarge the RIJV cross-sectional area are the Trendelenburg position and the Valsalva maneuver. OBJECTIVE: Compare the Trendelenburg position with upper-extremity venous return blockage using the tourniquet technique. DESIGN: Prospective clinical study. SETTING: University hospital. SUBJECTS AND METHODS: Healthy adult volunteers (American Society of Anesthesiologists class I) aged 18-45 years were included in the study. The first measurement was made when the volunteers were in the supine position. The RIJV diameter and cross-sectional area were measured from the apex of the triangle formed by the clavicle and the two ends of the sternocleidomastoid muscle, which is used for the conventional approach. The second measurement was performed in a 20 degrees Trendelenburg position. After the drainage of the veins using an Esbach bandage both arms were cuffed. The third measurement was made when tourniquets were inflated. MAIN OUTCOME MEASURE(S): Hemodynamic measurements and RIJV dimensions. RESULTS: In 65 volunteers the diameter and cross-sectional area of the RIJV were significantly widened in both Trendelenburg and tourniquet measurements compared with the supine position (P<.001 for both measures). Measurements using the upper extremity tourniquet were significantly larger than Trendelenburg measurements (P=.002 and <.001 for cross-sectional area and diameter, respectively). CONCLUSION: Channelling of the upper-extremity venous return to the jugular vein was significantly superior when compared with the Trendelenburg position and the supine position. LIMITATIONS: No catheterization and study limited to healthy volunteers.Publication Open Access Enhanced sinterability, thermal conductivity and dielectric constant of glass-ceramics with PVA and BN additions(Multidisciplinary Digital Publishing Institute (MDPI), 2022) Akkasoğlu, Ufuk; Çiçek, Buğra; N/A; Department of Chemistry; Arıbuğa, Dilara; Balcı, Özge; Researcher; Department of Chemistry; Koç University AKKİM Boron-Based Materials _ High-technology Chemicals Research _ Application Center (KABAM) / Koç Üniversitesi AKKİM Bor Tabanlı Malzemeler ve İleri Teknoloji Kimyasallar Uygulama ve Araştırma Merkezi (KABAM); Graduate School of Sciences and Engineering; College of Sciences; N/A; 295531With the rapid development of the microelectronics industry, many efforts have been made to improve glass-ceramics' sinterability, thermal conductivity, and dielectric properties, which are essential components of electronic materials. In this study, low-alkali borosilicate glass-ceramics with PVA addition and glass-BN composites were prepared and successfully sintered at 770 degrees C. The phase composition, density, microstructure, thermal conductivity, and dielectric constant were investigated. It was shown that PVA addition contributes to the densification process of glass-ceramics (~88% relative density, with closed/open pores in the microstructure) and improves the thermal conductivity of glass material from 1.489 to 2.453 W/K.m. On the other hand, increasing BN addition improves microstructures by decreasing porosities and thus increasing relative densities. A glass-12 wt. % BN composite sample exhibited almost full densification after sintering and presented apparent and open pores of 2.6 and 0.08%, respectively. A high thermal conductivity value of 3.955 W/K.m and a low dielectric constant of 3.00 (at 5 MHz) were observed in this material. Overall, the resulting glass-ceramic samples showed dielectric constants in the range of 2.40-4.43, providing a potential candidate for various electronic applications.Publication Open Access Improved superconducting properties in the Mg11B2 low activation superconductor prepared by low-temperature sintering(Nature Publishing Group (NPG), 2016) F. Cheng, Y.; Liu, Z. Ma; Hossain, M. S.; Department of Chemistry; Somer, Mehmet Suat; Faculty Member; Department of Chemistry; College of Sciences; 178882Mg11B2 has a great application prospect in the superconducting coils for fusion reactor as the “low activation superconductors”. The un-doped Mg11B2 and Cu-doped Mg11B2 bulks using 11B as a boron precursor were fabricated by low-temperature sintering in present work. It was found that the prepared Mg11B2 low activation superconductors exhibit better Jc performance than all of other Mg11B2 samples reported in previous studies. As for Cu doped Mg11B2, minor Cu addition can obviously improve the Mg11B2 grain crystallization and reduce the amount of MgO impurity. Hence, improved grain connectivity and higher Jc at low fields is obtained in Cu doped Mg11B2 samples. For un-doped samples, refined grains and more MgO impurity with proper size brought about more flux pinning centers, resulting in better Jc performance at high fields.Publication Open Access Highly sensitive optical sensor for hydrogen gas based on a polymer microcylinder ring resonator(Elsevier, 2020) Eryürek, Mustafa; Department of Physics; Department of Chemistry; Department of Electrical and Electronics Engineering; Bavili, Nima; Balkan, Timuçin; Morova, Berna; Uysallı, Yiğit; Kaya, Sarp; Kiraz, Alper; Researcher; Researcher; PhD Student; Faculty Member; Faculty Member; Department of Physics; Department of Chemistry; Department of Electrical and Electronics Engineering; Koç University Tüpraş Energy Center (KUTEM) / Koç Üniversitesi Tüpraş Enerji Merkezi (KÜTEM); Graduate School of Sciences and Engineering; College of Sciences; College of Engineering; N/A; N/A; N/A; N/A; 116541; 22542A highly sensitive platform is demonstrated for hydrogen gas (H-2) sensing based on a polymer microcylinder ring resonator (PMRR) obtained by an optical fiber coated with an inner nanofilm of amorphous palladium (Pd) and an outer polymer layer of polydimethylsiloxane (PDMS) permeable to H-2. The sensing scheme is based on monitoring the spectral shifts of high-quality optical resonances called whispering gallery modes (WGMs) that propagate in the vicinity of the outer rim of the PDMS layer without being affected by the absorption and scattering losses caused by the Pd nanofilm. WGMs are excited by a single-mode tapered optical fiber evanescently coupled to the PMRR. The observed reversible spectral shifts of the WGMs are induced by changes in the diameter of the PDMS layer caused by expansion or contraction of the Pd nanofilm exposed to varying concentrations of H-2. Maximum spectral shift sensitivity of 140 pm/% H-2, a minimum response time of 95 s, and minimum limit of detection of similar to 60 ppm were measured for sensors prepared with different thicknesses of the amorphous Pd nanofilm and tested in the H-2 concentration range up to 1%, having nitrogen gas (N-2) as a carrier. Experiments were also conducted with Pd nanofilms annealed in air or N-2 atmosphere after the deposition. In both cases, smaller sensitivities were observed due to the formation of larger grains within the film, resulting in slower diffusion and reduced solubility of H in the Pd layer. The impacts of oxygen gas and humidity on sensor performance were also studied.Publication Open Access Failures of the discourse of ethnicity: Turkey, Kurds, and the emerging Iraq(Sage, 2005) Department of Chemistry; Somer, Murat; Faculty Member; Department of Chemistry; College of Sciences; 110135This article analyzes the discursive-ideational barriers restricting regional cooperation by examining Turkey's relations with Iraqi Kurds from a critical, theoretical perspective in the context of Turkey's domestic reforms and its relations with the USA and the EU. It is argued that the ethnicity discourse undermines cooperation, insofar as it feeds the perception of rival groups with zero-sum interests. Presenting a simple model, the article argues that replacing the ethnicity discourse with alternative, post-ethnic discourses requires combining alternative discourses with policies that produce positive-sum interests, coordination between groups, and opportunities for joint collective actions. Hence, state capacity to formulate and implement such policies is crucial. Predictions and policy implications are generated accordingly. First, further reconciliation of Turkey's domestic Kurdish conflict through democratic and administrative reforms, EU integration, and the promotion of national-identity models that are more flexible and more reflective of diversity will facilitate cooperation with Iraqi Kurds. Second, prosperity and democratic stability in Iraq will help achieve a lasting resolution in Turkey. Third, regional cooperation requires that domestic and external actors promote the positive-sum perception of Turkish and Kurdish interests. Fourth, research can help by developing linguistic-analytical categories that transcend the narrow discourse of ethnicity in favor of discourses that reflect multiple and compatible group belongings.Publication Open Access CdTe quantum dot sensitized hexaniobate nanoscrolls and their photoelectrochemical properties(Royal Society of Chemistry (RSC), 2012) Department of Chemistry; Öztuna, Feriha Eylül Saraç; Akkaya, Ceren Yılmaz; Acar, Havva Funda Yağcı; Ünal, Uğur; PhD Student; Faculty Member; Department of Chemistry; Koç University Surface Science and Technology Center (KUYTAM) / Koç Üniversitesi Yüzey Teknolojileri Araştırmaları Merkezi (KUYTAM); College of Sciences; N/A; N/A; 178902; N/AWe have constructed hybrid quantum dot-layered niobate films with an electrophoretic deposition method. The structure and photoelectrochemical behaviour were demonstrated.Publication Open Access Weakening the strength of CO binding on subsurface alloyed Pt(111)(Elsevier, 2019) Ogasawara, Hirohito; Department of Chemistry; N/A; Kaya, Sarp; Gürlek, Sezen; Panahi, Mohammad; Solati, Navid; Faculty Member; PhD Student; Department of Chemistry; Koç University Tüpraş Energy Center (KUTEM) / Koç Üniversitesi Tüpraş Enerji Merkezi (KÜTEM); College of Sciences; Graduate School of Sciences and Engineering; 116541; N/A; N/A; N/AThe interaction of CO with Pt/3d/Pt(111) subsurface alloys (3d: Ni, Co, Fe) was investigated by combination of vibrational spectroscopy and temperature programmed desorption. The binding strength of CO is significantly reduced on Pt/Fe/Pt(111) and Pt/Co/Pt(111) and is sorted in the following order: Pt >Ni > Co approximate to Fe. Our analysis shows that the 3d admetal is stable in the subsurface region and CO is linearly bonded to the atop sites of the Pt(111) surface. At high CO coverage, compressed structures are obtained. At low CO coverage, the desorption activation energy of CO (similar to 143 kJ/mol for Pt(111)) drops to 124 kJ/mol for Pt/Ni/Pt(111), and goes further down to 111 and 110 kJ/mol for Pt/Co/Pt(111) and Pt/Fe/Pt(111), respectively. The enhancement in the surface activity is attributed to the modified backdonation to the antibonding states of adsorbed CO due to the downshifted 5d-band center of Pt upon embedding 3d metals in the subsurface region.Publication Open Access Grain boundary engineering with nano-scale InSb producing high performance InxCeyCo4Sb12+z skutterudite thermoelectrics(Elsevier, 2017) Li, Han; Su, Xianli; Tang, Xinfeng; Zhang, Qingjie; Uher, Ctirad; Snyder, G. Jeffrey; Department of Chemistry; Aydemir, Umut; Faculty Member; Department of Chemistry; College of Sciences; 58403Thermoelectric semiconductors based on CoSb3 hold the best promise for recovering industrial or automotive waste heat because of their high efficiency and relatively abundant, lead-free constituent elements. However, higher efficiency is needed before thermoelectrics reach economic viability for widespread use. In this study, n-type InxCeyCo4Sb12+z skutterudites with high thermoelectric performance are produced by combining several phonon scattering mechanisms in a panoscopic synthesis. Using melt spinning followed by spark plasma sintering (MS-SPS), bulk InxCeyCo4Sb12+z alloys are formed with grain boundaries decorated with nano-phase of InSb. The skutterudite matrix has grains on a scale of 100-200 nm and the InSb nano-phase with a typical size of 5-15 nm is evenly dispersed at the grain boundaries of the skutterudite matrix. Coupled with the presence of defects on the Sb sublattice, this multi-scale nanometer structure is exceptionally effective in scattering phonons and, therefore, InxCeyCo4Sb12/InSb nano-composites have very low lattice thermal conductivity and high zT values reaching in excess of 1.5 at 800 K.Publication Open Access Synthesis of stable gold nanoparticles using linear polyethyleneimines and catalysis of both anionic and cationic azo dye degradation(Royal Society of Chemistry (RSC), 2020) Abkenar, Sirous Khabbaz; Ow-Yang, Cleva W.; N/A; Department of Chemistry; Çavuşlar, Özge; Acar, Havva Funda Yağcı; Faculty Member; Department of Chemistry; Graduate School of Sciences and Engineering; College of Sciences; N/A; N/A; N/A; 178902Reduction of auric acid with polyethyleneimine (PEI) provides a simple, low-cost alternative for the production of cationic gold nanoparticles (GNPs). However, linear PEI (lPEI) failed to produce small, colloidally stable GNPs, so far. Since lPEI is a polyelectrolyte, pH should be an important factor both in reduction and stabilization of GNPs and may be optimized to produce small and stable lPEI/GNPs. Cationic GNPs were produced by the direct reduction of auric acid in water with lPEI utilizing two different methods to dissolve the polymer: by protonation or at high temperature. The influence of pH on the particle formation and properties was studied over a wide pH range (3.5 to 10). The impacts of the PEI/Au mass ratio, polymer molecular weight (2.5 and 25 kDa) and post-synthetic pH on the particle properties were also studied. Best is to dissolve lPEI by protonation and to clean the GNPs via controlled centrifugal precipitation. The MW did not influence the hydrodynamic size, stability or particle shape, but low MW lPEI provided faceted particles. This simple one pot synthesis of small, stable cationic GNPs in water is a valuable, simple alternative for producing new cationic GNPs with even low molecular weight lPEI. Additionally, these GNPs were evaluated as catalysts in the degradation of methyl orange (MO) (anionic-zwitterionic) and methylene blue (MB) (cationic) azo dyes at different pH values. The fastest degradation of MO and MB was recorded at pH 7.5 and 3.5, respectively. Overall, this is a rare case where a single catalyst quickly and effectively catalyzes the degradation of both cationic and anionic dyes.