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The purpose of this research is to analyze the factors that influence the quality of remuneration services for educators and educational staff at Universitas Muhammadiyah Sorong as a BLU and to analyze the impact of the quality of remuneration services on the satisfaction levels of educators and educational staff at Universitas Muhammadiyah Sorong as a BLU. The research method used is a survey with statistical testing. The sample used consists of the Implementing Elements and Academic Supporting Elements of Universitas Muhammadiyah Sorong, which represent all users of services at Universitas Muhammadiyah Sorong. Data analysis uses the Importance-Performance Analysis method. The research results show that all dimensions of remuneration service quality (tangible evidence, assurance, responsiveness, and reliability) have a positive and significant impact on satisfaction levels, except for the empathy dimension, which does not have a significant impact. The increase in satisfaction is more driven by the quick responsiveness of the remuneration service, followed by tangible evidence, reliability, and assurance. The implication for Muhammadiyah University of Sorong is the need to prioritize improvements in these dimensions in an effort to enhance the satisfaction of lecturers and educational staff through the provision of optimal remuneration services.

Bovine xenografting is a method of grafting bovine bones to other species. This study aimed to determine the effect of the administration of bovine xenografts on accelerated healing in domestic dogs with femoral fractures. This study used a total of 4 dogs (two individuals as the treatment group and other two as the control group) diagnosed with diaphyseal femoral fractures. The bovine xenograft in the form of hydroxyapatite (Ca10(PO4)6(OH)) was synthesized in this study. The femur fracture surgery was carried out using the open reduction and internal fixation (ORIF) method, followed by the administration of 10 grams of Hydroxyapatite powder from the bovine bone in the fracture area, in the treatment group. The control group was not treated with Hydroxyapatite. Radiographic examinations were carried out on days 0, 14, and 45 post-operation. The parameters observed included the formation of radiopaque mass on the radiographic imaging, indicating the formation of calli around the fracture area. The radiographic examination showed that in the treatment group, the radiopaque mass was apparent on day 14 post-operation while it was not observable in the control group. On day 45 post-operation, the mass was more clearly visible in the treatment group, while it was barely visible in the control group. This research indicated that bovine xenograft has the potential to accelerate the fracture healing process in domestic dogs

Judul: Rancang bangun pembangkit listrik tenaga sampah (PLTSa) di lingkungan Universitas Singaperbangsa Karawang Title: Design and build a waste power plant (WPP) at the University of Singaperbangsa KarawangSampah merupakan salah satu permasalahan yang terus dicari solusinya. Volume sampah dari hari ke hari terus meningkat dan menjadi masalah yang serius di Kota Karawang khususnya lingkungan Universitas Singaperbangsa Karawang. Salah satu pemanfaatan sampah yaitu mengubahnya menjadi energi listrik. Salah satu alternatif untuk mengolah sampah menjadi energi listrik yaitu dengan menggunakan pembangkit listrik tenaga sampah (PLTSa). Pembangkit listrik tenaga sampah terdiri dari komponen-komponen utama seperti boiler, incinerator, turbin, generator, control panel, dan juga rangka utama. Material yang dibutuhkan untuk membuat PLTSa adalah plat stainless steel, plat besi, besi behel, kuningan, besi L, besi hollow, batu bata, semen, pipa besi, dan pipa stainless steel. Dalam proses pengujian didapat data pembakaran dengan sampah heterogen atau campuran selama 180 menit didapat tekanan maksimal 5 bar, temperatur ruang bakar 162,2°C, dan menghasilkan tegangan alternator sebesar 21,9 volt. Pada pembakaran dengan kayu selama 135 menit didapat tekanan 5 bar dan temperatur ruang bakar 205,4 menghasilkan tegangan alternator 22,1 volt.Garbage is one of the issues that are still being resolved. The trash volume continues to grow and has developed into a severe issue in Karawang, particularly at the University of Singaperbangsa Karawang. Converting trash into electrical energy is one of the waste applications. Utilizing a waste power plant (WPP) is one method of converting garbage to electrical energy. The waste energy plant comprises many significant components, including boilers, incinerators, turbines, generators, control panels, and the mainframe. Stainless steel plates, iron plates, stirrup iron, brass, L iron, hollow iron, bricks, cement, iron pipes, and stainless steel pipes are the materials required to manufacture WPP. The test procedure produced a maximum pressure of 5 bar, a combustion chamber temperature of 162.2°C, and an alternator voltage of 21.9 volts using data acquired from 180 minutes of burning with heterogeneous or mixed trash. After 135 minutes of burning wood, the pressure in the combustion chamber is 5 bars, and the temperature is 205.4 degrees, producing an alternator voltage of 22.1 volts.

This study aims to determine whether there are clear differences between groups on the dependent variable. This analysis uses the independent variable Life Expectancy (X1), Number of Health Facilities (Puskesmas) (X2), Number of Facilities (Supporting Puskesmas) (X3), Polindes Facilities (X4), percentage of households that do not use electricity (X5). The dependent variable is the regencies / cities lagging behind and developing in West Papua. The research sample uses secondary data, which are the results of the 2017 National Socio-Economic Survey (SUSENAS) conducted by the West Papua Statistics Agency (BPS). The discriminatory method is to test the difference between the stipulation of disadvantaged districts / cities and the stipulation of a Presidential Decree. 131 of 2015, concerning disadvantaged districts / cities in West Papua with normality test data. The object applied is all districts / cities in West Papua. Discriminant analysis can separate lagging and developing districts / cities in West Papua province by calculating function scores by comparing with interrupted scores, the results of the study are 5 districts / cities classified as disadvantaged districts and 6 districts / cities classified as developing districts/city. the influencing factor is facilities (village polyclinic) and the percentage of households that do not use electricity with a percentage decision 100%, theoretical evidence that the five variables prove that the discriminant analysis method shows the same results as the results issued by the Presidential Decree. 131 of 2015 with the percentage of decisions is 100%.

Some optical and electrical properties of 3-diethylamino-1-propylsulfonamide substituted zinc and metal-free phthalocyanines are presented. These materials are sensitive to NO2 even at concentrations as low as 0.1-2.5 ppm. Electrical conductivity and photoconductivity were used as the detection methods. [ABSTRACT FROM AUTHOR]

A comparative study of electrical properties of films fabricated from a series of polymeric core shell particles and microgels is presented. The core shell particles consist of spherical polystyrene core covered by electrically conductive poly[3,4-(ethylenedioxy)thiophene] (PEDOT). Microgels are composed of PEDOT grains embedded into crosslinked, electrically insulating polymer bodies. The electrical resistivity of the films changes from 12 GΩ⋅cm to 100Ω⋅cm; the value depends on the thickness of the shell cover and the type of oxidant used for PEDOT polymerization. Electrical conductivity in the films of core shell particles is thermally activated and obeys the inverse Meyer--Neldel rule, which indicates that the electrical conductivity is governed by a common transport mechanism. Electrical conductivity depends, among others, on the humidity in the surrounding environment. In films consisting of particles with a high PEDOT content (and thus high conductivity) the resistivity increases as the humidity increases. Conversely, when the films are formed from particles having a low PEDOT content, the humidity has a reverse effect. An explanation for this behaviour is proposed. The frequency dependences of ac conductivities of high conductivity "core shell" and "microgel" films suggest existence of hopping charge carrier transport mechanism for large humidity scale. [ABSTRACT FROM AUTHOR]

Photoalignment ability of poly[methyl(phenyl)silylene] (PMPSi) films makes possible to use them as hole transporting substrates for the preparation of organic oriented films. PMPSi layer prepared by spin coating was after drying irradiated with linearly polarized UV light. Then, water soluble hydroxyaluminium phthalocyaninesulfonate sodium salt [Al(OH)Pc(SO 3 Na) 1–2 ] was deposited by casting. The cell ITO/PMPSi/Al(OH)Pc(SO 3 Na) 1–2 /Al showed non-linear current-voltage characteristics. For applied voltages higher than 20 V, a polarized electroluminescence was observed. Its polarizing anisotropy R EL = F ? /F | was ca. 2 and 2.1 for phthalocyanine film prepared from solution and by vacuum evaporation, respectively. [ABSTRACT FROM AUTHOR]

Jamu yang mengandung ramuan darah ular kobra merupakan salah satu jamu tradisional yang dipercaya memiliki banyak khasiat bagi kesehatan tubuh manusia. Di sisi lain belum diketahui seberapa besar cemaran bakteri yang terdapat pada ramuan darah tersebut. Staphylococcus aureus sebagai bakteri yang dapat menyebabkan keracunan pangan dan umumnya terisolasi dari produk makanan. Penelitian ini mengungkap keberadaan Staphylococcus aureus pada jamu darah ular kobra. Penelitian ini menggunakan 10 sampel darah segar ular kobra dan 10 sampel ramuan jamu tradisional dengan darah ular kobra. Isolasi Staphylococcus aureus menggunakan media Vogel Jhonson Agar (VJA). Hasil penelitian menunjukkan cemaran Staphylococcus aureus terdeteksi pada swab gelas, darah segar, dan ramuan darah ular kobra. Analisis variansi (ANOVA) dari rerata cemaran Staphylococcus aureus menunjukkan tidak ada perbedaan antara swab gelas, darah dan ramuan darah ular kobra. Walaupun demikian, jamu yang mengandung darah ular kobra berpotensi mengandung Staphylococcus aureus yang membahayakan konsumen.

Introduction: Oncoplastic breast conserving surgery (OBCS) aims to provide safe and satisfying surgery for breast cancer patients. The American Society of Breast Surgeons (ASBrS) classification system is based on volumetric displacement cut-offs (level I for <20% of breast volume; level II for 20-50%). It aims to facilitate communication among treating physicians and patients. Here, we investigate whether the extent of OBCS as classified by ASBrS independently predicts postoperative complications., Materials and Methods: This retrospective analysis of a prospectively maintained database included patients with stage I-III breast cancer who underwent OBCS between 03/2011 and 12/2020 at a Swiss university hospital. Outcomes included short-term (≤30 days) complications and chronic (>30 days) pain after surgery. Multivariate logistic regression models were used to identify independent predictors., Results: In total, 439 patients were included, 314 (71.5%) received ASBrS level I surgery, and 125 (28.5%) underwent ASBrS level II surgery. ASBrS level II was found to be an independent predictor of delayed wound healing (odds ratio [OR] 9.75, 95% confidence intervals (CI) 2.96-32.10). However, ASBrS level did not predict chronic postoperative pain (incidence rate ratio [IRR] 1.20, 95%CI 0.85-1.70), as opposed to age (IRR 1.19, 95%CI 1.11-1.27 per 5 years decrease), and weight disorders (underweight [BMI <18.5] vs. normal weight [BMI 18.5 < 25]: IRR 4.02, 95%CI 1.70-9.54; obese [BMI ≥30] vs. normal weight: IRR 2.07, 95%CI 1.37-3.13)., Conclusion: ASBrS level II surgery predicted delayed wound healing, warranting close clinical follow-up and prompt treatment to avoid delays in adjuvant therapy., Competing Interests: Declaration of competing interest No competing interests in the current work were reported. The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Kurzeder: C. Kurzeder received consulting fees from GSK, Astra Zeneca, Novartis, Roche, Eli Lilly S.A., Pfizer, Genomic Health, Merck MSD, Novartis, PharmaMar, Tesaro; sits on advisory boards of GSK, Astra Zeneca, Novartis, Roche, Eli Lilly S.A., Pfizer, Genomic Health, Merck MSD, Novartis, PharmaMar, Tesaro; received travel support from GSK, Astra Zeneca, Roche. Weber: W.P. Weber received research support from Agendia paid to the University Hospital Basel for the TAXIS study (OPBC-03, SAKK 23/16, IBCSG 57-18, ABCSG-53, GBG 101). All other authors declare no competing interests., (© 2023 Published by Elsevier Ltd.)

Degenerative disorders of the retina (including age-related macular degeneration), which originate primarily at or within the retinal pigmented epithelial (RPE) layer, lead to a progressive disorganization of the retinal anatomy and the deterioration of visual function. The substitution of damaged RPE cells (RPEs) with in vitro cultured RPE cells using a subretinal cell carrier has shown potential for re-establishing the anatomical structure of the outer retinal layers and is, therefore, being further studied. Here, we present the principles of a surgical technique that allows for the effective subretinal transplantation of a cell carrier with cultivated RPEs into minipigs. The surgeries were performed under general anesthesia and included a standard lens-sparing three-port pars plana vitrectomy (PPV), subretinal application of a balanced salt solution (BSS), a 2.7 mm retinotomy, implantation of a nanofibrous cell carrier into the subretinal space through an additional 3.0 mm sclerotomy, fluid-air exchange (FAX), silicone oil tamponade, and closure of all the sclerotomies. This surgical approach was used in 29 surgeries (18 animals) over the past 8 years with a success rate of 93.1%. Anatomic verification of the surgical placement was carried out using in vivo fundus imaging (fundus photography and optical coherence tomography). The recommended surgical steps for the subretinal implantation of RPEs on a carrier in minipig eyes can be used in future preclinical studies using large-eye animal models.

Purpose: The development of primary human retinal pigmented epithelium (hRPE) for clinical transplantation purposes on biodegradable scaffolds is indispensable. We hereby report the results of the subretinal implantation of hRPE cells on nanofibrous membranes in minipigs., Methods: The hRPEs were collected from human cadaver donor eyes and cultivated on ultrathin nanofibrous carriers prepared via the electrospinning of poly(L-lactide-co-DL-lactide) (PDLLA). "Libechov" minipigs (12-36 months old) were used in the study, supported by preoperative tacrolimus immunosuppressive therapy. The subretinal implantation of the hRPE-nanofibrous carrier was conducted using general anesthesia via a custom-made injector during standard three-port 23-gauge vitrectomy, followed by silicone oil endotamponade. The observational period lasted 1, 2, 6 and 8 weeks, and included in vivo optical coherence tomography (OCT) of the retina, as well as post mortem immunohistochemistry using the following antibodies: HNAA and STEM121 (human cell markers); Bestrophin and CRALBP (hRPE cell markers); peanut agglutining (PNA) (cone photoreceptor marker); PKCα (rod bipolar marker); Vimentin, GFAP (macroglial markers); and Iba1 (microglial marker)., Results: The hRPEs assumed cobblestone morphology, persistent pigmentation and measurable trans-epithelial electrical resistance on the nanofibrous PDLLA carrier. The surgical delivery of the implants in the subretinal space of the immunosuppressed minipigs was successfully achieved and monitored by fundus imaging and OCT. The implanted hRPEs were positive for HNAA and STEM121 and were located between the minipig's neuroretina and RPE layers at week 2 post-implantation, which was gradually attenuated until week 8. The neuroretina over the implants showed rosette or hypertrophic reaction at week 6. The implanted cells expressed the typical RPE marker bestrophin throughout the whole observation period, and a gradual diminishing of the CRALBP expression in the area of implantation at week 8 post-implantation was observed. The transplanted hRPEs appeared not to form a confluent layer and were less capable of keeping the inner and outer retinal segments intact. The cone photoreceptors adjacent to the implant scaffold were unchanged initially, but underwent a gradual change in structure after hRPE implantation; the retina above and below the implant appeared relatively healthy. The glial reaction of the transplanted and host retina showed Vimentin and GFAP positivity from week 1 onward. Microglial activation appeared in the retinal area of the transplant early after the surgery, which seemed to move into the transplant area over time., Conclusions: The differentiated hRPEs can serve as an alternative cell source for RPE replacement in animal studies. These cells can be cultivated on nanofibrous PDLLA and implanted subretinally into minipigs using standard 23-gauge vitrectomy and implantation injector. The hRPE-laden scaffolds demonstrated relatively good incorporation into the host retina over an eight-week observation period, with some indication of a gliotic scar formation, and a likely neuroinflammatory response in the transplanted area despite the use of immunosuppression.

Managing the excited-state decay by a supramolecular structure is a crucial issue for organic photovoltaics. We show that in thin films of metallo-supramolecular polymers made of bis(terpyridine-4'-yl)terthiophenes and Z n 2 + coupling ions, the photoexcited states generated by ultrashort laser pulses at the wavelength of 440 nm decay by the bi-molecular annihilation predominantly controlled by the Förster transfer between singlet states. During this bi-molecular annihilation of singlet states, intermediate hot triplet pairs are formed, which subsequently dissociate into long-living diffusing triplet states. It explains a significant shortening of the triplet state rise time with increasing pump fluence. The diffusion coefficient of triplets showed power-law time dependence, with its exponent proportional to the pump fluence, decreasing thus the diffusivity of triplets., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Menšík, Rais, Thottappali, Güloğlu, Toman, Vohlídal and Pfleger.)

Purpose: Medical students are at increased risk of poor mental health and need to regularly engage in preventive programs to maintain well-being. However, many do not and it remains an open question whether these programs should be mandatory. We implemented a RCT to examine the effectiveness of assigning medical students to a wellness intervention on adherence to engagement in the assigned intervention and on psychological and academic outcomes., Method: Medical students participated in a 12-week randomized controlled intervention involving one-hour wellness sessions of either (1) yoga; (2) mindfulness; or (3) walking, held twice-weekly. Students completed standardized psychological assessments at baseline and following the intervention., Results: Students randomized to the wellness intervention group engaged in more minutes of assigned activities than students randomized to the control. There was a significant difference in the change from pre- to post- intervention on measures of state anxiety and perceived stress, with better outcomes for the intervention group., Conclusions: The assignment of twice-weekly wellness intervention sessions protects medical students from state anxiety and perceived stress with no negative impact on academic performance. Students adhered to the sessions and reported enjoying the sessions once trying them. Actual engagement is more important than wellness activity type.

Fluorophores functionalized with heavy elements show enhanced intersystem crossing due to increased spin-orbit coupling, which in turn shortens the fluorescence decay lifetime (τPL). This phenomenon is known as the heavy-atom effect (HAE). Here, we report the observation of increased τPL upon functionalisation of near-infrared photoluminescent gold nanoclusters with iodine. The heavy atom-mediated increase in τPL is in striking contrast with the HAE and referred to as inverse HAE. Femtosecond and nanosecond transient absorption spectroscopy revealed overcompensation of a slight decrease in lifetime of the transition associated with the Au core (ps) by a large increase in the long-lived triplet state lifetime associated with the Au shell, which contributed to the observed inverse HAE. This unique observation of inverse HAE in gold nanoclusters provides the means to enhance the triplet excited state lifetime.

The singlet fission (SF) process discovered in bis(thienyl)diketopyrrolopyrroles (TDPPs) can boost their potential for photovoltaics (PV). The crystal structures of TDPP analogs carrying n-hexyl, n-butyl, or 2-(adamant-1-yl)ethyl substituents are similar, but contain increasingly slipped stacked neighbor molecules. The observed SF rate constants, k SF , (7±4), (9±3) and (5.6±1.9) ns -1 for thin films of the three compounds, respectively, are roughly equal, but the triplet quantum yields vary strongly: (120±40), (160±40) and (70±16), respectively. The recent molecular pair model reproduces the near equality of all three k SF at the crystal geometries and identifies all possible pair arrangements in which SF is predicted to be faster, by up to two orders of magnitude. However, it is also clear that the presently non-existent ability to predict the rates of processes competing with SF is pivotal for providing a guide for efforts to optimize the materials for PV., (© 2020 Wiley-VCH GmbH.)

This chapter provides an overview of the biosynthesis and structure of lignin. Moreover, examples of the commercial use of lignin and its promising future implementation are briefly described. Many applications are still hampered by the properties of technical lignins. Thus, the major challenge is the conversion of lignins into suitable building blocks or aromatics in order to open up new avenues for the usage of this renewable raw material. This chapter focuses on details about natural lignin degradation by fungi and bacteria, which harbor potential tools for lignin degradation and modification, which might help to develop eco-efficient processes for lignin utilization.

The localized surface plasmon (LSP) photophysical phenomenon occurring in metal nanostructures is often presented as a way to effectively couple light into sub-wavelength-scale photovoltaic devices, which would otherwise suffer from a weak light absorption. The simultaneous complementary effect of localized optical field depletion receives far less attention. We studied a system consisting of a planar gold nanoparticles array (AuNP) deposited at the surface of a semiconducting polymer thin film (P3HT). By comparing the UV-vis spectra of P3HT with and without the AuNP array, we have estimated that the AuNPs screen the optical absorption in the interfacial layer of about 3.8 nm effective thickness due the near-field depletion effect. It suggests that the AuNP array may be used to practically "hide" a thin semiconductor layer, e.g., in order to tune the perceived color of the photovoltaic cell embedded in architecture, or in wearable devices.

Localized surface plasmon (LSP) photophysical phenomena occurring in metal nanostructures are often presented as a method to effectively couple light into photovoltaic devices of sub-wavelength-scale thickness. However, the excitation of LSP is also associated with rapid energy dissipation leading to local heating, which affects the excitation energy pathway. We studied a system consisting of a planar gold nanoparticle (AuNP) array deposited at the surface of a semiconducting polymer thin film (P3HT). We observed heat transfer from laser pulse excited AuNPs into the P3HT, which was evidenced as a long-living thermochromic effect on transient optical absorption. By modeling of the ultrafast kinetics of exciton population evolution, we determined that their decay was caused by their mutual annihilation. The decay rate was controlled by a phonon-assisted one-dimensional diffusion mechanism with a diffusion constant of 2.2 nm 2 ps -1 . The transferred heat resulted in an increase of the diffusion constant by a factor of almost 2, compared to the control system of P3HT without AuNPs. These results are of practical use for the design of plasmon-enhanced optoelectronic devices.

Pseudonocardia autotrophica strain DSM 43083 is a filamentous actinobacterium and was described to degrade or modify lignin. Here, we present its draft genome sequence, with a size of 5.8 Mb, to unravel the gene set coding for promising monooxygenases, dioxygenases, and DyP-type peroxidases associated with aromatic metabolism and lignin modification., (Copyright © 2017 Grumaz et al.)

α,ω-Bis(terpyridyl)oligothiophenes spontaneously assemble with Zn(II) ions giving conjugated constitutional dynamic polymers (dynamers) of the metallo-supramolecular class, which potentially might be utilized in optoelectronics. Their photophysical properties, which are of great importance in this field of application, are strongly influenced by the dynamic morphology. It was assessed in this study by using ultrafast pump-probe optical absorption spectroscopy. We identified and characterized relaxation processes running in photoexcited molecules of these oligomers and dynamers and show impacts of disturbed coplanarity of adjacent rings (twisting the thiophene-thiophene and thiophene-terpyridyl bonds by attached hexyl side groups) and Zn(II) ion couplers on these processes. Major effects are seen in the time constants of rotational relaxation, intersystem crossing, and de-excitation lifetimes. The photoexcited states formed on different repeating units within the same dynamer chain do not interact with each other even at very high excitation density. The method is presented that allows determining the equilibrium fraction of unbound oligothiophene species in a dynamer solution, from which otherwise hardly accessible values of the average degree of polymerization of constitutionally dynamic chains in solution can be estimated.

Nickel phthalocyanine (NiPc) complexes are known to show a rapid nonradiative deactivation of the photoexcited state through the internal conversion. This could be exploited in practical applications, such as photoprotection and photodynamic therapy. The butoxy substitution of NiPc plays an important role for drug delivery but also greatly influences its photophysics. We prepared novel peripherally substituted 2,3,9,10,16,17,23,24-octabutoxy nickel(II) phthalocyanine and characterized the deactivation pathway of its photoexcited state in solution by femtosecond transient absorption spectroscopy and quantum chemical calculations. We bring experimental evidence for the kinetic model, in which the photoexcitation evolves in two independent branches. In the first branch, assigned to the monomer, it undergoes ultrafast intersystem crossing to a triplet state, which subsequently decays to the ground state through a pathway involving lower-lying triplet states, with a ground-state recovery lifetime of 814 ps. It is about three-times longer than the lifetime published for unsubstituted NiPc. In the second branch, the photoexcitation decayed to a triplet state with an orders of magnitude longer lifetime, with the quantum yield of about 4%. This state showed spectral features of J-aggregates. These findings are important for the applications that rely on singlet oxygen formation or fast nonradiative deactivation of the excited state.

Room temperature photolysis of aminoborylene complexes, [(CO)(5)M=B=N(SiMe(3))(2)] (1: M = Cr, 2: Mo) in the presence of a series of alkynes and diynes, 1,2-bis(4-methoxyphenyl)ethyne, 1,2-bis(4-(trifluoromethyl)phenyl)ethyne, 1,4-diphenylbuta-1,3-diyne, 1,4-bis(4-methoxyphenyl)buta-1,3-diyne, 1,4-bis(trimethylsilylethynyl)benzene and 2,5-bis(4-N,N-dimethylaminophenylethynyl)thiophene led to the isolation of novel mono and bis-bis-(trimethylsilyl)aminoborirenes in high yields, that is [(RC=CR)(mu-BN(SiMe(3))(2)], (3: R = C(6)H(4)-4-OMe and 4: R = C(6)H(4)-4-CF(3)); [{(mu-BN(SiMe(3))(2)(RC=C-)}(2)], (5: R = C(6)H(5) and 6: R = C(6)H(4)-4-OMe); [1,4-bis-{(mu-BN(SiMe(3))(2)(SiMe(3)C=C)}benzene], 7 and [2,5-bis-{(mu-BN(SiMe(3))(2) ((C(6)H(4)NMe(2))C=C)}-thiophene], 8. All borirenes were isolated as light yellow, air and moisture sensitive solids. The new borirenes have been characterized in solution by (1)H, (11)B, (13)C NMR spectroscopy and elemental analysis and the structural types were unequivocally established by crystallographic analysis of compounds 6 and 7. DFT calculations were performed to evaluate the extent of pi-conjugation between the electrons of the carbon backbone and the empty p(z) orbital of the boron atom, and TD-DFT calculations were carried out to examine the nature of the electronic transitions.

The first catalytic application of the Group VI metal borylene complexes [(CO)(5)M[double bond]BN(SiMe(3))(2)] involves the demercuration reaction of bis(alkynyl)mercurials, [Hg(C[triple bond]CR)(2)], with formation of a series of buta-1,3-diynes.

Transition-metal-borylene complexes of the type [(OC)(5)M=BR] {M=Cr, Mo, W; R=N(SiMe(3))(2), 1a-3a, Si(SiMe(3))(3), 4a} and [(OC)(4)Fe=B=N(SiMe(3))(2)] (8) were prepared by salt elimination reactions. Synthesis of the latter complex was accompanied by the formation of substantial amounts of an unusual dinuclear iron complex [Fe(2){mu-C(2)O(2)(BN(SiMe(3))(2))}(2)(CO)(6)] (9). The aminoborylene complexes of Group 6 metals were converted to trans-[(Cy(3)P)(CO)(4)M=B=N(SiMe(3))(2)] (5a-7a) by irradiation in the presence of PCy(3). Structural and spectroscopic parameters were discussed with respect to the trans-effect of the borylene ligand and the degree of M-B d(pi)-p(pi)-backbonding. Computational studies were performed on Group 6-borylene complexes. The population and topological analyses as well as the molecular orbital composition are consistent with the presence of both sigma-and pi-type interactions. There are, however, indications that the d(pi)-p(pi)-backbonding in the silylborylene complex is significantly more pronounced than in the aminoborylene complexes.

A series of platinum(II) boryl complexes of general formula trans-[(Cy(3)P)2Pt(Br)(BX2)], including the rare dibromoboryl species trans-[(Cy(3)P)2Pt(Br)(BBr2)], were synthesized by oxidative addition of the B-Br bond of a number of bromoboranes to [Pt(PCy3)2]. X-ray diffraction studies were performed on several such compounds. Comparison of the Pt--Br bond lengths allowed an empirical assessment of the trans-influence of different boryl ligands. A trans-influence scale was thus deduced and the results were compared with those previously computed for compounds of the type trans-[(Me(3)P)2Pt(Cl)(BX2)].

Since the publication of the last review in 1998, the transition-metal chemistry of boron has continued to raise unceasing interest. Boryl complexes, representing the most extensive subclass, have remained a focus of intense research, particularly for their implication in the metal-mediated functionalization of organic substrates. Absolute novelties such as borane complexes and terminal borylene complexes have been structurally authenticated. Upon further elaboration of these compounds, the known coordination modes of boron-based ligands have grown considerably. Combined structural and theoretical investigations have contributed to elucidate the fundamental electronic characteristics of the transition-metal-boron bond and are leading to applications of these compounds. The most useful synthetic strategies for the generation of transition-metal-boron bonds are highlighted here, and the most recent and intriguing compounds that have been reported are outlined and discussed.