Trends in worldwide nanotechnology patent applications: 1991 to 2008

Nanotechnology patent applications published during 1991–2008 have been examined using the “title–abstract” keyword search on esp@cenet “worldwide” database. The longitudinal evolution of the number of patent applications, their topics, and their respective patent families have been evaluated for 15 national patent offices covering 98% of the total global activity. The patent offices of the United States (USA), People’s Republic of China (PRC), Japan, and South Korea have published the largest number of nanotechnology patent applications, and experienced significant but different growth rates after 2000. In most repositories, the largest numbers of nanotechnology patent applications originated from their own countries/regions, indicating a significant “home advantage.” The top applicant institutions are from different sectors in different countries (e.g., from industry in the US and Canada patent offices, and from academe or government agencies at the PRC office). As compared to 2000, the year before the establishment of the US National Nanotechnology Initiative (NNI), numerous new invention topics appeared in 2008, in all 15 patent repositories. This is more pronounced in the USA and PRC. Patent families have increased among the 15 patent offices, particularly after 2005. Overlapping patent applications increased from none in 1991 to about 4% in 2000 and to about 27% in 2008. The largest share of equivalent nanotechnology patent applications (1,258) between two repositories was identified between the US and Japan patent offices.     

Longitudinal Nanotechnology Development (1991--2002): National Science Foundation Funding and its Impact on Patents

Nanotechnology holds the promise to revolutionize a wide range of products, processes and applications. It is recognized by over sixty countries as critical for their development at the beginning of the 21st century. A significant public investment of over $1 billion annually is devoted to nanotechnology research in the United States. This paper provides an analysis of the National Science Foundation (NSF) funding of nanoscale science and engineering (NSE) and its relationship to the innovation as reflected in the United States Patent and Trade Office (USPTO) patent data. Using a combination of bibliometric analysis and visualization tools, we have identified several general trends, the key players, and the evolution of technology topics in the NSF funding and commercial patenting activities. This study documents the rapid growth of innovation in the field of nanotechnology and its correlation to funding. Statistical analysis shows that the NSF-funded researchers and their patents have higher impact factors than other private and publicly funded reference groups. This suggests the importance of fundamental research on nanotechnology development. The number of cites per NSF-funded inventor is about 10 as compared to 2 for all inventors of NSE-related patents recorded at USPTO, and the corresponding Authority Score is 20 as compared to 1.8.     

Biogenic iron compounds: XRD, Mossbauer and FTIR study

Materials based on biogenic iron oxides, which are a product of the metabolic activities of the neutrophilic iron-oxidizing bacteria (NIOB) from Sphaerotilus-Leptothrix group, were investigated. Natural microbial probes were collected from freshwater flow from Vitosha Mountain (Bulgaria) and cultivated under laboratory conditions in respect to select suitable cultures and conditions (nutrition media) for biomaterial accumulation of biogenic oxides. Samples were studied by physicochemical methods: X-ray diffraction, Mossbauer spectroscopy and IR spectroscopy. Their phase composition and physicochemical properties were obtained. Presence of both amorphous and crystal phase (ultra- and highly dispersed particles) was proved. Iron-containing compound in the natural biomass consists of α-FeOOH. The cultivated materials have more complex composition with iron-containing ingredients as α-FeOOH, Γ-FeOOH, Γ-Fe₂O₃ and Fe₃O₄. The sample of natural biomass was tested in reaction of CO oxidation and it showed potential to be used as catalyst support.      

A Weyl type formula for Fourier spectra and frames

We prove qualitative and quantitative results concerning the asymptotic density in dilates of centered convex bodies of the frequency vectors of orthogonal exponential bases and frames associated to bounded domains in Euclidean space.

     

A semi-analytical model for the behavior of saturated viscoplastic materials containing two populations of voids of different sizes

This paper presents a micromechanical model for a porous viscoplastic material containing two populations of pressurized voids of different sizes. Three scales are distinguished: the microscopic scale (corresponding to the size of the small voids), the mesoscopic scale (corresponding to the size of the large voids) and the macroscopic scale. It is assumed that the first homogenization step is performed at the microscopic scale, and, at the mesoscopic scale, the matrix is taken to be homogeneous and compressible. At the mesoscopic scale, the second homogenization step, on which the present study focuses, is based on a simplified representative volume element: a hollow sphere containing a pressurized void surrounded by a nonlinear viscoplastic compressible matrix. The nonlinear behavior of the matrix, which is expressed using the results obtained in the first homogenization step, is approached using a modified secant linearization procedure involving the discretization of the hollow sphere into concentric layers. Each layer has uniform secant moduli. The predictions of the model are compared with the more accurate numerical results obtained using the finite element method. Good agreement is found to exist with all the macroscopic stress triaxialities and all the porosity and nonlinearity values studied.     

Cyano-bridged homodinuclear copper(II) complexes

The synthesis and structural analysis (single crystal X-ray data) of two mononuclear ([Cu(L(1))(CN)]BF(4) and [Cu(L(3))(CN)](BF(4))) and three related, cyanide-bridged homodinuclear complexes ([{Cu(L(1))}(2)(CN)](BF(4))(3)·1.35 H(2)O, [{Cu(L(2))}(2)(CN)](BF(4))(3) and [{Ni(L(3))}(2)(CN)](BF(4))(3)) with a tetradentate (L(1)) and two isomeric pentadentate bispidine ligands (L(2), L(3); bispidines are 3,7-diazabicyclo[3.3.1]nonane derivatives) are reported, together with experimental magnetic, electron paramagnetic resonance (EPR), and electronic spectroscopic data and a ligand-field-theory-based analysis. The temperature dependence of the magnetic susceptibilities and EPR transitions of the dicopper(II) complexes, together with the simulation of the EPR spectra of the mono- and dinuclear complexes leads to an anisotropic set of g- and A-values, zero-field splitting (ZFS) and magnetic exchange parameters (Cu1: g(z) = 2.055, g(x) = 2.096, g(y) = 2.260, A(z) = 8, A(x) = 8, A(y) = 195 × 10(-4) cm(-1), Cu2: g and A as for Cu(1) but rotated by the Euler angles α = -6°, β = 100°, D(exc) = -0.07 cm(-1), E(exc)/D(exc) = 0.205 for [{Cu(L(1))}(2)(CN)](BF(4))(3)·1.35 H(2)O; Cu1,2: g(z) = 2.025, g(x) = 2.096, g(y) = 2.240, A(z) = 8, A(x) = 8, A(y) = 190 × 10(-4)cm(-1), D(exc) = -0.159 cm(-1), E(exc)/D(exc) = 0.080 for [{Cu(L(2))}(2)(CN)](BF(4))(3)). Thorough ligand-field-theory-based analyses, involving all micro states and all relevant interactions (Jahn-Teller and spin-orbit coupling) and DFT calculations of the magnetic exchange leads to good agreement between the experimental observations and theoretical predictions. The direction of the symmetric magnetic anisotropy tensor D(exc) in [{Cu(L(2))}(2)(CN)](BF(4))(3) is close to the Cu···Cu vector (22°), that is, nearly perpendicular to the Jahn-Teller axis of each of the two Cu(II) centers, and this reflects the crystallographically observed geometry. Antisymmetric exchange in [{Cu(L(1))}(2)(CN)](BF(4))(3)·1.35 H(2)O causes a mixing between the singlet ground state and the triplet excited state, and this also reflects the observed geometry with a rotation of the two Cu(II) sites around the Cu···Cu axis.     

Modified rate equation model including the photon�Cphoton resonance

We show that, when the longitudinal confinement factor in an edge-emitting laser is treated as a dynamic variable, the modulation transfer function has an extra term. This term produces a supplementary photon?Cphoton resonance peak in the modulation response at a frequency corresponding to the frequency separation between longitudinal modes, when these modes are phase-locked long enough (quasi-phase-locked). The photon?Cphoton resonance peak is strongest when two consecutive quasi-phase-locked dominant longitudinal modes have similar longitudinal envelopes and share equally the photon population.     

Unprecedented synthesis of 1,3-dimethylcyclobutadiene in the solid state and aqueous solution

Cyclobutadiene ( CBD ), the smallest cyclic hydrocarbon bearing conjugated double bonds, has long intrigued chemists because of its chemical characteristics. The question of whether the molecule could be prepared at all has been answered, but the parent compound and its unperturbed derivatives have eluded crystallographic characterization or synthesis “in water”. Different approaches have been used to generate and to trap cyclobutadiene in a variety of confined environments: a) an Ar matrix at cryogenic temperatures, b) a hemicarcerand cage enabling the characterization by NMR spectroscopy in solution, and c) a crystalline guanidinium–sulfonate–calixarene G₄C matrix that is stable enough to allow photoreactions in the solid state. In the latter case, the 4,6‐dimethyl‐α‐pyrone precursor, Me₂1 , has been immobilized in a guanidinium–sulfonate–calixarene G₄C crystalline network through a combination of non‐covalent interactions. UV irradiation of the crystals transforms the entrapped Me₂1 into a 4,6‐dimethyl‐Dewar‐β‐lactone intermediate, Me₂2 , and rectangular‐bent 1,3‐dimethylcyclobutadiene, Me₂CBD^R , which are sufficiently stable under the confined conditions at 175 K to allow a conventional structure determination by X‐ray diffraction. Further irradiation drives the reaction towards Me₂3&Me₂CBD^S /CO₂ (63.7 %) and Me₂CBD^R (37.3 %) superposed crystalline architectures and the amplification of Me₂CBD^R . The crystallographic models are supported by additional FTIR and Raman experiments in the solid state and by ¹H NMR spectroscopy and ESI mass spectrometry experiments in aqueous solution. Amazingly, the 4,6‐dimethyl‐Dewar‐β‐lactone, Me₂2 , the cyclobutadiene‐carboxyl zwitterion, Me₂3 , and 1,3‐dimethylcyclobutadiene, Me₂CBD , were obtained by ultraviolet irradiation of an aqueous solution of G₄C{Me₂1} . 1,3‐Dimethylcyclobutadiene is stable in water at room temperature for several weeks and even up to 50 °C as demonstrated by ¹H NMR spectroscopy.